CN1062151A - Harmless antifouling paint with full-inorganic of permanent preservative property - Google Patents
Harmless antifouling paint with full-inorganic of permanent preservative property Download PDFInfo
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- CN1062151A CN1062151A CN 91111406 CN91111406A CN1062151A CN 1062151 A CN1062151 A CN 1062151A CN 91111406 CN91111406 CN 91111406 CN 91111406 A CN91111406 A CN 91111406A CN 1062151 A CN1062151 A CN 1062151A
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- China
- Prior art keywords
- coating
- silicate
- sio
- mol ratio
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003973 paint Substances 0.000 title claims abstract description 16
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 14
- 230000002335 preservative effect Effects 0.000 title claims description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 52
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- -1 iron ion Chemical class 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 8
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000003086 colorant Substances 0.000 claims abstract description 6
- 150000001413 amino acids Chemical class 0.000 claims abstract description 3
- 239000000084 colloidal system Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 230000028327 secretion Effects 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 230000002939 deleterious effect Effects 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000013535 sea water Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 2
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 239000008204 material by function Substances 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000003248 secreting effect Effects 0.000 abstract description 2
- 238000007348 radical reaction Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000269799 Perca fluviatilis Species 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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- 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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
-
- 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/003—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hybrid binders other than those of the polycarboxylate type
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
-
- 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
- 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
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/67—Biocides
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
- C04B2111/00525—Coating or impregnation materials for metallic surfaces
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
- C04B2111/0056—Coating or impregnation materials for ship decks
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of with denatured silicate as vehicle with the coating of pure aluminium silicate as dispersate.Because the free radical reaction of silanol, coating of the present invention can form a kind of functional membrane special, that be similar to the full-inorganic of polymer organic coating, and described film has netted chemical structure form.Described film has stoped the loss of iron ion, therefore, has corrosion-resisting function, and can decompose the secretory product amino acid calcium colloid of ocean adhesivity biology and have harmless anti-fouling effect.Coating of the present invention also can be used as the inside and outside coating and the paint colorant of structural part, has nonvolatil smokeless, humidity control, antibiotic and anti-static function.
Description
The present invention relates to a kind of harmless antifouling paint with full-inorganic of permanent preservative property.
Developed since nineteen thirty-seven since the heat curing coating (Australian Patent number 1,042,317) of a kind of DAYMETCOAT by name, (USP 246263 to adopt the chemosetting method, 1970) and the self cure method (USP 4,086,616, the phosphoric acid method, USP 2,536, and 871, zinc oxide method), now developed the water glass coating series.But, when it is used as protective system, needs to increase zinc concentration bar none and just can prevent corrosion.
After thermal curing methods occurred, the water glass coating series was considered to for heavy equipment, is used for the steel structure of specific purposes, particularly is in those of desert and ocean environment, has preservative effect.But, having in most cases, it is used as the priming paint of coating or is used in combination with organic coating.
Phosphoric acid and phosphoric acid salt, for example silicon polyphosphate, titanium phosphate and metal oxide are the solidifying agent of known water glass coating as calcium oxide, aluminum oxide etc.; Glass fibre, carbon fiber etc. are then as its toughener.In addition, also has a large amount of this patents on the one hand that relates to.But, the main drawback of water glass coating series, for example non-watertight, inflexibility and tarnish etc. still do not solve.Therefore, use organic-inorganic composition coating usually, or replace with alkyl silicate coating.
In addition, the functional membrane that does not also have a patent to relate to by forming a kind of special inorganic acid salt solves anticorrosion and antifouling problem.
Recently, prevent to pollute international organization and ban use of deleterious antifouling paint by legal procedure.But, up to the present also do not have a kind of effective harmless coating to occur.
The purpose of this invention is to provide a kind of harmless antifouling paint with full-inorganic of permanent preservative property, described coating is according in ocean environment, and the adhering research of the mechanism of corrosion of iron and the adhesivity biology in the ocean is developed.
Another object of the present invention provides a kind of coating of coating structure thing ectonexine and colorant that is used to paint of being used for, and they have excellent tackiness, water-repellancy, humidity control, antistatic, antibacterium performance and make the will never fade performance of color.
A back purpose of the present invention directly relates to better succession and develops our ancestors' the lofty task of valuable cultural heritage, these legacy reside on the wall of grave and China Kongwryo on the colourful drawing that stays and pattern (make its will never fade).
The present invention and coating can prepare with diverse ways by its purposes.
