EP1204621A1 - Method for treating architectural material - Google Patents
Method for treating architectural materialInfo
- Publication number
- EP1204621A1 EP1204621A1 EP00956628A EP00956628A EP1204621A1 EP 1204621 A1 EP1204621 A1 EP 1204621A1 EP 00956628 A EP00956628 A EP 00956628A EP 00956628 A EP00956628 A EP 00956628A EP 1204621 A1 EP1204621 A1 EP 1204621A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- type
- compounds
- family
- photocatalytic
- dispersions
- 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.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 71
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 230000001699 photocatalysis Effects 0.000 claims abstract description 38
- 239000007791 liquid phase Substances 0.000 claims abstract description 23
- 238000005470 impregnation Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 4
- 230000001737 promoting effect Effects 0.000 claims abstract description 4
- 239000002318 adhesion promoter Substances 0.000 claims description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 30
- 238000011282 treatment Methods 0.000 claims description 21
- 239000000284 extract Substances 0.000 claims description 16
- 239000004567 concrete Substances 0.000 claims description 15
- -1 terracotta Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 10
- 230000003373 anti-fouling effect Effects 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 150000004760 silicates Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 230000000922 anti-bactericidal effect Effects 0.000 claims description 4
- 230000000843 anti-fungal effect Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 3
- 239000010438 granite Substances 0.000 claims description 3
- 239000004579 marble Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 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 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001723 carbon free-radicals Chemical class 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 239000004111 Potassium silicate Substances 0.000 claims 1
- 239000000834 fixative Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 239000011505 plaster Substances 0.000 claims 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims 1
- 235000019353 potassium silicate Nutrition 0.000 claims 1
- 238000009877 rendering Methods 0.000 claims 1
- 239000010454 slate Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000000758 substrate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000000750 progressive effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- KLDYRXHGQNGJKS-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1.CC(=O)CC(=O)C1=CC=CC=C1 KLDYRXHGQNGJKS-UHFFFAOYSA-N 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- RIPZIAOLXVVULW-UHFFFAOYSA-N pentane-2,4-dione Chemical compound CC(=O)CC(C)=O.CC(=O)CC(C)=O RIPZIAOLXVVULW-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- ZVTQDOIPKNCMAR-UHFFFAOYSA-N sulfanylidene(sulfanylideneboranylsulfanyl)borane Chemical compound S=BSB=S ZVTQDOIPKNCMAR-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide 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
- C04B41/45—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- 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
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
-
- 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
- Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]
Definitions
- the present invention relates to a method of processing architectural materials, aiming to give them a new functionality.
- the materials more particularly targeted are those used in building as a facade material, cladding, roofing or soil and capable of offering a certain porosity / permeability vis-à-vis relatively fluid liquids, such as water, to a detectable depth, for example at least one to a few microns.
- These include materials of the type coated with facades, concrete slabs and pavers, architectural concrete, tiles, slates and all materials of various shapes based on cement composition, concrete, terracotta, or stone of the granite type. or marble.
- the new functionality that the invention seeks to confer on them relates to anti-fouling, anti-fungal and / or bactericidal properties, obtained using semiconductor materials based on sulphide or metal oxide, in particular based on titanium oxide crystallized in anatase form, exhibiting photocatalytic activity: these materials are in fact capable, in known manner, of initiating radical reactions causing the oxidation and degradation of organic products under the effect of long radiation adequate wave, ultraviolet for titanium oxide.
- these materials used in construction tend to quickly lose their new appearance due on the one hand to their presence in dirty environments and on the other hand to their porosity and / or surface roughness which facilitate the attachment of the soiling.
- the dirt frequently encountered is for example microorganisms which affect not only the appearance, but also, ultimately, the structural properties of the material.
- the tiles are covered with algae, lichens or moss in a humid environment.
- facade plasters also constitute a substrate conducive to the development of plants of this type.
- Dirt also comes from fouling generated by urban organic pollution, consisting in particular of automobile or industrial soot, soot which also tends to favor the attachment of mineral dust to the material, creating dark crusts on its surface.
- patent application WO97 / 10185 describes the deposition of photocatalytic coatings on glass substrates, coatings comprising particles of photocatalytic TiO 2 and an inorganic binder resulting from the thermal decomposition at high temperature of organometallic precursors.
- the object of the invention is therefore to improve the treatment of architectural substrates of the "permeable" type, (this term having been explained above), by photocatalytic compounds, an improvement aimed in particular at greater simplicity and / or greater flexibility. in its implementation, as well as greater resistance of these compounds to said substrates.
- the invention firstly relates to a method of treatment by impregnation of "permeable" architectural material, method comprising the projection onto the material of one or more dispersions in liquid phase of at least one type of photocatalytic compounds and d at least one type of compound promoting adhesion of said photocatalytic compounds to said architectural material.
- Permeable material is understood to mean any material used in construction which is capable of allowing liquid phases of the aqueous type to penetrate over a certain thickness, for example over at least 20 nm up to in particular 100 or 50 ⁇ m, in particular over at least 1 to 10 ⁇ m, or in particular all the types of materials mentioned in the preamble to the present application. It is understood by “impregnation” the fact that the main part of the treatment leads not only to a coating containing the photocatalytic compounds and situated only on the surface of the material, but also to an introduction of these compounds into the very thickness of the material thanks to the vector liquid phase and its natural porosity.
- the photocatalytic compounds (hereinafter called “active” for the sake of brevity) will diffuse over a certain thickness in a surface area of the material, by being flush with its surface, this impregnation possibly being “completed” by the formation of a coating on top of the material, coating which is preferably thin or even discontinuous
- the concentration of active elements in the material decreases as one moves away from its external surface: a concentration gradient is established with the highest concentration in the zone flush with the external surface of the material .
- the compounds "active" with respect to photocatalysis are based on metal oxide (s) optionally doped, for example zinc oxide, tungsten oxide or l 'tin oxide.
- metal oxide s
- the preferred example according to the invention relates to titanium oxide at least partially crystallized in anatase form, which is the crystallized phase which gives TiO2 its photocatalytic properties.
- They may also be semiconductors belonging to the family of sulfides, also at least partially crystallized, such as zinc or boron sulfide. (In the following text, for simplicity, we will rather mention the oxide of titanium, it being understood that the indications given are equally valid for the other semiconductor materials mentioned above).
- these “active” compounds of the TiO 2 type are used in the form of particles with an average diameter of at most 150 or 100 nm, in particular between 20 and 60 nm, particles preferably being in colloidal suspension in a liquid phase, especially essentially aqueous. This avoids at best that the particles do not agglomerate, which would significantly reduce their effectiveness. This facilitates their homogeneous dispersion on the material, while avoiding modification of its appearance.
- the adhesion promoter is an important characteristic of the invention: preferably, it is soluble / dispersible in essentially aqueous phase, like the "active" compounds.
- the choice of water mainly, even if it can be added with miscible organic solvents in small quantities, is particularly advantageous in view of the materials to be treated: indeed, its cost, its availability, its absence of polluting elements are very interesting when it comes to using it in large quantities both in the factory for manufacturing architectural material (tiles, slabs), and directly on site when the material is laid (facade plasters), or , alternatively, after a cleaning or cleaning operation, in the context of building renovations for example.
- the adhesion promoter is preferably chosen so as to be chemically compatible with both the "active" compounds and the architectural material, to best ensure the homogeneous distribution and permanent fixation of the compounds on the material.
- it is chosen in particular so that it is capable, once projected onto the material, of fixing itself to it by hardening, caused by a chemical and / or physical modification depending on its nature.
- This modification can be done in a relatively short time after spraying or more gradually, without there being any need to cause this hardening by a specific treatment of the heating type. Indeed, especially if the treatment is done on site, when laying or renovating construction materials, it is important that the implementation of the treatment is as simple as possible, (besides the fact that some of the materials may not be able to withstand treatments individuals).
- this spontaneous chemical and / or physical modification upon exposure to the ambient atmosphere, can be carbonation, a crosslinking type reaction and / or hydrolysis.
- a physical change can be a coalescence.
- adhesion promoters are interesting. It is possible to choose only one type of adhesion promoter or to combine several of them, in one or more liquid dispersions.
- a first family is that of organometallic compounds, in particular the tetraalkoxides of form M (OR) 4, with M the metal of the Ti or Zr type and R a carbon radical of the linear or branched alkyl type, all identical or different, having in particular from 1 to 6 C. Mention may in particular be made of titanium or zirconium tetrabutoxide or tetrapropoxide. It can also be trialkoxides of the MR '(OR) 3 type with R and R' of the same or different radicals of the type of the radicals described above. It may also be a metal halide, in particular chloride such as TiC14.
- All these compounds are highly hydrolyzable and it is therefore preferable, for them to remain stable until they are used, to combine them in their liquid phase with at least one chelating / stabilizing agent, for example of the ⁇ -diketone type such as acetylacetone (2,4-pentanedione), benzoylacetone (1-phenyl-1, 3 butanedione), disopropylacetylacetone, acetic acid, diethanolamine or compounds of the glycol family such as ethylene glycol or tetraoctylene glycol.
- ⁇ -diketone type such as acetylacetone (2,4-pentanedione), benzoylacetone (1-phenyl-1, 3 butanedione), disopropylacetylacetone, acetic acid, diethanolamine or compounds of the glycol family such as ethylene glycol or tetraoctylene glycol.
- All these metal compounds will tend, once projected onto the material to be hydrolyzed gradually, to degrade by condensation / crosslinking to form a network having metal-oxygen bonds having a particularly high affinity with the active elements in the form of particles of metal oxides of the TiO2 type and being insoluble in water.
- a second family is that of silicon alkoxides (silanes), for example of the general formula Si (OR) 3R ', with R and R' having the same type of radical as in the case of the first family. It has proven to be advantageous to associate an adhesion promoter of the first family with an adhesion promoter of the second, given the similarity of their reactivity / behavior and their good compatibility.
- a third family of adhesion promoter is the family of alkali and / or alkaline earth silicates or aluminosilicates, such as sodium, potassium or lithium silicate.
- alkali and / or alkaline earth silicates or aluminosilicates such as sodium, potassium or lithium silicate.
- mineral type this type of compound will also harden by a polycondensation type reaction, crosslinking leading to the formation of a mineral network with silicon-oxygen bonds insoluble in water and chemically close to architectural materials of the tile, earth type. particularly cooked.
- a fourth family of adhesion promoter is that of polysiloxanes, silicon compounds such as silicates but already under a polymeric form. Their progressive hardening is a reaction similar to crosslinking of the polymers in question. They can be in the form of micro-emulsions of siloxanes or of a mixture of silane (s) and siloxane (s). It can be seen that the choice of the type of adhesion promoter can be made from a wide variety of materials, which can be of the hydrolysable metal compound, silicon or organo-silicon compound type, in polymer form or not, depending in particular on the type of material to be treated. and the type of active elements.
- the first variant consists in projecting onto the architectural material a single dispersion in the liquid phase, comprising both the photocatalytic "active" compounds and the adhesion promoter (s).
- This variant has the advantage of simplicity, by using a single product, a single liquid dispersion minimizing any risk of error on the part of the manipulator.
- the formulation of the dispersion can prove to be more complex to ensure the compatibility of the active elements and of the adhesion promoters, without sedimentation. Additives make it possible to obtain stable dispersions, but sometimes, depending on the case, with a storage time once conditioned which may prove to be insufficient.
- the second variant makes it possible to overcome this constraint: it consists in using several dispersions in liquid phases, one or more of the dispersions containing active elements and one or more others containing the adhesion promoters, plurality of dispersions that can be projected jointly or one after the other against the material to be treated.
- the particularly preferred embodiment of this variant consists in first projecting a dispersion containing the active elements of the TiO2 particle type and, secondly, a dispersion containing the adhesion promoter which acts as a fixer. -vis particles already lodged in the pores of the material. Between the two projections, it is preferable to allow a sufficient time to pass for the material to dry (that is to say that a substantial part of the water of the first dispersion has evaporated).
- an impregnation of the material with the dispersion (s) up to at most 400 ⁇ m, in particular up to at most 100 or 200 ⁇ m is sufficient to obtain a notable anti-fouling effect.
- This impregnation depth will correspond to the penetration depth of the active elements in the material, once fixed permanently after drying and hardening of the adhesion promoter.
- An advantageous implementation of the method according to the invention consists in preparing and conditioning the liquid phase dispersion (s) in concentrated form, the dilution and / or mixing of the dispersions being carried out just before use. This is particularly recommended when treating building materials during installation or their renovation on site, to avoid the storage of dispersions with high dilution therefore bulky and / or to allow adjustment of the dilution according to the material to be treat from standardized concentrated dispersions.
- suitable additives in particular organic compounds such as ⁇ -diketones, acids or bases to control their pH such as acetic acid or nitric acid, polycarboxylates, stabilizers such as compounds of the glycol family or compounds known to be coupling agents such as silanes.
- ⁇ -diketones are capable of stabilizing organo-metallic compounds of type M (OR) 4 or MR '(OR) 3 in the form of a complex which can serve as adhesion promoters.