The method I
M
2O/SiO
2Mol ratio is 0.4～0.25 silicate (M
2OSiO
2) solution mixes with ammonium chloride, makes NH
4Cl/SiO
2Mol ratio reaches wherein M=K of 0.2～0.5(, Na, and Li, Rb).Following reaction takes place subsequently:
Na
2O·nSiO
2+2NH
4Cl+H
2O＝2NaCl+2NH
3↑+nSiO
2+2H
2O
Silica gel slaking certain hour that obtains by above-mentioned reaction and the denaturant gel attitude aminopropyl silica gel (xH that obtains being adsorbed with ammonia through washing
2SiO
3NH
4OHyH
2O), its NH
4OH/SiO
2Mol ratio preferably 0.25～0.5, this mixture and M
2O/SiO
2Mol ratio be 0.25～0.5 silicate solutions with 1～50: 100 weight ratio is mixed, and MX solution is distributed in this solution that obtains, and makes its MX/SiO
2Mol ratio reaches 0.01～0.05, obtains full-bodied denatured silicate solution (vehicle) (M wherein is K, Na, Li, Rb, Ba, Zn, Ca, Al, and X is Cl, F, Br) thus.
If in above-mentioned denatured silicate solution, add filler, pure aluminium silicate dispersate, metal oxide and metal-powder, then will obtain a kind of coating (pure aluminium silicate described herein is the M(I)
2The OM(II) OAl
2O
3NSiO
2MH
2O, wherein M(I) and the M(II) being respectively unit price and two valency metallic cation, n is SiO
2/ Al
2O
3Mol ratio, m is the mole number of water).SiO
2/ Al
2O
3Mol ratio preferably in 0.5～20 scope, Na
2Preferably in 1～10 scope, ion exchange capacity is 5～40 milligramequivalents/100 grams to the O/CaO mol ratio.The granular size of filler is 250～300 orders preferably.Vehicle preferably adds with pure aluminium silicate, and what add simultaneously also has one or both to be selected from ZnO, TiO
2, Fe
2O
3, BaO, Al
2O
3In metal oxide and one or both be selected from metal-powder among Zn, Fe, Al and the Cu, their add-on is respectively 30～40%(weight), 0～20%(weight) and 0～20%(weight).
When this coating uses, a kind of film with ionic adsorption and ion-exchange capacity will be obtained.
According to the mol ratio of filler and its add-on, the ion adsorption capacity of the film that is formed by coating changes in the scope of 90～110 milligramequivalents/100 grams, and ion-exchange capacity changes in the scope that 10～30 milligramequivalents/100 restrain.
When the application of paints that according to said method makes during in hull bottom, will form a kind of mineral membrane, this film is to cationic adsorptive power, and is higher 3 times than natural zeolite in cationic adsorptive capacity, to Ca
2+Ionic absorption more so (sees Table 1).
Infrared absorption spectrum analysis, X-ray diffraction analysis, the analysis of X-ray photoelectric and differential thermal analysis result show that described film has a kind of tridimensional network, thereby make it have ion-exchange and adsorption function.
The bio secretion that is adsorbed in hull bottom goes out a kind of viscous substance, and amino acid calcium colloid, this viscous substance will be transformed into a kind of polymer cohesiveness material with very strong cohesive force, and adhere to the hull bottom surface securely.
Because the surface of described film is contained and had very highly active alkali metal cation, it can be easily and other metallic cation generation ion exchanges.Therefore, described film can be with Ca from the adhesivity secretion generation-amino acid calcium colloidal solution that ocean adhesivity bio secretion goes out
2+Ionic adsorption is come out, thus weaken the adhesion strength of described adhesivity biology and they can not perch in the hull bottom surface.
Table 2 film is to the absorption and the exchange capacity of calcium ion
Adsorptive power 100 milligramequivalents of per 100 grams
Every square centimeter adsorptive power 0.06 milligramequivalent
Exchange capacity 17 milligramequivalents of per 100 grams
Every square centimeter exchange capacity 0.01 milligramequivalent
The juice equivalents 2 * 10 of ocean adhesivity biology
-5Milligramequivalent
(every square centimeter)
As shown in table 2, the ion-exchange capacity of every square centimeter of described film is 0.01 milligramequivalent, and the amount of the calcium that ocean adhesivity bio secretion goes out is 2 * 10
-5Milligramequivalent.When showing described film, a little data the exchange capacity of calcium is much higher than the secretory volume of the calcium of described ocean adsorptivity biology.