- polycarboxylates are capable of stabilizing the colloidal dispersion of photocalytic particles.
- the glycol derivatives and the acids have a favorable stabilizing effect with respect to some of the adhesion promoters and / or certain of the active compounds of the invention.
- the concentrations of active compounds and of adhesion promoter in the dispersions are appropriately adjusted.
- the values of dry extract indicated in the present text are those of the "ready to projection" dispersions mentioned above. It is customary, to do this, to choose as characteristic the dry extract of these dispersions, measured in a known manner by heat treatment of the order of 100 ° C, for example according to standard NF-T30-011.
- the dry extract of the dispersions corresponding to the photocatalytic compounds is at most 30%, in particular at most 20, 15 or 10%, and preferably at least 0.5%. The preferred range is for example of the order of 1 to 5%.
- the dry extract of the "ready-to-spray" dispersions corresponding to the adhesion promoter (s) is preferably adjusted to a value of at most 20% or at most 15%, or at most 10 or 5%, in particular at least 0.2%, for example between 0.25 and 2%.
- the material can be treated with a single dispersion containing all the compounds, or with several dispersions, in particular one containing the active elements and the other the adhesion promoter.
- dispersion should in fact be understood by any predominantly liquid phase which contains solid and / or liquid compounds which may be in suspension (solid particles) or in dispersion, for example a dispersion colloidal, or which create emulsions or which are dissolved, dissolved, for example, a dispersion within the meaning of the invention may relate to a liquid phase comprising only the adhesion promoter completely dissolved in the liquid.
- the parameters of these dispersions and the quantities projected are preferably chosen so that the quantity of "solid" material (essentially the “active" compounds and the adhesion promoters, and possibly all the other additives) actually fixed by the architectural material is at most 10 g / m 2 and for example at least 0.5 g / m 2 , preferably between 1 g / m 2 and 8 g / m 2 , again with the double objective of anti-fouling performance and minimization of appearance modification linked to treatment. It is a "theoretical" quantity calculated according to the quantity of dispersion projected and the concentration of compounds of interest to the invention in the projected dispersion (s) (after evaporation of the water).
- a big advantage of the invention lies in the fact that the elimination of the liquid phase of the dispersions and the hardening of the adhesion promoter (s) after spraying onto the material can be done in an ambient atmosphere. , spontaneously, without requiring post-treatment of the heat treatment type.
- dispersions themselves, in particular those combining in the same liquid phase the "active" compounds and the adhesion promoter (s), with a dry extract of all of these compounds.
- dispersions “ready for projection” generally between 0.5 and 25%, especially between 1 and 5%, decomposing in about 50 to 80% of this dry extract into “active” compounds and in about 20 to 50% of this dry extract in adhesion promoter (s).
- the subject of the invention is also the architectural material described above once treated, namely having the anti-fouling, anti-fungal and / or bactericidal properties by impregnation over a thickness of in particular 400 ⁇ m at most, in particular of the order at most 100 ⁇ m, and preferably at least 20 nm, by photocatalytic metal oxide or sulphide particles, associated with one or more "fixers” resulting from the curing of compounds which are the adhesion promoters described above and possibly one or more additives.
- the impregnation depth of the material depends on a certain number of parameters including the porosity of the material. Porosity, however, can be defined according to different criteria and can be measured by different methods.
- An interesting criterion is the diameter of the pores, in particular of the open pores, those which are accessible to the impregnation. To give an order of magnitude no limiting, it is generally considered that the pores in the coatings have a diameter which can range from a few tens of nanometers to one or a few millimeters, which can be measured for example by the known method of mercury porosity. For tiles, the diameter is around 15 nanometers to 15 ⁇ m. Concrete slabs or pavers have a diameter of pores substantially identical to that of plasters.
- porosity rate of the material is the accessible porosity rate of the material, which can vary widely depending on the material. Thus, for tiles in particular, this rate is around 10 to 40%, especially around 20 to 25%.
- porosity is measured by water absorption tests, by mass (standardized tests for slabs and pavers) which can be converted into volume: schematically, a part of the material is immersed to saturate it in water, then it is dried in an oven and the masses of the product are compared before and after drying (standard NF-P-31 301).
- the first variant consists in treating the materials from an aqueous dispersion containing both the active compounds and the adhesion promoter.
- the materials necessary for the treatment according to the invention are the following:
- the photocatalytic compound used is in the form of particles P of titanium dioxide at least partially crystallized in anatase form, with a diameter of about 40 nm, in colloidal suspension in water,
- a first series of tests was carried out on facade plasters, consisting of hydraulic plasters marketed by the company Weber and Broutin and composed, in a known manner, of cement, of fillers (fibers, limestone of dimensions of the from 20 to 100 ⁇ m), aggregates (quartz, mica, sand of the order of 100 ⁇ m to 4 mm), additives and pigments.
- the coating treated here is a white coating, scraped and washed, dried before treatment: the dispersions are sprayed towards the coating, in an amount making it possible to fix approximately 0.5 g / m 2 of the compounds contained in the dispersions (after evaporation of the water).
- the second variant consists in treating the materials with two dispersions, by first spraying the material with a solution containing the Ti02 particles, then a second containing the adhesion promoters, this second spraying being carried out in a sufficient time after the first for the material to be substantially dry to the touch.
- the second dispersion thus comes to play the role of fixator compared to the particles of Ti02 already introduced on and in the architectural material.
- a series of tests was carried out on the slabs described above, using a first solution S5 of TiO2 particles at 1.25% in water then two types of solutions containing the adhesion promoter:
- the S5 solution is sprayed so as to leave 2 g of material per m 2 treated.
- the soil degradation properties by photocatalysis of all these treated materials were tested as follows: ** • the measurement of the photocatalytic activity of a material consists in depositing a model soiling and in determining its disappearance during irradiation with ultraviolet. As the materials treated here are opaque, the optical measure chosen is colorimetry.
- the model soiling is a black organic ink, ** • the procedure is as follows: the ink used is the Pébéo 8050 photographic retouching ink. After dilution to 20% in water, the ink is sprayed onto the sample using an air pistol.
- a Minolta CR-200 colorimeter is used to measure the color (L, a, b).
- the presence of ink induces a variation of L of the order of 20 units.
- the sample is exposed to UV in a light box comprising 5 Philips Cleo Performance tubes, generating a dose of 5 W / m 2 .
- the variation of L is a function of time, averaged over 3 measurement points.
- the measured value is subtracted from that of a reference sample not containing T1O2.
- this value is translated as a percentage of degradation.
- the variation in L for the reference sample is of the order of 10% after 18 hours of lighting. It can reach 100% for a very active sample. The results obtained can be summarized as follows:
- the slab treated with SI degraded 22% of the soiling, that treated with S2 14% of the fouling, that treated with S3 about 33% of the fouling, and that treated with S4 about 8% of the dirt.
- the slab treated with S3 is the best performing, having degraded 30% of the dirt (25% for the slab treated by SI, 23% for the slab treated by S2, 13% for the slab treated with S4),
- the degradations are at least 35% (treatment with SI), in particular from 57% for the tiles treated with S4 and S3, up to 70% for the tiles processed by S2. After 10 hours, the degradation is at least 40%
- Dispersions associating TiO2 particles and mono-component adhesion promoters titanium dioxide (titanates hydrolyzing and crosslinking progressively at least in part into TiO2) or bi-component (with in addition a silane transforming in the same way at least in part, in SiO2) are therefore effective.
- the method according to the invention provides various embodiments which can be adjusted as a function of the material to be treated, of the place of treatment, which are generally easy to implement (a simple water sprayer was used) with anti- light soiling.
- the invention can also include steps before or after the treatment, making it possible in particular to confer additional functionalities on the material (water-repellent treatment for example) or to improve the effectiveness of the anti-fouling treatment (primer pretreatment ).
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Abstract
The invention concerns a method for treating by impregnation a permeable architectural material which consists in spraying on the architectural material to be treated one or several dispersions in liquid phase of at least a type of photocatalytic compound based on metal oxide or sulphide and at least a type of compound promoting the bonding of said photocatalytic compounds to the architectural material. The invention also concerns the liquid dispersions used and the resulting treated architectural materials.
Description
PROCEDE DE TRAITEMENT DE MATERIAU ARCHITECTURAL PROCESS FOR TREATING ARCHITECTURAL MATERIAL
La présente invention concerne un procédé de traitement de matériaux architecturaux, visant à leur conférer une nouvelle fonctionnalité . Les matériaux plus particulièrement visés sont ceux utilisés dans le bâtiment en tant que matériau de façade, de bardage, de toiture ou de sol et susceptibles d'offrir une certaine porosité /perméabilité vis-à-vis de liquides relativement fluides, tels que l'eau, sur une profondeur décelable, par exemple d'au moins un à quelques microns. Il s'agit notamment de matériaux du type enduits de façade, dalles et pavés de béton, béton architectonique, tuiles, ardoises et tous matériaux de formes variées à base de composition cimentaire, de béton, de terre cuite, ou de pierre du type granit ou marbre.The present invention relates to a method of processing architectural materials, aiming to give them a new functionality. The materials more particularly targeted are those used in building as a facade material, cladding, roofing or soil and capable of offering a certain porosity / permeability vis-à-vis relatively fluid liquids, such as water, to a detectable depth, for example at least one to a few microns. These include materials of the type coated with facades, concrete slabs and pavers, architectural concrete, tiles, slates and all materials of various shapes based on cement composition, concrete, terracotta, or stone of the granite type. or marble.
La nouvelle fonctionnalité que l'invention cherche à leur conférer concerne des propriétés anti-salissures, anti-fongiques et/ou bactéricides, obtenues à l'aide de matériaux semi-conducteurs à base de sulfure ou d'oxyde métallique, notamment à base d'oxyde de titane cristallisé sous forme anatase, présentant une activité photocatalytique : ces matériaux sont en effet aptes, de manière connue, à initier des réactions radicalaires provoquant l'oxydation et la dégradation de produits organiques sous l'effet d'un rayonnement de longueur d'onde adéquate, des ultraviolets en ce qui concerne l'oxyde de titane.The new functionality that the invention seeks to confer on them relates to anti-fouling, anti-fungal and / or bactericidal properties, obtained using semiconductor materials based on sulphide or metal oxide, in particular based on titanium oxide crystallized in anatase form, exhibiting photocatalytic activity: these materials are in fact capable, in known manner, of initiating radical reactions causing the oxidation and degradation of organic products under the effect of long radiation adequate wave, ultraviolet for titanium oxide.
Il y a actuellement une réelle demande pour ce nouveau type de fonctionnalité : ces matériaux utilisés dans la construction ont en effet tendance à perdre très vite leur aspect neuf en raison d'une part de leur présence dans des environnements salissants et d'autre part de leur porosité et/ ou rugosité de surface qui facilitent l'accrochage de la
salissure. Les salissures fréquemment rencontrées sont par exemple les micro-organismes qui affectent non seulement l'aspect, mais aussi, à terme, les propriétés structurelles du matériau. Ainsi, les tuiles se recouvrent d'algues, de lichens ou de mousse en environnement humide. II en est de même pour les dalles ou pavés de béton quand ils sont utilisés pour faire des terrasses ou dans l'aménagement des jardins, et les enduits de façade constituent aussi un substrat propice au développement de végétaux de ce type.There is currently a real demand for this new type of functionality: these materials used in construction tend to quickly lose their new appearance due on the one hand to their presence in dirty environments and on the other hand to their porosity and / or surface roughness which facilitate the attachment of the soiling. The dirt frequently encountered is for example microorganisms which affect not only the appearance, but also, ultimately, the structural properties of the material. Thus, the tiles are covered with algae, lichens or moss in a humid environment. The same is true for concrete slabs or pavers when they are used to make terraces or in landscaping gardens, and facade plasters also constitute a substrate conducive to the development of plants of this type.
Des salissures proviennent également de l'encrassement généré par la pollution organique urbaine, constituée notamment de suies automobiles ou industrielles, suies qui tendent en outre à favoriser l'accrochage de poussières minérales sur le matériau, créant à sa surface des croûtes sombres.Dirt also comes from fouling generated by urban organic pollution, consisting in particular of automobile or industrial soot, soot which also tends to favor the attachment of mineral dust to the material, creating dark crusts on its surface.
On peut aussi mentionner les salissures affectant les dalles de sol du type huile de vidange, graisse, et les façades, comme les graffitis.We can also mention the dirt affecting the floor tiles of the drain oil, grease type, and the facades, such as graffiti.
Apporter à tous ces matériaux une fonction " auto-nettoyante " par des éléments actifs photocatalytique apparaît donc donner une réponse au moins partielle à ce problème, en permettant à tout le moins d'espacer les opérations de nettoyage, ces éléments actifs favorisant la dégradation d'espèces organiques en présence d'oxygène, d'eau et d'un rayonnement approprié de type U.V., c'est-à-dire généralement dans les conditions d'exposition à l'atmosphère ambiante naturelle.Bringing all these materials a "self-cleaning" function with active photocatalytic elements therefore appears to give an at least partial answer to this problem, by at least allowing space for cleaning operations, these active elements promoting the degradation of organic species in the presence of oxygen, water and appropriate UV-type radiation, that is to say generally under the conditions of exposure to the natural ambient atmosphere.
Des publications font déjà état de l'utilisation de particules d'oxyde de titane photocatalytique pour traiter des matériaux architecturaux en vue d'obtenir un effet anti-salissures.Publications have already reported on the use of photocatalytic titanium oxide particles for treating architectural materials with a view to obtaining an anti-fouling effect.
Ainsi, la demande de brevet WO97/ 10185 décrit le dépôt de revêtements photocatalytiques sur des substrats verriers, revêtements comprenant des particules de Ti02 photocatalytique et un liant minéral issu de la décomposition thermique à haute température de précurseurs organo-métalliques.Thus, patent application WO97 / 10185 describes the deposition of photocatalytic coatings on glass substrates, coatings comprising particles of photocatalytic TiO 2 and an inorganic binder resulting from the thermal decomposition at high temperature of organometallic precursors.
On peut également citer la demande de brevet WO98/05601 décrivant l'incorporation de particules de TiO2 photocatalytique
directement dans un liant hydraulique pour composition cimentaire pour faire des enduits de façade, et la demande de brevet EP-0 633 064 Al décrivant des revêtements associant des particules de Ti02 photocatalytique et un adhésif peu susceptible de dégradation photocatalytique du type polymère fluoré, pour traiter des substrats en verre ou en métal notamment.Mention may also be made of patent application WO98 / 05601 describing the incorporation of photocatalytic TiO2 particles directly in a hydraulic binder for cementitious composition for making facade coatings, and patent application EP-0 633 064 A1 describing coatings associating photocatalytic TiO 2 particles and an adhesive little susceptible to photocatalytic degradation of the fluoropolymer type, for treating glass or metal substrates in particular.
L'invention a alors pour but d'améliorer le traitement de substrats architecturaux du type " perméable ", (ce terme ayant été explicité plus haut), par des composés photocatalytiques, amélioration visant notamment une plus grande simplicité et/ ou une plus grande souplesse dans sa mise en œuvre, ainsi qu'une plus grande tenue de ces composés auxdits substrats.The object of the invention is therefore to improve the treatment of architectural substrates of the "permeable" type, (this term having been explained above), by photocatalytic compounds, an improvement aimed in particular at greater simplicity and / or greater flexibility. in its implementation, as well as greater resistance of these compounds to said substrates.
L'invention a tout d'abord pour objet un procédé de traitement par imprégnation de matériau architectural " perméable ", procédé comportant la projection sur le matériau d'une ou plusieurs dispersions en phase liquide d'au moins un type de composés photocatalytiques et d'au moins un type de composés promoteur d'adhérence desdits composés photocatalytiques audit matériau architectural.The invention firstly relates to a method of treatment by impregnation of "permeable" architectural material, method comprising the projection onto the material of one or more dispersions in liquid phase of at least one type of photocatalytic compounds and d at least one type of compound promoting adhesion of said photocatalytic compounds to said architectural material.
On comprend par matériau " perméable " tout matériau utilisé dans la construction qui est susceptible de laisser pénétrer sur une certaine épaisseur des phases liquides du type aqueux, par exemple sur au moins 20 nm jusqu'à notamment 100 ou 50 μm, notamment sur au moins 1 à lOμ, soit notamment tous les types de matériaux cités dans le préambule de la présente demande. On comprend par " imprégnation " le fait que l'essentiel du traitement conduit non seulement à un revêtement contenant les composés photocatalytiques et situé uniquement en surface du matériau, mais aussi à une introduction de ces composés dans l'épaisseur même du matériau grâce à la phase liquide vecteur et à sa porosité naturelle. Une fois le matériau traité, de la façon détaillée ci-dessous, les composés photocatalytiques (dits ci-après " actifs " par souci de concision) vont diffuser sur une certaine épaisseur dans une zone superficielle du
matériau, en affleurant à sa surface, cette imprégnation étant éventuellement " complétée " par la formation d'un revêtement au dessus du matériau, revêtement qui est préférentiellement mince voire discontinu“Permeable” material is understood to mean any material used in construction which is capable of allowing liquid phases of the aqueous type to penetrate over a certain thickness, for example over at least 20 nm up to in particular 100 or 50 μm, in particular over at least 1 to 10 μm, or in particular all the types of materials mentioned in the preamble to the present application. It is understood by "impregnation" the fact that the main part of the treatment leads not only to a coating containing the photocatalytic compounds and situated only on the surface of the material, but also to an introduction of these compounds into the very thickness of the material thanks to the vector liquid phase and its natural porosity. Once the material has been treated, as detailed below, the photocatalytic compounds (hereinafter called "active" for the sake of brevity) will diffuse over a certain thickness in a surface area of the material, by being flush with its surface, this impregnation possibly being "completed" by the formation of a coating on top of the material, coating which is preferably thin or even discontinuous
(ou inexistant). En général, la concentration en éléments actifs dans le matériau diminue au fur et à mesure qu'on s'éloigne de sa surface extérieure : un gradient de concentration s'établit avec la concentration la plus élevée dans la zone affleurant la surface extérieure du matériau.(or non-existent). In general, the concentration of active elements in the material decreases as one moves away from its external surface: a concentration gradient is established with the highest concentration in the zone flush with the external surface of the material .
Cette imprégnation qui tire partie des caractéristiques intrinsèques de porosité des matériaux traités est particulièrement avantageuse : en effet, d'une part on a observé une plus grande pérennité dans le temps de l'effet anti-salissures quand les éléments actifs diffusaient dans le matériau plutôt que lorsqu'ils restaient en surface, une telle diffusion rendant leur " accrochage " au substrat plus aisé et donc leur donnant une plus grande durabilité. D'autre part, même s'il y a une usure progressive du matériau, l'effet anti-salissures va perdurer du fait de cette diffusion, l'usure découvrant progressivement une nouvelle zone active. Enfin, il s'est avéré plus facile de conserver l'aspect visuel du matériau en évitant de former véritablement une couche en surface. Il est en effet généralement requis dans le domaine des matériaux de construction que tout traitement postérieur à la fabrication de ceux-ci, n'entraîne pas, ou le moins possible, de modification d'aspect, notamment de teinte, d'intensité de couleur, de brillance ou d'aspect mat.This impregnation which takes advantage of the intrinsic porosity characteristics of the treated materials is particularly advantageous: in fact, on the one hand, a greater durability over time has been observed of the anti-fouling effect when the active elements diffuse in the material rather that when they remained on the surface, such diffusion making their "attachment" to the substrate easier and therefore giving them greater durability. On the other hand, even if there is a progressive wear of the material, the anti-fouling effect will persist due to this diffusion, the wear gradually discovering a new active area. Finally, it has proved easier to maintain the visual appearance of the material by avoiding actually forming a surface layer. It is in fact generally required in the field of construction materials that any treatment subsequent to the manufacture of these, not result, or as little as possible, in modification of appearance, in particular of hue, of color intensity , gloss or matt appearance.
De préférence, les composés " actifs " vis-à-vis de la photocatalyse sont à base d'oxyde (s) métallique (s) éventuellement dopé, par exemple de l'oxyde de zinc, de l'oxyde de tungstène ou de l'oxyde d'étain. L'exemple préféré selon l'invention concerne l'oxyde de titane au moins partiellement cristallisé sous forme anatase, qui est la phase cristallisée qui confère au Ti02 ses propriétés photocatalytiques. Il peut aussi s'agir de semi- conducteurs appartenant à la famille des sulfures, également au moins partiellement cristallisés comme le sulfure de zinc ou de bore. (Dans la suite du texte, pour plus de simplicité, on mentionnera plutôt l'oxyde de
titane, étant entendu que les indications données sont tout aussi valables pour les autres matériaux semi- conducteurs cités plus haut).Preferably, the compounds "active" with respect to photocatalysis are based on metal oxide (s) optionally doped, for example zinc oxide, tungsten oxide or l 'tin oxide. The preferred example according to the invention relates to titanium oxide at least partially crystallized in anatase form, which is the crystallized phase which gives TiO2 its photocatalytic properties. They may also be semiconductors belonging to the family of sulfides, also at least partially crystallized, such as zinc or boron sulfide. (In the following text, for simplicity, we will rather mention the oxide of titanium, it being understood that the indications given are equally valid for the other semiconductor materials mentioned above).
Avantageusement, ces composés " actifs " du type TiO2 sont utilisés sous forme de particules de diamètre moyen d'au plus de 150 ou 100 nm, notamment compris entre 20 et 60 nm, particules se trouvant de préférence en suspension colloïdale dans une phase liquide, notamment essentiellement aqueuse. On évite ainsi au mieux que les particules ne s'agglomèrent, ce qui dirninuerait notablement leur efficacité. On facilite ainsi leur dispersion homogène sur le matériau, tout en évitant la modification de son aspect.Advantageously, these “active” compounds of the TiO 2 type are used in the form of particles with an average diameter of at most 150 or 100 nm, in particular between 20 and 60 nm, particles preferably being in colloidal suspension in a liquid phase, especially essentially aqueous. This avoids at best that the particles do not agglomerate, which would significantly reduce their effectiveness. This facilitates their homogeneous dispersion on the material, while avoiding modification of its appearance.
Le promoteur d'adhérence est une caractéristique importante de l'invention : de préférence, il est soluble/dispersable en phase essentiellement aqueuse, tout comme les composés " actifs ". Le choix de l'eau (majoritairement, même s'il peut être additionné de solvants organiques miscibles en petite quantité), est particulièrement avantageux au vu des matériaux à traiter : en effet, son coût, sa disponibilité, son absence d'éléments polluant sont très intéressants quand il s'agit de l'utiliser en quantité importante aussi bien dans l'usine de fabrication du matériau architectural (tuiles, dalles), que directement sur chantier lors de la pose même du matériau (enduits de façade), ou, alternativement, après une opération de nettoyage ou de ravalement, dans un contexte de rénovation de bâtiments par exemple.The adhesion promoter is an important characteristic of the invention: preferably, it is soluble / dispersible in essentially aqueous phase, like the "active" compounds. The choice of water (mainly, even if it can be added with miscible organic solvents in small quantities), is particularly advantageous in view of the materials to be treated: indeed, its cost, its availability, its absence of polluting elements are very interesting when it comes to using it in large quantities both in the factory for manufacturing architectural material (tiles, slabs), and directly on site when the material is laid (facade plasters), or , alternatively, after a cleaning or cleaning operation, in the context of building renovations for example.
Le promoteur d'adhérence est choisi préférentiellement de manière à être compatible chimiquement à la fois avec les composés " actifs " et le matériau architectural, pour assurer au mieux la répartition homogène et la fixation permanente des composés sur le matériau. Pour ce faire, on le choisit notamment de façon à ce qu'il soit apte, une fois projeté sur le matériau, à s'y fixer par durcissement, provoqué par une modification chimique et/ ou physique dépendant de sa nature. Cette modification peut se faire dans un temps relativement court après projection ou plus progressivement, sans qu'il y ait nécessité de provoquer ce durcissement par un traitement spécifique du type chauffage. En effet, notamment si le
traitement se fait sur chantier, lors de la pose ou de la rénovation de matériaux de construction, il est important que la mise en œuvre du traitement soit la plus simple possible, (outre le fait que certains des matériaux peuvent ne pas pouvoir supporter des traitements particuliers). Avantageusement, cette modification chimique et/ ou physique spontanée, à l'exposition à l'atmosphère ambiante, peut être une carbonatation, une réaction de type réticulation et/ ou une hydrolyse. Une modification de type physique peut être une coalescence.The adhesion promoter is preferably chosen so as to be chemically compatible with both the "active" compounds and the architectural material, to best ensure the homogeneous distribution and permanent fixation of the compounds on the material. To do this, it is chosen in particular so that it is capable, once projected onto the material, of fixing itself to it by hardening, caused by a chemical and / or physical modification depending on its nature. This modification can be done in a relatively short time after spraying or more gradually, without there being any need to cause this hardening by a specific treatment of the heating type. Indeed, especially if the treatment is done on site, when laying or renovating construction materials, it is important that the implementation of the treatment is as simple as possible, (besides the fact that some of the materials may not be able to withstand treatments individuals). Advantageously, this spontaneous chemical and / or physical modification, upon exposure to the ambient atmosphere, can be carbonation, a crosslinking type reaction and / or hydrolysis. A physical change can be a coalescence.