Therefore, described film not only has the ability that absorption ocean adhesivity biology comprises all calcium that fungus secretion goes out, simultaneously also because in seawater, the absorption-desorption process of calcium and sodium is the constant reversible reaction.Therefore, as long as described film exists, it is to ocean adhesivity biology, and the antifouling ability that comprises fungi will be nonvolatil.
Described film also can obtain explaining that described film has prevented to adsorb owing to ionic the loss of the iron ion that produces from ionic absorption and fixed mechanism to the anti-corrosion capability of iron.
Brief Description Of Drawings:
Fig. 1 is the sub-analysis chart of X-ray photoelectric of film of the present invention.
Embodiment
Make vehicle by method 1.This vehicle mixes with filler according to described proportion of composing, and the application of paints that obtains is solidified a week in hull bottom, carries out exposure test and actual service test subsequently.
Form (weight percent)
Vehicle 40～60
Pure aluminium silicate 20～30
Metal oxide 5～20
Zinc powder 5～16
The result shows, the actual use after 15 years, and the antifouling and corrosion proof function of formed film still keeps good.
The method II
Polyoxyethylene glycol (n=1～2000) joins M
2O/SiO
2Mol ratio is in 0.4～0.25 the silicate solutions.Polyoxyethylene glycol and silicate generation neutralization reaction obtain polysilicate elastomerics (PSE).
Sedimentary PSE is scattered in the silicate solutions, makes PSE/SiO
2Mol ratio reaches 0.1～10.0, toward wherein adding aluminum salt solution, makes Al then
2O
3/ SiO
2Mol ratio reaches 0.01～5.0, and obtains vehicle 100 ℃ of heating.
This vehicle and barium sulfate, calcium phosphate, 1～2 kind of metal oxide, for example aluminum oxide, titanium white, zinc oxide etc., part by weight with 5: 1～10 mixes, be made into paste, obtain coating or paint colorant as the inside and outside coating of works, they have excellent smokeless property, and humidity is controlled, antibacterium and static resistance.
The coating that makes thus can be used for fiber, concrete slab, glass, iron, slabstone and stone etc., but can not be used for resin and the material that is suitable for the undercoat of greasepaint.
Embodiment
The vehicle that obtains by the method II mixes with dispersate according to following proportion of composing, is applied on the cement plate then, and solidifies a week.
Form (weight percent)
Vehicle 40～60
Titanium oxide 5～10
Zinc oxide 5～10
Barium sulfate 10～25
The main character of table 3 film
Humidity control performance 5～7g/m
2.h.atm
Anti-microbial property JIS test is passed through
Exposing test in 8 years passes through
Antistatic property 10
3Ohm
1000 ℃ of following no changes of fire resistance
As shown in table 3, when coating of the present invention is used as the internal and external ornament coating of buildings and structural part, have excellent humidity control, antibiotic and antistatic property, and fire prevention, smokeless.Therefore, its work-ing life is very long, and good hygienic condition are provided.Further, form because it is a full-inorganic, so it also has ageing resistance simultaneously.
Actual service test
When organic coating during as the internal and external ornament coated material of buildings, in moist growing environment (humidity is about 90%, and temperature is at 20～30 ℃), will be mouldy in one month, will be contaminated within 1 year, therefore need inevitably to apply again.
And when coating of the present invention during as the colorant of the inside and outside coating of works and paint, uses 8 after yet discovery mould growth is arranged, even in the mould-growth environment, body surface does not have contaminated yet.
Claims (14)
1, has the harmless antifouling paint of the full-inorganic of permanent preservative property, it is characterized in that M
2O/SiO
2Mol ratio is the silicate (M of 0.4-0.25
2OnSiO
2) solution mixes with ammonium chloride, obtains NH
4Cl/SiO
2Mol ratio is the silica gel of 0.2-0.5, and wherein M is K, Na, Li, Rb, and described silica gel slaking certain hour also obtains a gel state mixture through washing, and this mixture absorbs ammonia, obtains NH
4OH/SiO
2Mol ratio is the ammonium silicate of 0.25-0.5, (xH
2SiO
3NH
4OHyH
2O), it is joined M
2O/SiO
2Mol ratio is the silicate (M of 0.25-0.5
2OnSiO
2) in the solution, the ratio of described ammonium silicate and described silicate is 1～50: in 100 the scope, MX is distributed in the denatured silicate colloidal solution that obtains obtains MX/SiO
2Mol ratio is the denatured silicate solution (vehicle) of 0.01-0.05, and wherein M is Li, Na, K, Ba, Ca, Al, and X is F, Br, Cl, adds pure aluminium silicate in described denatured silicate solution, and one or both are selected from ZnO, TiO
2, Fe
2O
3, BaO, Al
2O
3In metal oxide, and one or both metal-powders, the harmless antifouling paint that obtains having permanent preservative property.