Il est avantageux que cette transformation chimique les rende essentiellement insolubles en phase aqueuse, notamment dans une large gamme de pH (3-12). En effet, sans promoteur d'adhérence, les éléments " actifs " sous forme de particules ne parviennent pas à se fixer et sont lessivés par exemple par l'eau de pluie, dans un temps très court. Le rôle du promoteur d'adhérence est donc d'abord, en étant soluble/dispersable dans une phase liquide comme les composés " actifs ", de bien se mélanger, s'associer à eux. Puis le promoteur d'adhérence va les fixer définitivement au substrat en servant de liant, de matrice, du fait de son durcissement. S'il restait très soluble dans l'eau, le simple ruissellement d'eau de pluie entraînerait très vite les éléments actifs hors du matériau. Il est également important que le promoteur d'adhérence une fois durci résiste lui-même au mieux à l'effet de dégradation photocatalytique induite par son contact étroit avec les éléments " actifs ".It is advantageous that this chemical transformation makes them essentially insoluble in the aqueous phase, especially in a wide pH range (3-12). In fact, without an adhesion promoter, the "active" elements in the form of particles fail to settle and are leached, for example by rainwater, in a very short time. The role of the adhesion promoter is therefore firstly, by being soluble / dispersible in a liquid phase like the "active" compounds, to mix well, to associate with them. Then the adhesion promoter will permanently fix them to the substrate by serving as a binder, as a matrix, due to its hardening. If it remained very soluble in water, the simple trickling of rainwater would very quickly lead the active elements out of the material. It is also important that the adhesion promoter, once cured, resists at best the effect of photocatalytic degradation induced by its close contact with the "active" elements.
Plusieurs familles de promoteur d'adhérence sont intéressantes. On peut choisir qu'un seul type de promoteur d'adhérence ou en associer plusieurs, en une ou plusieurs dispersions liquides.Several families of adhesion promoters are interesting. It is possible to choose only one type of adhesion promoter or to combine several of them, in one or more liquid dispersions.
Une première famille est celle des composés organo-métalliques, notamment les tétraalkoxydes de forme M(OR)4, avec M le métal du type Ti ou Zr et R un radical carboné du type alkyl linéaire ou ramifié, tous identiques ou différents, ayant notamment de 1 à 6 C. On peut citer notamment le tétrabutoxyde ou tétrapropoxyde de titane ou de zirconium. Il peut aussi s'agir de trialkoxydes du type MR'(OR)3 avec R et R' des radicaux identiques ou différents du type des radicaux décrits plus haut.
Il peut également s'agir d'halogénure métallique, notamment de chlorure comme TiC14.A first family is that of organometallic compounds, in particular the tetraalkoxides of form M (OR) 4, with M the metal of the Ti or Zr type and R a carbon radical of the linear or branched alkyl type, all identical or different, having in particular from 1 to 6 C. Mention may in particular be made of titanium or zirconium tetrabutoxide or tetrapropoxide. It can also be trialkoxides of the MR '(OR) 3 type with R and R' of the same or different radicals of the type of the radicals described above. It may also be a metal halide, in particular chloride such as TiC14.
Tous ces composés sont hautement hydrolysables et il est donc préférable, pour qu'ils restent stables jusqu'à leur utilisation, de les associer dans leur phase liquide avec au moins un agent chélatant/ stabilisant, par exemple du type β-dicétone comme l'acétylacétone (2,4-pentanedione), le benzoylacétone (l-phényl-1 ,3 butanedione), le disopropylacétylacétone, l'acide acétique, la diéthanolamine ou des composés de la famille des glycols comme l'éthylène glycol ou le tétraoctylèneglycol.All these compounds are highly hydrolyzable and it is therefore preferable, for them to remain stable until they are used, to combine them in their liquid phase with at least one chelating / stabilizing agent, for example of the β-diketone type such as acetylacetone (2,4-pentanedione), benzoylacetone (1-phenyl-1, 3 butanedione), disopropylacetylacetone, acetic acid, diethanolamine or compounds of the glycol family such as ethylene glycol or tetraoctylene glycol.
Tous ces composés métalliques vont tendre, une fois projetés sur le matériau à s'hydrolyser progressivement, se dégrader par condensation/réticulation pour faire un réseau présentant des liaisons métal-oxygène ayant une affinité particulièrement élevée avec les éléments actifs sous forme de particules d'oxydes métalliques du type TiO2 et étant insoluble dans l'eau.All these metal compounds will tend, once projected onto the material to be hydrolyzed gradually, to degrade by condensation / crosslinking to form a network having metal-oxygen bonds having a particularly high affinity with the active elements in the form of particles of metal oxides of the TiO2 type and being insoluble in water.
Une seconde famille est celles des alkoxydes de silicium (silanes), par exemple de formule générale Si(OR)3R', avec R et R' présentant le même type de radical que dans le cas de la première famille. II s'est révélé intéressant d'associer un promoteur d'adhérence de la première famille à un promoteur d'adhérence de la seconde, vu la similitude de leur réactivité /comportement et leur bonne compatibilité.A second family is that of silicon alkoxides (silanes), for example of the general formula Si (OR) 3R ', with R and R' having the same type of radical as in the case of the first family. It has proven to be advantageous to associate an adhesion promoter of the first family with an adhesion promoter of the second, given the similarity of their reactivity / behavior and their good compatibility.
Une troisième famille de promoteur d'adhérence est la famille des silicates ou aluminosilicates d'alcalins et/ou d'alcalino-terreux, comme le silicate de sodium, de potassium ou de lithium. De type minéral, ce type de composé va durcir également par une réaction de type polycondensation, réticulation conduisant à la formation d'un réseau minéral avec des liaisons silicium-oxygène insoluble à l'eau et proche chimiquement des matériaux architecturaux du type tuile, terre cuite tout particulièrement.A third family of adhesion promoter is the family of alkali and / or alkaline earth silicates or aluminosilicates, such as sodium, potassium or lithium silicate. Of mineral type, this type of compound will also harden by a polycondensation type reaction, crosslinking leading to the formation of a mineral network with silicon-oxygen bonds insoluble in water and chemically close to architectural materials of the tile, earth type. particularly cooked.
Une quatrième famille de promoteur d'adhérence est celle des polysiloxanes, composés siliciés comme les silicates mais déjà sous une
forme polymère. Leur durcissement progressif est une réaction assimilable à une réticulation des polymères en question. Ils peuvent se présenter sous forme de micro-émulsions de siloxanes ou d'un mélange de silane(s) et de siloxane(s). On voit que le choix du type de promoteur d'adhérence peut se faire parmi des matériaux très variés pouvant être de type composés métalliques hydrolysables, composés siliciés ou organo-siliciés, sous forme polymère ou non, en fonction notamment du type de matériau à traiter et du type d'éléments actifs. Tous ont le point commun d'être aptes, par durcissement progressif, à créer une matrice venant piéger et fixer les particules photocatalytiques au matériau architectural, durcissement pouvant se faire sans aucun traitement postérieur à la projection et " démarrant " conjointement avec l'évaporation de la phase liquide choisie pour faire les dispersions, généralement majoritairement de l'eau. Deux variantes sont possibles concernant la mise en œuvre du procédé de traitement, la façon de projeter les dispersions sur le matériau à traiter.A fourth family of adhesion promoter is that of polysiloxanes, silicon compounds such as silicates but already under a polymeric form. Their progressive hardening is a reaction similar to crosslinking of the polymers in question. They can be in the form of micro-emulsions of siloxanes or of a mixture of silane (s) and siloxane (s). It can be seen that the choice of the type of adhesion promoter can be made from a wide variety of materials, which can be of the hydrolysable metal compound, silicon or organo-silicon compound type, in polymer form or not, depending in particular on the type of material to be treated. and the type of active elements. All have the common point of being able, by progressive hardening, to create a matrix coming to trap and fix the photocatalytic particles to the architectural material, hardening being able to be done without any treatment after the projection and "starting" jointly with the evaporation of the liquid phase chosen to make the dispersions, generally mainly water. Two variants are possible concerning the implementation of the treatment process, the way of projecting the dispersions on the material to be treated.
La première variante consiste à projeter sur le matériau architectural une seule dispersion en phase liquide, comprenant à la fois les composés " actifs " photocatalytiques et le(s) promoteur(s) d'adhérence.The first variant consists in projecting onto the architectural material a single dispersion in the liquid phase, comprising both the photocatalytic "active" compounds and the adhesion promoter (s).
Cette variante a l'avantage de la simplicité, en ayant recours à un seul produit, une seule dispersion liquide minimisant tout risque d'erreur de la part du manipulateur. En revanche, la formulation de la dispersion peut s'avérer plus complexe pour assurer la compatibilité des éléments actifs et des promoteurs d'adhérence, sans sédimentation. Des additifs permettent l'obtention de dispersions stables, mais parfois, selon les cas, avec une durée de stockage une fois conditionnée qui peut s'avérer insuffisante.This variant has the advantage of simplicity, by using a single product, a single liquid dispersion minimizing any risk of error on the part of the manipulator. On the other hand, the formulation of the dispersion can prove to be more complex to ensure the compatibility of the active elements and of the adhesion promoters, without sedimentation. Additives make it possible to obtain stable dispersions, but sometimes, depending on the case, with a storage time once conditioned which may prove to be insufficient.
La seconde variante permet de s'affranchir de cette contrainte : elle consiste à utiliser plusieurs dispersions en phases liquides, une ou plusieurs des dispersions contenant des éléments actifs et une ou plusieurs autres contenant les promoteurs d'adhérence, pluralité de
dispersions que l'on peut projeter conjointement ou l'une après l'autre contre le matériau à traiter. Le mode de réalisation particulièrement préféré de cette variante consiste à projeter dans un premier temps une dispersion contenant les éléments actifs du type particules de TiO2 et dans un second temps une dispersion contenant le promoteur d'adhérence qui vient jouer le rôle de fixateur vis-à-vis des particules déjà logées dans les pores du matériau. Entre les deux projections, il est préférable de laisser s'écouler un laps de temps suffisant pour que le matériau sèche (c'est-à-dire qu'une partie substantielle de l'eau de la première dispersion se soit évaporée).The second variant makes it possible to overcome this constraint: it consists in using several dispersions in liquid phases, one or more of the dispersions containing active elements and one or more others containing the adhesion promoters, plurality of dispersions that can be projected jointly or one after the other against the material to be treated. The particularly preferred embodiment of this variant consists in first projecting a dispersion containing the active elements of the TiO2 particle type and, secondly, a dispersion containing the adhesion promoter which acts as a fixer. -vis particles already lodged in the pores of the material. Between the two projections, it is preferable to allow a sufficient time to pass for the material to dry (that is to say that a substantial part of the water of the first dispersion has evaporated).
Dans les deux variantes, il est bon d'ajuster la quantité de liquide projetée de façon à ne pas avoir un phénomène de ruissellement de liquide sur le matériau, mais plutôt d'imprégnation complète bien répartie sur toute la surface du matériau, quantité dépendant du niveau de perméabilité du matériau.In both variants, it is good to adjust the quantity of liquid projected so as not to have a phenomenon of liquid runoff on the material, but rather of complete impregnation well distributed over the entire surface of the material, quantity dependent on the material permeability level.
Avantageusement, on considère qu'une imprégnation du matériau par la ou les dispersions jusqu'au plus 400 μm, notamment jusqu'au plus 100 ou 200 μm est suffisante pour obtenir un effet anti-salissures notable. Cette profondeur d'imprégnation va correspondre à la profondeur de pénétration des éléments actifs dans le matériau, une fois fixés de manière permanente après séchage et durcissement du promoteur d'adhérence.Advantageously, it is considered that an impregnation of the material with the dispersion (s) up to at most 400 μm, in particular up to at most 100 or 200 μm is sufficient to obtain a notable anti-fouling effect. This impregnation depth will correspond to the penetration depth of the active elements in the material, once fixed permanently after drying and hardening of the adhesion promoter.
Une mise en œuvre avantageuse du procédé selon l'invention consiste à préparer et à conditionner la ou les dispersions en phase liquide sous forme concentrée, la dilution et/ou le mélange des dispersions se faisant juste avant emploi. Cela est tout particulièrement recommandé quand on traite des matériaux de construction lors de la pose ou de leur rénovation sur chantier, pour éviter le stockage de dispersions à forte dilution donc encombrantes et/ ou pour permettre l'ajustement de la dilution en fonction du matériau à traiter à partir de dispersions concentrées standardisées. On peut en effet commercialiser la dispersion " prête à l'emploi ", où l'utilisateur utilise la dispersion telle quelle, ou une dispersion " concentrée ", que l'utilisateur aura à diluer de
façon appropriée. L'important est d'avoir les concentrations adéquates, dans les dispersions " prêtes à la projection ".An advantageous implementation of the method according to the invention consists in preparing and conditioning the liquid phase dispersion (s) in concentrated form, the dilution and / or mixing of the dispersions being carried out just before use. This is particularly recommended when treating building materials during installation or their renovation on site, to avoid the storage of dispersions with high dilution therefore bulky and / or to allow adjustment of the dilution according to the material to be treat from standardized concentrated dispersions. We can indeed market the "ready to use" dispersion, where the user uses the dispersion as it is, or a "concentrated" dispersion, which the user will have to dilute appropriately. The important thing is to have the adequate concentrations, in the dispersions "ready for projection".