2, coating as claimed in claim 1 is characterized in that, NH
4OH/SiO
2Mol ratio be the ammonium silicate of 0.25-0.5 with 1～50: 100 part by weight is added to M
2O/SiO
2Mol ratio is the silicate (M of 0.25-0.5
2OnSiO
2) in the solution, obtain denatured silicate colloidal solution.
3, coating as claimed in claim 1 or 2 adds MX in the denatured silicate colloidal solution that it is characterized in that obtaining by claim 2, makes MX/SiO
2Mol ratio reaches 0.01-0.05, obtains sex change high viscosity silicate solutions (vehicle).
4, as the coating of one of claim 1 to 3, it is characterized in that its dispersate pure aluminium silicate M(I)
2The OM(II) OAl
2O
3NSiO
2MH
2(wherein M(I) or M(II among the O) be unit price or two valency positively charged ion, n is SiO
2/ Al
2O
3Mol ratio, m is the mole number of water), Na
2The mol ratio of O/CaO in the scope of 1-10, SiO
2/ Al
2O
3Mol ratio in the scope of 0.5-2.0, its ion exchange capacity is in 5-40 milligramequivalent/100 gram scopes.
5,, it is characterized in that described sex change sodium silicate solution and one or both are selected from ZnO, TiO as the coating of one of claim 1 to 4
2, Fe
2O
3, BaO, Al
2O
3In metal oxide, pure aluminium silicate powder and one or both metal-powders that is selected among Zn, Fe, Al, the Cu mix mutually, its consumption is respectively 0～20,30～40,0～20%(weight).
6, as the coating of one of claim 1 to 5, it is characterized in that described coating forms three-dimensional chemical structure kenel in coated object surfaces, therefore can decompose the oozy viscous secretion amino acid calcium of hull adhesivity bio secretion thing colloid, thereby have anti-fouling effect.
7,, it is characterized in that described coating does not use deleterious material and has harmless anti-fouling effect as the coating of one of claim 1 to 6.
8,, it is characterized in that described coating has preservative effect by the loss that prevents iron ion as the coating of one of claim 1 to 7.
9, as the coating of one of claim 1 to 8, it is characterized in that described coating because ionic adsorption and ion-exchange in seawater is reversing process, therefore have permanent anticorrosion, anti-fouling effect and expire until the usage period of ship.
10, as the inside and outside coating of works and the full-inorganic coating of paint colorant, it is characterized in that polyoxyethylene glycol is added to M
2O/SiO
2Mol ratio is in 0.4～0.25 the silicate solutions, to obtain polysilicate elastomerics (PSE), and this elastomerics is added in the silicate solutions, makes PSE/SiO
2Mol ratio is 0.1～10, adds aluminum salt solution in the solution that obtains and makes Al
2O
3/ SiO
2Mol ratio is 0.01～5.0, and be heated to 100 ℃, obtain denatured silicate vehicle colloidal solution, be selected from pigment in barium sulfate, calcium phosphate, aluminum oxide, titanium white, zinc oxide and other pigment toward wherein adding one or both, obtain paste, single liquid (mono-liquid) coating, this coating is suitable for as the inside and outside coating of structural part and the functional materials such as colorant of paint.
11,, it is characterized in that polyoxyethylene glycol (n=1～2000) is joined M as the coating of claim 10
2O/SiO
2Mol ratio is in 0.4～0.25 the silicate solutions, to obtain polysilicate elastomerics (PSE).
12, as the coating of claim 10 or 11, it is characterized in that PSE is joined in the silicate of claim 11, make PSE/SiO
2Mol ratio reaches 0.1～10, adds aluminium salt in the solution that obtains and makes Al
2O
3/ SiO
2Mol ratio reaches 0.01～5.0 and 100 ℃ of heating, obtains denatured silicate vehicle colloidal solution.
13,, it is characterized in that adding in the described denatured silicate vehicle colloidal solution one or both and be selected from BaSO as the coating of one of claim 10 to 12
4, CaCO
3, TiO
2With the pigment of other pigment, the part by weight of adding is 5: 1～10.