Comme mentionné plus haut, notamment pour stabiliser le promoteur d'adhérence mais aussi éventuellement pour stabiliser les éléments actifs en suspension colloïdale, il est préférable d'ajouter aux dispersions des additifs appropriés, notamment des composés organiques comme des β-dicétones, des acides ou des bases pour contrôler leur pH comme l'acide acétique ou l'acide nitrique, des polycarboxylates, des stabilisants comme les composés de la famille du glycol ou des composés connus pour être des agents de couplage comme des silanes.As mentioned above, in particular to stabilize the adhesion promoter but also possibly to stabilize the active elements in colloidal suspension, it is preferable to add to the dispersions suitable additives, in particular organic compounds such as β-diketones, acids or bases to control their pH such as acetic acid or nitric acid, polycarboxylates, stabilizers such as compounds of the glycol family or compounds known to be coupling agents such as silanes.
Il est ainsi connu que les β-dicétones sont capables de stabiliser sous forme de complexe des composés organo-métalliques du type M(OR)4 ou MR'(OR)3 pouvant servir de promoteurs d'adhérence.It is thus known that β-diketones are capable of stabilizing organo-metallic compounds of type M (OR) 4 or MR '(OR) 3 in the form of a complex which can serve as adhesion promoters.
De même, les polycarboxylates sont aptes à stabiliser la dispersion colloïdale de particules photocalytiques. Les dérivés du glycol et les acides ont un effet favorable de stabilisation vis-à-vis de certains des promoteurs d'adhérence et/ ou de certains des composés actifs de l'invention.Likewise, polycarboxylates are capable of stabilizing the colloidal dispersion of photocalytic particles. The glycol derivatives and the acids have a favorable stabilizing effect with respect to some of the adhesion promoters and / or certain of the active compounds of the invention.
On règle de façon appropriée les concentrations en composés actifs et en promoteur d'adhérence dans les dispersions. Par convention, les valeurs d'extrait sec indiquées dans le présent texte sont celles des dispersions " prêtes à la projection " évoquées plus haut. On a coutume, pour ce faire, de choisir comme caractéristique l'extrait sec de ces dispersions, mesuré de façon connue par traitement thermique de l'ordre de 100°C, par exemple selon la norme NF-T30-011. De préférence, l'extrait sec des dispersions correspondant aux composés photocatalytiques est d'au plus 30%, notamment d'au plus 20, 15 ou 10%, et de préférence d'au moins 0,5%. La gamme préférée est par exemple de l'ordre de 1 à 5%.The concentrations of active compounds and of adhesion promoter in the dispersions are appropriately adjusted. By convention, the values of dry extract indicated in the present text are those of the "ready to projection" dispersions mentioned above. It is customary, to do this, to choose as characteristic the dry extract of these dispersions, measured in a known manner by heat treatment of the order of 100 ° C, for example according to standard NF-T30-011. Preferably, the dry extract of the dispersions corresponding to the photocatalytic compounds is at most 30%, in particular at most 20, 15 or 10%, and preferably at least 0.5%. The preferred range is for example of the order of 1 to 5%.
De même, l'extrait sec des dispersions " prêtes à la projection " correspondant au(x) promoteur(s) d'adhérence est de préférence ajusté à une valeur d'au plus 20% ou au plus 15%, ou au plus 10 ou 5%, notamment d'au moins 0,2%, par exemple entre 0,25 et 2%.
Comme on l'a vu plus haut, on peut traiter le matériau avec une seule dispersion contenant tous les composés, ou avec plusieurs dispersions, notamment une contenant les éléments actifs et l'autre le promoteur d'adhérence. Tout au long du présent brevet, il faut en fait comprendre le terme de " dispersion " par toute phase majoritairement liquide qui contient des composés solides et/ ou liquides qui peuvent se trouver en suspension (particules solides) ou en dispersion, par exemple une dispersion colloïdale, ou qui créent des émulsions ou qui se trouvent solubilisés, dissous,
par exemple, une dispersion au sens de l'invention peut concerner une phase liquide ne comprenant que le promoteur d'adhérence complètement solubilisé dans le liquide.Likewise, the dry extract of the "ready-to-spray" dispersions corresponding to the adhesion promoter (s) is preferably adjusted to a value of at most 20% or at most 15%, or at most 10 or 5%, in particular at least 0.2%, for example between 0.25 and 2%. As seen above, the material can be treated with a single dispersion containing all the compounds, or with several dispersions, in particular one containing the active elements and the other the adhesion promoter. Throughout this patent, the term "dispersion" should in fact be understood by any predominantly liquid phase which contains solid and / or liquid compounds which may be in suspension (solid particles) or in dispersion, for example a dispersion colloidal, or which create emulsions or which are dissolved, dissolved, for example, a dispersion within the meaning of the invention may relate to a liquid phase comprising only the adhesion promoter completely dissolved in the liquid.
Ces sélections de taux d'extrait sec résultent d'un compromis optimal entre différents critères à respecter. En effet, la concentration en composés actifs doit être suffisante pour obtenir la fonctionnalité recherchée, cependant une concentration trop importante n'est pas dénuée d'inconvénients, notamment en ce qui concerne l'aspect du matériau. Ainsi, les particules d'oxydes de titane projetées en trop grande quantité et/ ou si elles s'amalgament sur le matériau architectural tendent à le blanchir et à le rendre plus brillant, ce qui n'est pas jugé souhaitable en général. La sélection du taux de promoteur d'adhérence tient compte du taux de composés actifs à fixer. On voit qu'un rapport de là 10, notamment de 3 à 5 entre les deux extraits secs (composés actifs par rapport au promoteur d'adhérence) est souhaitable.These dry extract rate selections result from an optimal compromise between different criteria to be respected. Indeed, the concentration of active compounds must be sufficient to obtain the desired functionality, however too high a concentration is not without drawbacks, in particular as regards the appearance of the material. Thus, the particles of titanium oxides projected in too large quantity and / or if they amalgamate on the architectural material tend to whiten it and to make it more shiny, which is not considered desirable in general. The selection of the rate of adhesion promoter takes account of the rate of active compounds to be fixed. It can be seen that a ratio of there 10, in particular 3 to 5, between the two dry extracts (compounds active with respect to the adhesion promoter) is desirable.
De manière générale, on choisit de préférence les paramètres de ces dispersions et les quantités projetées de façon à ce que la quantité de matériau " solide " (essentiellement les composés " actifs " et les promoteurs d'adhérence, et éventuellement tous les autres additifs) effectivement fixée par le matériau architectural soit d'au plus 10 g/m2 et par exemple d'au moins 0,5 g/m2, de préférence entre 1 g/m2 et 8 g/m2, là encore avec le double objectif de performance anti-salissures et de minimisation de modification d'aspect lié au traitement. Il s'agit d'une quantité " théorique " calculée en fonction de la quantité de dispersion
projetée et de la concentration en composés intéressant l'invention dans la ou les dispersions projetées (après évaporation de l'eau).In general, the parameters of these dispersions and the quantities projected are preferably chosen so that the quantity of "solid" material (essentially the "active" compounds and the adhesion promoters, and possibly all the other additives) actually fixed by the architectural material is at most 10 g / m 2 and for example at least 0.5 g / m 2 , preferably between 1 g / m 2 and 8 g / m 2 , again with the double objective of anti-fouling performance and minimization of appearance modification linked to treatment. It is a "theoretical" quantity calculated according to the quantity of dispersion projected and the concentration of compounds of interest to the invention in the projected dispersion (s) (after evaporation of the water).
Comme mentionné plus haut, un gros avantage de l'invention réside dans le fait que l'élimination de la phase liquide des dispersions et le durcissement du ou des promoteur(s) d'adhérence après projection sur le matériau peut se faire en atmosphère ambiante, spontanément, sans nécessiter de post-traitement de type traitement thermique.As mentioned above, a big advantage of the invention lies in the fact that the elimination of the liquid phase of the dispersions and the hardening of the adhesion promoter (s) after spraying onto the material can be done in an ambient atmosphere. , spontaneously, without requiring post-treatment of the heat treatment type.
Généralement, on projette de l'ordre de 100ml à 10 litres de dispersion par m2 de matériau à traiter. L'invention a également pour objet les dispersions elles-mêmes, notamment celles associant dans une même phase liquide les composés " actifs " et le(s) promoteur(s) d'adhérence, avec un extrait sec de l'ensemble de ces composés dans les dispersions " prêtes à la projection " généralement compris entre 0,5 et 25%, notamment entre 1 et 5%, se décomposant en environ 50 à 80% de cet extrait sec en composés " actifs " et en environ 20 à 50% de cet extrait sec en promoteur(s) d'adhérence.Generally, about 100 ml is projected at 10 liters of dispersion per m2 of material to be treated. The subject of the invention is also the dispersions themselves, in particular those combining in the same liquid phase the "active" compounds and the adhesion promoter (s), with a dry extract of all of these compounds. in dispersions "ready for projection" generally between 0.5 and 25%, especially between 1 and 5%, decomposing in about 50 to 80% of this dry extract into "active" compounds and in about 20 to 50% of this dry extract in adhesion promoter (s).
L'invention a également pour objet le matériau architectural décrit plus haut une fois traité, à savoir présentant les propriétés anti- salissures, anti-fongiques et/ou bactéricides par imprégnation sur une épaisseur de notamment 400 μm au plus, notamment de l'ordre d'au plus 100 μm, et de préférence au moins 20 nm, par des particules d'oxyde ou de sulfure métalliques photocatalytiques, associées à un ou plusieurs " fixateurs " issus du durcissement de composés qui sont les promoteurs d'adhérence décrits plus haut et éventuellement à un ou plusieurs additifs.The subject of the invention is also the architectural material described above once treated, namely having the anti-fouling, anti-fungal and / or bactericidal properties by impregnation over a thickness of in particular 400 μm at most, in particular of the order at most 100 μm, and preferably at least 20 nm, by photocatalytic metal oxide or sulphide particles, associated with one or more "fixers" resulting from the curing of compounds which are the adhesion promoters described above and possibly one or more additives.
Comme évoqué plus haut, la profondeur d'imprégnation du matériau dépend d'un certain nombre de paramètres dont la porosité du matériau. La porosité, cependant, peut se définir selon différents critères et être mesurée par différentes méthodes. Un critère intéressant est le diamètre des pores, notamment des pores ouverts, ceux qui sont accessibles à l'imprégnation. Pour donner un ordre de grandeur non
limitatif, on considère généralement que les pores dans les enduits ont un diamètre pouvant aller de quelques dizaines de nanomètres à un ou quelques millimètres, ce que l'on peut mesurer par exemple par la méthode connue de porosité au mercure. Pour les tuiles, le diamètre est de l'ordre de 15 nanomètres à 15 μm. Les dalles ou pavés de béton ont un diamètre de pores sensiblement identique à celui des enduits.As mentioned above, the impregnation depth of the material depends on a certain number of parameters including the porosity of the material. Porosity, however, can be defined according to different criteria and can be measured by different methods. An interesting criterion is the diameter of the pores, in particular of the open pores, those which are accessible to the impregnation. To give an order of magnitude no limiting, it is generally considered that the pores in the coatings have a diameter which can range from a few tens of nanometers to one or a few millimeters, which can be measured for example by the known method of mercury porosity. For tiles, the diameter is around 15 nanometers to 15 μm. Concrete slabs or pavers have a diameter of pores substantially identical to that of plasters.
Un autre critère est le taux de porosité accessible du matériau, qui peut largement varier selon le matériau. Ainsi, par les tuiles notamment, ce taux est d'environ 10 à 40%, notamment autour de 20 à 25%. Pour les bétons, la porosité est mesurée par des essais d'absorption d'eau, en masse (essais normalisés pour les dalles et les pavés) que l'on peut convertir en volume : schématiquement, on immerge une partie du matériau pour le saturer en eau, puis on le dessèche en étuve et on compare les masses du produit avant et après dessèchement (norme NF- P-31 301).Another criterion is the accessible porosity rate of the material, which can vary widely depending on the material. Thus, for tiles in particular, this rate is around 10 to 40%, especially around 20 to 25%. For concrete, porosity is measured by water absorption tests, by mass (standardized tests for slabs and pavers) which can be converted into volume: schematically, a part of the material is immersed to saturate it in water, then it is dried in an oven and the masses of the product are compared before and after drying (standard NF-P-31 301).
D'autres détails et caractéristiques avantageuses de l'invention ressortent de la description ci-après d'exemples de réalisation non limitatifs :Other details and advantageous characteristics of the invention appear from the following description of nonlimiting exemplary embodiments:
*- la première variante consiste à traiter les matériaux à partir d'une dispersion aqueuse contenant à la fois les composés actifs et le promoteur d'adhérence.* - the first variant consists in treating the materials from an aqueous dispersion containing both the active compounds and the adhesion promoter.
Dans tous les exemples, les matières nécessaires au traitement selon l'invention sont les suivantes :In all the examples, the materials necessary for the treatment according to the invention are the following:
**• le composé photocatalytique utilisé se présente sous la forme de particules P de dioxyde de titane au moins partiellement cristallisées sous forme anatase, de diamètre environ 40 nm, en suspension colloïdale dans l'eau,** • the photocatalytic compound used is in the form of particles P of titanium dioxide at least partially crystallized in anatase form, with a diameter of about 40 nm, in colloidal suspension in water,
*+- un premier promoteur d'adhérence est le tétrabutoxyde de titane r TBT "), **• un second promoteur d'adhérence est le glycidoxypropyle- triméthoxysilane (" glymo "),
»•*• différents additifs sont utilisés : l'acide nitrique (HNO3), l'acétylacétone (" acac "), le polyéthylèneglycol (" PEG ") notamment de faible masse moléculaire (200), agissant comme dispersants ou stabilisants. > Deux solutions SI et S2 d'imprégnation ont été préparées ainsi :* + - a first adhesion promoter is titanium tetrabutoxide r TBT "), ** • a second adhesion promoter is glycidoxypropyle-trimethoxysilane (" glymo "), » • * • various additives are used: nitric acid (HNO3), acetylacetone (" acac "), polyethylene glycol (" PEG "), in particular of low molecular weight (200), acting as dispersants or stabilizers. > Two solutions SI and S2 for impregnation were prepared as follows:
® - 25 g de PEG, 25 g d'eau à 0,7% volumique d'HNO3 sont ajoutés à 19 g d'acac et 31 g de TBT, on obtient une solution " A ",® - 25 g of PEG, 25 g of water at 0.7% by volume of HNO3 are added to 19 g of acac and 31 g of TBT, a solution "A" is obtained,
® - puis on ajoute à 10 g de la solution " A " 80 g d'eau à 0,08% volumique d'HNO3, on obtient une solution " Bl ", (D - on ajoute à 20 g de la solution " Bl " 10 g de particules de TiO2 dans® - then 80 g of water at 0.08% by volume of HNO3 are added to 10 g of solution "A", a "Bl" solution is obtained, (D - 20 g of the "Bl" solution are added "10 g of TiO2 particles in
170 g d'eau, on obtient la solution " SI ", ' - on ajoute à 40 g de la solution " Bl " 10 g de particules de TiO2 dans170 g of water, the solution "SI" is obtained, - 10 g of TiO2 particles are added to 40 g of the solution "Bl" in
150 g d'eau, on obtient la solution " S2 ". Deux solutions S3 et S4 ont été préparées ainsi : ® - 25 g de PEG, 25 g d'eau à 0,7% volumique d'HNO3 sont ajoutés à 19 g d'acac et 31 g de TBT, on obtient une solution " A ",150 g of water, the solution "S2" is obtained. Two solutions S3 and S4 were prepared as follows: ® - 25 g of PEG, 25 g of water at 0.7% by volume of HNO3 are added to 19 g of acac and 31 g of TBT, a solution is obtained " AT ",
(D - puis on ajoute à 10 g de la solution " A " 80 g d'eau à 0,08% d'HNO3 et(D - then 80 g of water containing 0.08% HNO3 are added to 10 g of solution "A" and
2,5 g de glymo ", on obtient une solution " B2 ",2.5 g of glymo ", we obtain a solution" B2 ",
(D - on ajoute à 20 g de la solution " B2 " 10 g de particules de T1O2 dans 170 g d'eau, on obtient la solution " S3 ",(D - 10 g of T1O2 particles in 170 g of water are added to 20 g of the solution "B2", the solution "S3" is obtained,
®' - on ajoute à 40 g de la solution " B2 " 10 g de particules de Ti02 dans® '- 10 g of Ti02 particles are added to 40 g of the "B2" solution
150 g d'eau, on obtient la solution " S4 ".150 g of water, the solution "S4" is obtained.
Le tableau ci-dessous résume la formulation de ces quatre solutions, avec l'extrait sec (global), celui correspondant au TiO2, celui correspondant à chacun des deux promoteurs, et, exprimés en pourcentages en poids par rapport à la phase aqueuse, les différents additifs.The table below summarizes the formulation of these four solutions, with the dry extract (overall), that corresponding to TiO2, that corresponding to each of the two promoters, and, expressed in percentages by weight relative to the aqueous phase, the different additives.
Pour la mesure de l'extrait sec du TBT, on considère qu'il s'est transformé à 100% en TiO2, et par celle du " glymo ", on considère qu'il est transformé à 100% en Si02.
TABLEAU 1For the measurement of the dry extract of TBT, it is considered that it has transformed 100% into TiO2, and by that of "glymo", it is considered that it is transformed to 100% into SiO2. TABLE 1
Ces solutions ont été appliquées par pulvérisation sur les matériaux pour atteindre une couverture de l'ordre de 0,3 à 1 g/m2 mesurée par pesée, (c'est-à-dire que 0,3 à 1 g de l'ensemble des composés figurant dans le tableau 1 sont fixés par m2 de matériau traité).These solutions were applied by spraying on the materials to achieve coverage of the order of 0.3 to 1 g / m 2 measured by weighing, (that is to say 0.3 to 1 g of the all of the compounds shown in Table 1 are fixed per m 2 of material treated).
Z> Une première série d'essais a été effectuée sur des enduits de façade, constitués d'enduits hydrauliques commercialisés par la société Weber et Broutin et composés, de façon connue, de ciment, de charges (fibres, calcaire de dimensions de l'ordre de 20 à 100 μm), de granulats (quartz, mica, sable de l'ordre de 100 μm à 4 mm), d'additifs et de pigments. L'enduit traité ici est un enduit blanc de finition gratté et lavé, séché préalablement au traitement : les dispersions sont pulvérisées en direction de l'enduit, dans une quantité permettant de fixer environ 0,5 g/m2 des composés contenus dans les dispersions (après évaporation de l'eau).Z> A first series of tests was carried out on facade plasters, consisting of hydraulic plasters marketed by the company Weber and Broutin and composed, in a known manner, of cement, of fillers (fibers, limestone of dimensions of the from 20 to 100 μm), aggregates (quartz, mica, sand of the order of 100 μm to 4 mm), additives and pigments. The coating treated here is a white coating, scraped and washed, dried before treatment: the dispersions are sprayed towards the coating, in an amount making it possible to fix approximately 0.5 g / m 2 of the compounds contained in the dispersions (after evaporation of the water).
Z> Une seconde série d'essais a été effectuée sur des dalles de béton commercialisées par la société Stradal, sous la référence " 6512 polie " : les solutions ont été pulvérisées en direction de ces dalles de façon à fixer environ 0,3 g de matière par m2. Z> Une troisième série d'essais a été effectuée sur des tuiles commercialisées par la Société Tuiles Briqueterie Française sous la dénomination commerciale " Romanée-Canal Rouge " : les solutions étant pulvérisées de façon à ce qu'environ 0,6 g de matière soit fixée par m2.Z> A second series of tests was carried out on concrete slabs sold by the company Stradal, under the reference "6512 polished": the solutions were sprayed in the direction of these slabs so as to fix approximately 0.3 g of material per m 2 . Z> A third series of tests was carried out on tiles sold by the Société Tuiles Briqueterie Française under the trade name "Romanée-Canal Rouge": the solutions being sprayed so that approximately 0.6 g of material is fixed by m 2 .
•*- La seconde variante consiste à traiter les matériaux avec deux dispersions, en pulvérisant d'abord sur le matériau une solution contenant les particules de Ti02, puis une seconde contenant le ou les
promoteurs d'adhérence, cette seconde pulvérisation s'effectuant dans un laps de temps suffisant après la première pour que le matériau soit substantiellement sec au toucher. La seconde dispersion vient ainsi jouer le rôle de fixateur par rapport aux particules de Ti02 déjà introduites sur et dans le matériau architectural. Une série d'essais a été effectuée sur les dalles décrites plus haut, utilisant une première solution S5 de particules de TiO2 à 1,25 % dans l'eau puis deux types de solutions contenant le promoteur d'adhérence :• * - The second variant consists in treating the materials with two dispersions, by first spraying the material with a solution containing the Ti02 particles, then a second containing the adhesion promoters, this second spraying being carried out in a sufficient time after the first for the material to be substantially dry to the touch. The second dispersion thus comes to play the role of fixator compared to the particles of Ti02 already introduced on and in the architectural material. A series of tests was carried out on the slabs described above, using a first solution S5 of TiO2 particles at 1.25% in water then two types of solutions containing the adhesion promoter:
**• soit une solution S6 sous forme d'une micro-émulsion de siloxane commercialisée par Wacker sous la dénomination " SMK 2100 ",** • either an S6 solution in the form of a siloxane microemulsion sold by Wacker under the name "SMK 2100",
^ soit une solution S6' sous forme d'une solution à base de sel d'ammonium de lactate de titane hydrosoluble.^ or a solution S6 'in the form of a solution based on ammonium salt of water-soluble titanium lactate.
La pulvérisation de la solution S5 est réalisée de façon à laisser 2 g de matière par m2 traité. La pulvérisation des solutions S6 et S6' est réalisée de façon à laisser 0,3 et 0,6 g/m2 pour S6 (S6-1 et S6-2), 0,2 et 0,6 g/m2 pour S6' (S6'- l et S6'-2).The S5 solution is sprayed so as to leave 2 g of material per m 2 treated. The solutions S6 and S6 'are sprayed so as to leave 0.3 and 0.6 g / m 2 for S6 (S6-1 and S6-2), 0.2 and 0.6 g / m 2 for S6 '(S6'- l and S6'-2).
Les propriétés de dégradation des salissures par photocatalyse de tous ces matériaux traités ont été testées de la façon suivante : **• la mesure de l'activité photocatalytique d'un matériau consiste à déposer une salissure modèle et à doser sa disparition au cours d'une irradiation par des ultraviolets. Comme les matériaux traités ici sont opaques, la mesure optique retenue est la colorimétrie. La salissure modèle est une encre organique noire, **• le mode opératoire est le suivant : l'encre utilisée est l'encre de retouche photographique Pébéo 8050. Après dilution à 20% dans l'eau, l'encre est pulvérisée sur l'échantillon à l'aide d'un pistolet à air comprimé.The soil degradation properties by photocatalysis of all these treated materials were tested as follows: ** • the measurement of the photocatalytic activity of a material consists in depositing a model soiling and in determining its disappearance during irradiation with ultraviolet. As the materials treated here are opaque, the optical measure chosen is colorimetry. The model soiling is a black organic ink, ** • the procedure is as follows: the ink used is the Pébéo 8050 photographic retouching ink. After dilution to 20% in water, the ink is sprayed onto the sample using an air pistol.
Un colorimètre Minolta CR-200 est employé pour mesurer la couleur (L, a, b). La présence d'encre induit une variation de L de l'ordre de 20 unités. Après séchage 2 heures, l'échantillon est exposé aux U.V. dans une boîte à lumière comportant 5 tubes Philips Cleo Performance, générant une dose de 5 W/m2. On note ainsi la variation de L en fonction du temps,
moyennée sur 3 points de mesure. Pour chaque échantillon, on soustrait la valeur mesurée à celle d'un échantillon de référence ne contenant pas de T1O2. Enfin cette valeur est traduite en pourcentage de dégradation. La variation de L pour l'échantillon de référence est de l'ordre de 10% après 18 heures d'éclairage. Elle peut atteindre 100% pour un échantillon très actif Les résultats obtenus peuvent se résumer de la façon suivante :A Minolta CR-200 colorimeter is used to measure the color (L, a, b). The presence of ink induces a variation of L of the order of 20 units. After drying for 2 hours, the sample is exposed to UV in a light box comprising 5 Philips Cleo Performance tubes, generating a dose of 5 W / m 2 . We thus note the variation of L as a function of time, averaged over 3 measurement points. For each sample, the measured value is subtracted from that of a reference sample not containing T1O2. Finally, this value is translated as a percentage of degradation. The variation in L for the reference sample is of the order of 10% after 18 hours of lighting. It can reach 100% for a very active sample. The results obtained can be summarized as follows:
Z> Pour les essais selon la première variante (pulvérisation à partir d'une seule dispersion),Z> For the tests according to the first variant (spraying from a single dispersion),
*•* en ce qui concerne les enduits, tous les enduits traités quelle que soit la solution SI à S4 utilisées, montrent une capacité à dégrader au moins 20% de la salissure en 1 heure. Au bout de 5 heures, l'enduit traité par SI a dégradé environ 25% de la salissure, celui traité par S2 environ 28% de la salissure, celui traité par S3 environ 37% de la salissure et celui traité par S4 environ 43% de la salissure. Le témoin présente une activité photocatalytique nulle,* • * with regard to the plasters, all the plasters treated, whatever the solution SI to S4 used, show an ability to degrade at least 20% of the dirt in 1 hour. After 5 hours, the coating treated with SI degraded about 25% of the dirt, that treated with S2 about 28% of the dirt, that treated with S3 about 37% of the dirt and that treated with S4 about 43% of dirt. The witness has zero photocatalytic activity,
**• en ce qui concerne les dalles, au bout de 5 heures, la dalle traitée par SI a dégradé 22% de la salissure, celle traitée par S2 14% de la salissure, celle traitée par S3 environ 33% de la salissure, et celle traitée par S4 environ 8% de la salissure. Au bout de 10 heures, c'est la dalle traitée par S3 qui est la plus performante, en ayant dégradé 30% de la salissure (25% pour la dalle traitée par SI , 23% pour la dalle traitée par S2, 13% pour la dalle traitée par S4),** • with regard to the slabs, after 5 hours, the slab treated with SI degraded 22% of the soiling, that treated with S2 14% of the fouling, that treated with S3 about 33% of the fouling, and that treated with S4 about 8% of the dirt. After 10 hours, the slab treated with S3 is the best performing, having degraded 30% of the dirt (25% for the slab treated by SI, 23% for the slab treated by S2, 13% for the slab treated with S4),
^ en ce qui concerne les tuiles, au bout de 5 heures, les dégradations sont d'au moins 35% (traitement avec SI), notamment de 57% pour les tuiles traitées par S4 et S3, jusqu'à 70% pour les tuiles traitées par S2. Au bout de 10 heures, la dégradation est d'au moins 40%^ as regards the tiles, after 5 hours, the degradations are at least 35% (treatment with SI), in particular from 57% for the tiles treated with S4 and S3, up to 70% for the tiles processed by S2. After 10 hours, the degradation is at least 40%
(SI), notamment 65% (S3 et S4), jusqu'à 90% avec S2.(SI), in particular 65% (S3 and S4), up to 90% with S2.