14,, it is characterized in that described coating can be applicable to fiber, cement plate, glass, steel plate, slabstone or stone, but can not be used for resin and the base plate that is suitable for greasepaint as the coating of one of claim 1 to 13.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KP287990 | 1990-12-05 | ||
| KP90-2879 | 1990-12-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1062151A true CN1062151A (en) | 1992-06-24 |
Family
ID=19198155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91111406 Pending CN1062151A (en) | 1990-12-05 | 1991-12-05 | Harmless antifouling paint with full-inorganic of permanent preservative property |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0526594A1 (en) |
| CN (1) | CN1062151A (en) |
| DE (1) | DE9116748U1 (en) |
| WO (1) | WO1992010546A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100378181C (en) * | 2005-03-24 | 2008-04-02 | 金贞夏 | Inorganic coating composition regulated by pH value and its preparation method and use |
| CN103881431A (en) * | 2014-03-24 | 2014-06-25 | 浙江大学 | Silane coupling agent modified lithium silicate base coating and preparation method thereof |
| CN115849868A (en) * | 2022-12-07 | 2023-03-28 | 山东电盾科技股份有限公司 | Self-cleaning dry-hanging silicon porcelain plate curtain wall |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06240175A (en) * | 1993-02-17 | 1994-08-30 | Daiei Kikai:Kk | Multifunctional zinc-free water-glass paint and its production |
| JPH07166126A (en) * | 1993-12-14 | 1995-06-27 | Daiei Kikai:Kk | Production of polyfunctional water glass coating material |
| DE102005059757A1 (en) * | 2005-12-12 | 2007-06-14 | Beharrysingh-Pracejus, Ramona Brenda | Use of natural zeolite or a naturally or artificially produced zeolite- like compounds for combating fungus |
| CN102584090B (en) * | 2012-01-18 | 2013-12-18 | 厦门理工学院 | Addition agent for preventing marine concrete from being corroded by marine fouling organism and preparation method thereof |
| GB201412058D0 (en) * | 2014-07-07 | 2014-08-20 | Univ Dublin | Thermal control coating |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3893864A (en) * | 1973-12-20 | 1975-07-08 | Exxon Research Engineering Co | Quick-curing water resistant silica-alkali metal coatings and processes therefor |
| JPS5186529A (en) * | 1975-01-27 | 1976-07-29 | Dainippon Toryo Kk | SUIYOSEIJINKURITSU CHIPEINTOSOSEIBUTSU |
| JPS54133523A (en) * | 1978-04-07 | 1979-10-17 | Kansai Paint Co Ltd | Inorganic paint containing zinc powder |
| JPS5540717A (en) * | 1978-09-14 | 1980-03-22 | Shikoku Kaken Kogyo Co Ltd | Coating composition |
| JPS58108257A (en) * | 1981-12-21 | 1983-06-28 | Toshiba Corp | Preparation of self-cleaning type coating layer |
| EP0295834A1 (en) * | 1987-06-16 | 1988-12-21 | Minnesota Mining And Manufacturing Company | High temperature resistant inorganic composition |
-
1991
- 1991-10-24 EP EP91919771A patent/EP0526594A1/en not_active Withdrawn
- 1991-10-24 DE DE9116748U patent/DE9116748U1/en not_active Expired - Lifetime
- 1991-10-24 WO PCT/KP1991/000010 patent/WO1992010546A1/en not_active Application Discontinuation
- 1991-12-05 CN CN 91111406 patent/CN1062151A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100378181C (en) * | 2005-03-24 | 2008-04-02 | 金贞夏 | Inorganic coating composition regulated by pH value and its preparation method and use |
| CN103881431A (en) * | 2014-03-24 | 2014-06-25 | 浙江大学 | Silane coupling agent modified lithium silicate base coating and preparation method thereof |
| CN103881431B (en) * | 2014-03-24 | 2016-04-13 | 浙江大学 | A kind of silane coupler modified lithium silicate base coating and preparation method thereof |
| CN115849868A (en) * | 2022-12-07 | 2023-03-28 | 山东电盾科技股份有限公司 | Self-cleaning dry-hanging silicon porcelain plate curtain wall |
| CN115849868B (en) * | 2022-12-07 | 2023-11-07 | 山东电盾科技股份有限公司 | Self-cleaning dry-hanging silicon porcelain plate curtain wall |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992010546A1 (en) | 1992-06-25 |
| EP0526594A4 (en) | 1994-01-26 |
| DE9116748U1 (en) | 1993-09-23 |
| EP0526594A1 (en) | 1993-02-10 |
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