On constate donc que tous ces matériaux ont une activité photocatalytique notable, avec une activité particulièrement élevée pour les tuiles puisqu'elles peuvent dégrader jusqu'à 90% de la salissure modèle. C'est une preuve de l'importance de la nature du substrat choisi,
aussi bien quant à sa nature chimique que quant à sa texture /porosité par exemple.It is therefore found that all of these materials have a notable photocatalytic activity, with a particularly high activity for the tiles since they can degrade up to 90% of the model soiling. This is proof of the importance of the nature of the substrate chosen, as well as for its chemical nature as for its texture / porosity for example.
Des dispersions associant des particules de TiO2 et des promoteurs d'adhérence mono-composant (des titanates s'hydrolysant et réticulant progressivement au moins en partie en Ti02) ou bi-composant (avec en outre un silane se transformant de la même manière au moins en partie, en SiO2) sont donc efficaces.Dispersions associating TiO2 particles and mono-component adhesion promoters (titanates hydrolyzing and crosslinking progressively at least in part into TiO2) or bi-component (with in addition a silane transforming in the same way at least in part, in SiO2) are therefore effective.
D Pour les essais selon la deuxième variante (pulvérisation en deux étapes), au bout de 5 heures, les dalles traitées par S5 puis S6-1 dégradent environ 16% de la salissure et celles traitées par S5 puis S6-2 environ 25% de la salissure ; les dalles traitées par S5 puis S6'-l dégradent environ 34% de la salissure et celles traitées par S5 puis S6'-2 environ 42% de la salissure. Au bout de 10 heures, les résultats s'échelonnent de 26% (S5 + S6- 1), de 32% (S5 + S6-2), de 39% (S5 + S6'- l) jusqu'à 47% (S5 + S6'-2). Là encore, une activité anti- salissure notable a donc été observée pour les dalles, dépassant les 40% de dégradation contrairement aux dalles traitées en une fois.D For the tests according to the second variant (spraying in two stages), after 5 hours, the tiles treated with S5 then S6-1 degrade about 16% of the dirt and those treated with S5 then S6-2 about 25% of soiling; the tiles treated with S5 then S6'-l degrade approximately 34% of the soiling and those treated with S5 then S6'-2 approximately 42% of the soiling. After 10 hours, the results range from 26% (S5 + S6-1), 32% (S5 + S6-2), 39% (S5 + S6'- l) up to 47% ( S5 + S6'-2). Again, a significant anti-fouling activity was therefore observed for the slabs, exceeding 40% degradation, unlike the slabs treated at once.
On voit donc que le procédé selon l'invention propose différents modes de réalisation ajustables en fonction du matériau à traiter, du lieu de traitement, globalement faciles de mise en œuvre (un simple pulvérisateur d'eau a été utilisé) avec des performances anti-salissures claires.It can therefore be seen that the method according to the invention provides various embodiments which can be adjusted as a function of the material to be treated, of the place of treatment, which are generally easy to implement (a simple water sprayer was used) with anti- light soiling.
Il va de soi que l'invention peut comprendre aussi des étapes avant ou après le traitement permettant notamment de conférer des fonctionnalités supplémentaires au matériau (traitement hydrofuge par exemple) ou d'améliorer l'efficacité du traitement anti-salissures (prétraitement d'apprêt).It goes without saying that the invention can also include steps before or after the treatment, making it possible in particular to confer additional functionalities on the material (water-repellent treatment for example) or to improve the effectiveness of the anti-fouling treatment (primer pretreatment ).
Si une partie significative des composés actifs photocatalytiques par ce mode de dépôt par projection en phase liquide migre dans l'épaisseur même du matériau, il rentre aussi dans le cadre de l'invention qu'une partie reste en surface pour former un film continu ou discontinu, dont on
peut ajuster les caractéristiques pour qu'il soit de préférence essentiellement " neutre " sur le plan visuel.
If a significant part of the active photocatalytic compounds by this mode of deposition by projection in liquid phase migrates in the very thickness of the material, it also falls within the scope of the invention that a part remains on the surface to form a continuous film or discontinuous, which may adjust the characteristics so that it is preferably essentially "neutral" visually.
Claims
1. Procédé de traitement par imprégnation d'un matériau architectural " perméable " comportant la projection sur le matériau architectural à traiter d'une ou plusieurs dispersions en phase liquide d'au moins un type de composés photocatalytiques à base d'oxyde ou de sulfure métallique et d'au moins un type de composé promoteur d'adhérence desdits composés photocatalytiques audit matériau architectural.1. A method of treatment by impregnation of an "permeable" architectural material comprising the projection onto the architectural material to be treated of one or more dispersions in the liquid phase of at least one type of photocatalytic compounds based on oxide or sulphide metallic and at least one type of compound promoting adhesion of said photocatalytic compounds to said architectural material.
2. Procédé selon la revendication 1 , caractérisé en ce que le matériau architectural " perméable " est un enduit de façade, des dalles ou des pavés de béton, du béton architectonique, des tuiles et tout matériau à base de composition cimentaire, de béton, de terre cuite, d'ardoise, de pierre du type granit ou marbre.2. Method according to claim 1, characterized in that the "permeable" architectural material is a facade coating, concrete slabs or pavers, architectural concrete, tiles and any material based on cementitious composition, concrete, terracotta, slate, granite or marble type stone.
3. Procédé selon l'une des revendications précédentes, caractérisé en ce que les composés photocatalytiques sont à base d'oxyde de titane au moins partiellement cristallisé sous forme anatase.3. Method according to one of the preceding claims, characterized in that the photocatalytic compounds are based on titanium oxide at least partially crystallized in anatase form.
4. Procédé selon l'une des revendications précédentes, caractérisé en ce que les composés photocatalytiques sont sous forme de particules de diamètre moyen d'au plus 150, notamment d'au plus 100 nm, de préférence compris entre 20 et 60 nm, notamment en suspension colloïdale dans la phase liquide du type phase aqueuse.4. Method according to one of the preceding claims, characterized in that the photocatalytic compounds are in the form of particles with an average diameter of at most 150, especially at most 100 nm, preferably between 20 and 60 nm, in particular in colloidal suspension in the liquid phase of the aqueous phase type.
5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le(s) promoteur(s) d'adhérence est (sont) soluble(s)/dispersable(s) en phase aqueuse. 5. Method according to one of the preceding claims, characterized in that the adhesion promoter (s) is (are) soluble (s) / dispersible (s) in the aqueous phase.
6. Procédé selon l'une des revendications précédentes, caractérisé en ce que le(s) promoteur(s) d'adhérence est (sont) apte(s), une fois projeté(s) sur le matériau architectural, à s'y fixer par durcissement provoqué par une modification chimique et/ ou physique du type hydrolyse, carbonatation, réticulation, coalescence, durcissement le(s) rendant essentiellement insoluble(s) en phase aqueuse.6. Method according to one of the preceding claims, characterized in that the adhesion promoter (s) is (are) able, once projected (s) on the architectural material, to be there fix by hardening caused by a chemical and / or physical modification of the hydrolysis, carbonation, crosslinking, coalescence, hardening type (s) rendering it essentially insoluble (s) in aqueous phase.
7. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'un type de promoteur d'adhérence est la famille des composés organo-métalliques, notamment les tétralkoxydes de forme M(OR)4 ou des trialkoxydes de forme M(OR)3R\ avec M un métal du type Ti ou Zr et R, R' un radical carboné du type alkyl linéaire ou ramifié, tous identiques ou différents, ayant notamment 1 à 6 C, ou de la famille des halogénures métalliques comme T1C14 ou de la famille des alkoxydes de silicium.7. Method according to one of the preceding claims, characterized in that one type of adhesion promoter is the family of compounds organo-metallic, in particular tetralkoxides of form M (OR) 4 or trialkoxides of form M (OR) 3R \ with M a metal of the Ti or Zr type and R, R 'a carbon radical of the linear or branched alkyl type, all identical or different, having in particular 1 to 6 C, or of the family of metal halides such as T1C14 or of the family of silicon alkoxides.
8. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'un type de promoteur d'adhérence est la famille des silicates ou aluminosilicates d'alcalins et/ ou d'alcalino-terreux, comme le silicate de potassium, de sodium ou de lithium. 8. Method according to one of the preceding claims, characterized in that a type of adhesion promoter is the family of alkali and / or alkaline earth silicates or aluminosilicates, such as potassium silicate, sodium or lithium.
9. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'un type de promoteur d'adhérence est la famille des polysiloxanes.9. Method according to one of the preceding claims, characterized in that one type of adhesion promoter is the family of polysiloxanes.
10. Procédé selon l'une des revendications précédentes, caractérisé en ce que la ou les phase(s) liquide(s) de la ou des dispersions est (sont) essentiellement aqueuse(s). 10. Method according to one of the preceding claims, characterized in that the liquid phase (s) of the dispersion (s) is (are) essentially aqueous (s).
11. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on projette sur le matériau architectural une seule dispersion en phase liquide comprenant à la fois le(s) composé(s) photocatalytique(s) et le (s) promoteur (s) d'adhérence.11. Method according to one of the preceding claims, characterized in that a single dispersion in liquid phase is projected onto the architectural material comprising both the photocatalytic compound (s) and the promoter (s) (s) of grip.
12. Procédé selon l'une des revendications 1 à 10, caractérisé en ce qu'on projette simultanément ou les unes après les autres une ou plusieurs dispersions contenant les composés photocatalytiques et une ou plusieurs dispersions contenant les promoteurs d'adhérence, en projetant de préférence d'abord une dispersion contenant des composés photocatalytiques puis une ou plusieurs dispersions contenant le ou les promoteur(s) d'adhérence.12. Method according to one of claims 1 to 10, characterized in that one or several of the dispersions are projected simultaneously or one after the other containing the photocatalytic compounds and one or more dispersions containing the adhesion promoters, by projecting preferably first a dispersion containing photocatalytic compounds and then one or more dispersions containing the adhesion promoter (s).
13. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'imprégnation du matériau architectural se fait sur une épaisseur allant jusqu'au plus 400 μm ou 100 μm.13. Method according to one of the preceding claims, characterized in that the impregnation of the architectural material takes place over a thickness of up to 400 μm or 100 μm.
14. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on prépare et conditionne la ou les dispersions en phase liquide sous forme concentrée, la dilution et/ ou le mélange des dispersions se faisant juste avant emploi. 14. Method according to one of the preceding claims, characterized in that the liquid phase dispersions are dispersed and concentrated in concentrated form, the dilution and / or mixing of the dispersions being carried out just before use.
15. Procédé selon l'une des revendications précédentes, caractérisé en ce que la ou les dispersions comprennent des additifs visant à stabiliser la ou les dispersions en phase liquide, notamment du type agent chélatant/stabilisant tels que des β-dicétones, des acides comme l'acide acétique ou l'acide nitrique, des composés de la famille du glycol, des polycarboxylates, des composés de la famille des silanes.15. Method according to one of the preceding claims, characterized in that the dispersion (s) comprise additives intended to stabilize the dispersion (s) in the liquid phase, in particular of the chelating / stabilizing agent type such as β-diketones, acids such as acetic acid or nitric acid, compounds of the glycol family, polycarboxylates, compounds of the silane family.
16. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'extrait sec en composés photocatalytiques des dispersions prêtes à la projection sur le matériau architectural est ajusté à une valeur d'au plus 30%>, notamment d'au plus 10% et d'au moins 0,5%, de préférence compris entre 1 et 5%.16. Method according to one of the preceding claims, characterized in that the dry extract of photocatalytic compounds of the dispersions ready for projection onto the architectural material is adjusted to a value of at most 30%>, in particular at most 10% and at least 0.5%, preferably between 1 and 5%.
17. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'extrait sec en promoteur(s) d'adhérence des dispersions prêtes à la projection sur le matériau architectural est ajusté à une valeur d'au plus 20%, notamment d'au moins 0,2%, de préférence entre 0,25 et 2%.17. Method according to one of the preceding claims, characterized in that the dry extract in promoter (s) of adhesion of the dispersions ready for projection on the architectural material is adjusted to a value of at most 20%, in particular at least 0.2%, preferably between 0.25 and 2%.
18. Procédé selon l'une des revendications précédentes, caractérisé en ce que la quantité de composés photocatalytiques et de promoteurs d'adhérence fixée au matériau architectural par projection de la ou des dispersions qui les contiennent est d'au plus 10 g/m2 de surface traitée, notamment d'au moins 0,5 g/m2, de préférence entre 1 g/m2 et 10 g/m2.18. Method according to one of the preceding claims, characterized in that the quantity of photocatalytic compounds and adhesion promoters fixed to the architectural material by projection of the dispersion or dispersions which contain them is at most 10 g / m 2 surface area treated, in particular at least 0.5 g / m 2 , preferably between 1 g / m 2 and 10 g / m 2 .
19. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'élimination de la phase liquide des dispersions et le durcissement du ou des promoteurs d'adhérence après projection sur le matériau architectural se font en atmosphère ambiante, sans post- traitement du type traitement thermique.19. Method according to one of the preceding claims, characterized in that the elimination of the liquid phase of the dispersions and the hardening of the adhesion promoter (s) after spraying onto the architectural material are carried out in an ambient atmosphere, without post-treatment. of the heat treatment type.
20. Dispersion liquide en phase essentiellement aqueuse comprenant :20. Liquid dispersion in essentially aqueous phase comprising:
*•- des particules d'oxyde ou de sulfure métallique à propriétés photocatalytiques du type oxyde de titane au moins partiellement cristallisé sous forme anatase, notamment en suspension colloïdale,* • - particles of metal oxide or sulphide with photocatalytic properties of the titanium oxide type at least partially crystallized in anatase form, in particular in colloidal suspension,
**• un ou plusieurs types de promoteurs d'adhérence desdites particules appartenant à la famille des composés organo-métalliques et/ ou à la famille des silicates ou aluminosilicates d'alcalins ou d'alcalino-terreux et/ ou à la famille des polysiloxanes et/ ou celle des alkoxydes de silicium,** • one or more types of adhesion promoters of said particles belonging to the family of organometallic compounds and / or to the family of alkali or alkaline earth silicates or aluminosilicates and / or to the family of polysiloxanes and / or that of silicon alkoxides,
*•• éventuellement un ou plusieurs additifs visant à stabiliser la dispersion tels que des β-dicétones, des acides, des composés de la famille des glycols.* • • optionally one or more additives intended to stabilize the dispersion such as β-diketones, acids, compounds of the glycol family.
21. Dispersion liquide selon la revendication 20, caractérisée en ce que son extrait sec est compris entre 0,5% et 2%, avec notamment entre 50% et 80% de cet extrait sec sous forme de particules photocatalytiques et entre 20 à 50% de cet extrait sec sous forme de promoteur(s) d'adhérence.21. Liquid dispersion according to claim 20, characterized in that its dry extract is between 0.5% and 2%, with in particular between 50% and 80% of this dry extract in the form of photocatalytic particles and between 20 to 50% of this dry extract in the form of adhesion promoter (s).
22. Utilisation du procédé selon les revendications 1 à 19 ou de la dispersion selon les revendications 20 ou 21 pour traiter des matériaux architecturaux " perméables " du type enduit de façade, dalles ou pavés de béton, béton architectonique, tuiles et tout matériau à base de composition cimentaire, béton, terre cuite, pierre comme le marbre ou le granit, afin de leur conférer des propriétés anti-salissures, anti-fongiques et/ou bactéricides.22. Use of the method according to claims 1 to 19 or of the dispersion according to claims 20 or 21 for treating "permeable" architectural materials of the type coated with facades, concrete slabs or pavers, architectural concrete, tiles and any material based of cement, concrete, terracotta, stone such as marble or granite composition, in order to give them anti-soiling, anti-fungal and / or bactericidal properties.
23. Matériau architectural " perméable ", notamment sous forme d'enduit de façade, de dalles ou pavés de béton, de tuiles et tout matériau à base de composition cimentaire, béton, terre cuite ou pierre, caractérisé en ce qu'il présente des propriétés anti-salissures, anti-fongiques et/ou bactéricides par imprégnation, notamment sur une épaisseur d'au plus 400 μm, par des particules d'oxyde ou de sulfure métalliques photocatalytique du type TiO2 au moins partiellement cristallisé sous forme anatase, associés à un ou plusieurs fixateurs issus du durcissement de promoteurs d'adhérence appartenant à la famille des organo-métalliques et/ ou à la famille des silicates ou aluminosilicates d'alcalins ou d'alcalino-terreux et/ ou à la famille des polysiloxanes, et/ ou des alkoxydes de silicium et éventuellement des additifs. 23. "Permeable" architectural material, in particular in the form of a facade plaster, concrete slabs or pavers, tiles and any material based on a cementitious composition, concrete, terracotta or stone, characterized in that it has anti-fouling, anti-fungal and / or bactericidal properties by impregnation, in particular over a thickness of at most 400 μm, with photocatalytic metal oxide or sulphide particles of the TiO2 type at least partially crystallized in anatase form, associated with one or more fixatives resulting from the hardening of adhesion promoters belonging to the organometallic family and / or to the family of alkali or alkaline earth silicates or aluminosilicates and / or to the family of polysiloxanes, and / or silicon alkoxides and optionally additives.
24. Matériau architectural selon la revendication 23 caractérisé en ce que l'imprégnation se fait sur une épaisseur d'au moins 20 nm. 24. Architectural material according to claim 23 characterized in that the impregnation takes place over a thickness of at least 20 nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9910187 | 1999-08-05 | ||
| FR9910187A FR2797262B1 (en) | 1999-08-05 | 1999-08-05 | PROCESS FOR TREATING ARCHITECTURAL MATERIAL |
| PCT/FR2000/002255 WO2001010793A1 (en) | 1999-08-05 | 2000-08-04 | Method for treating architectural material |
Publications (1)
| Publication Number | Publication Date |
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| EP1204621A1 true EP1204621A1 (en) | 2002-05-15 |
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ID=9548926
Family Applications (1)
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|---|---|---|---|
| EP00956628A Withdrawn EP1204621A1 (en) | 1999-08-05 | 2000-08-04 | Method for treating architectural material |
Country Status (13)
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| EP (1) | EP1204621A1 (en) |
| JP (1) | JP2003506307A (en) |
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| AU (1) | AU6850700A (en) |
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| CZ (1) | CZ2002442A3 (en) |
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| HU (1) | HUP0203085A2 (en) |
| MY (1) | MY131809A (en) |
| PL (1) | PL202747B1 (en) |
| TW (1) | TWI238153B (en) |
| WO (1) | WO2001010793A1 (en) |
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| US6569520B1 (en) * | 2000-03-21 | 2003-05-27 | 3M Innovative Properties Company | Photocatalytic composition and method for preventing algae growth on building materials |
| FR2824321B1 (en) | 2001-05-02 | 2004-04-16 | Saint Gobain Mat Constr Sas | ARCHITECTURAL MATERIAL PROVIDED WITH A COATING AND METHOD FOR OBTAINING SAME |
| JP2002348183A (en) * | 2001-05-25 | 2002-12-04 | Inax Corp | Humidity controlling building material having purification function and method for manufacturing the same |
| EP1390320A1 (en) * | 2001-05-31 | 2004-02-25 | Akzo Nobel Coatings International B.V. | Coating biscuit tiles with an abrason- and scratch- resistant coat |
| US7811630B2 (en) * | 2003-06-20 | 2010-10-12 | Certainteed Corporation | Algae resistant roofing granules with controlled algaecide leaching rates, algae resistant shingles, and process for producing same |
| CN100487205C (en) * | 2004-06-15 | 2009-05-13 | 盛南工业株式会社 | Vegetation block and outer layer body for vegetation block |
| JP2008525188A (en) * | 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 | Automatic cleaning process of dirt by photocatalyst |
| US20060137708A1 (en) * | 2004-12-28 | 2006-06-29 | Council Of Scientific And Industrial Research | Photocatalytic auto-cleaning process of stains |
| FR2884111B1 (en) * | 2005-04-07 | 2007-05-18 | Saint Gobain Mat Constr Sas | BIOCIDAL GRANULE, IN PARTICULAR FOR THE MANUFACTURE OF ASPHALT SHINGLE |
| US7358218B2 (en) * | 2005-06-03 | 2008-04-15 | Research Foundation Of The University Of Central Florida, Inc. | Method for masking and removing stains from rugged solid surfaces |
| BRPI0600312A (en) * | 2006-01-20 | 2007-10-30 | Opto Eletronica S A | Method and process for producing self-cleaning nanostructured thin film on the surface of lenses and optical devices |
| US8012242B2 (en) * | 2006-08-31 | 2011-09-06 | The University Of North Dakota | Adsorbent mediated reduction of organic chemicals from solid building materials |
| FR2910014B1 (en) | 2006-12-18 | 2009-10-02 | Rhodia Recherches & Tech | TREATMENT FACILITATING THE REMOVAL OF A COATING AND / OR A SOIL ON A BUILDING MATERIAL. |
| CA2671772C (en) * | 2006-12-22 | 2015-10-06 | 3M Innovative Properties Company | Photocatalytic coating |
| CN101563150A (en) * | 2006-12-22 | 2009-10-21 | 3M创新有限公司 | Photocatalytic coating |
| EP2106288B1 (en) * | 2006-12-22 | 2021-03-31 | 3M Innovative Properties Company | A coated roofing granule, a method of making a coated roofing granule and a base roofing material in which said coated roofing material is partially embedded |
| BRPI0822504B1 (en) * | 2008-03-31 | 2018-12-11 | Rockwood Italia Spa | granulated material presenting photocatalytic activity, its uses and its production process, building material and its use |
| US8561862B2 (en) * | 2008-05-15 | 2013-10-22 | Jai Foggiato | Personal securing apparatus for handheld devices |
| CN102153369B (en) * | 2010-12-09 | 2012-09-26 | 东南大学 | Method for reinforcing autoclaved aerated concrete by using external reinforcing agent |
| WO2014118371A1 (en) * | 2013-02-03 | 2014-08-07 | Joma International A/S | A catalytic substrate surface containing particles |
| US9493378B2 (en) * | 2013-03-13 | 2016-11-15 | Pavement Technology, Inc. | Method of embedding photocatalytic titanium dioxide in concrete structures to reduce pollutants via photocatalytic reactions |
| US10407351B2 (en) | 2013-03-13 | 2019-09-10 | Pavement Technology, Inc. | Method of dispersing anatase titanium dioxide for penetration in concrete structures to reduce pollutants |
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| EP0857770B1 (en) * | 1997-02-06 | 2004-09-22 | Shin-Etsu Chemical Co., Ltd. | Coating compositions, hydrophilic films, and hydrophilic film-coated articles |
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1999
- 1999-08-05 FR FR9910187A patent/FR2797262B1/en not_active Expired - Fee Related
-
2000
- 2000-08-03 MY MYPI20003538A patent/MY131809A/en unknown
- 2000-08-04 HU HU0203085A patent/HUP0203085A2/en unknown
- 2000-08-04 JP JP2001515267A patent/JP2003506307A/en active Pending
- 2000-08-04 AU AU68507/00A patent/AU6850700A/en not_active Abandoned
- 2000-08-04 CZ CZ2002442A patent/CZ2002442A3/en unknown
- 2000-08-04 EP EP00956628A patent/EP1204621A1/en not_active Withdrawn
- 2000-08-04 TW TW89115730A patent/TWI238153B/en not_active IP Right Cessation
- 2000-08-04 PL PL353136A patent/PL202747B1/en not_active IP Right Cessation
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- 2000-08-04 BR BR0012983A patent/BR0012983B1/en not_active IP Right Cessation
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Non-Patent Citations (1)
| Title |
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Also Published As
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| US6919104B2 (en) | 2005-07-19 |
| TWI238153B (en) | 2005-08-21 |
| AU6850700A (en) | 2001-03-05 |
| CZ2002442A3 (en) | 2003-01-15 |
| MY131809A (en) | 2007-09-28 |
| FR2797262B1 (en) | 2001-12-07 |
| PL202747B1 (en) | 2009-07-31 |
| JP2003506307A (en) | 2003-02-18 |
| BR0012983B1 (en) | 2012-07-24 |
| WO2001010793A1 (en) | 2001-02-15 |
| PL353136A1 (en) | 2003-10-20 |
| HUP0203085A2 (en) | 2002-12-28 |
| US20020182334A1 (en) | 2002-12-05 |
| BR0012983A (en) | 2002-04-23 |
| FR2797262A1 (en) | 2001-02-09 |
| AR025039A1 (en) | 2002-11-06 |
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| 18D | Application deemed to be withdrawn |
Effective date: 20050302 |