EP1204621A1 - Procede de traitement de materiau architectural - Google Patents

Procede de traitement de materiau architectural

Info

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Withdrawn
Application number
EP00956628A
Other languages
German (de)
English (en)
French (fr)
Inventor
Christian Marzolin
Roman Gerusz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Materiaux de Construction SAS
Original Assignee
Saint Gobain Materiaux de Construction SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Saint Gobain Materiaux de Construction SAS filed Critical Saint Gobain Materiaux de Construction SAS
Publication of EP1204621A1 publication Critical patent/EP1204621A1/fr
Withdrawn legal-status Critical Current

Links

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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Paints Or Removers (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
EP00956628A 1999-08-05 2000-08-04 Procede de traitement de materiau architectural Withdrawn EP1204621A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9910187 1999-08-05
FR9910187A FR2797262B1 (fr) 1999-08-05 1999-08-05 Procede de traitement de materiau architectural
PCT/FR2000/002255 WO2001010793A1 (fr) 1999-08-05 2000-08-04 Procede de traitement de materiau architectural

Publications (1)

Publication Number Publication Date
EP1204621A1 true EP1204621A1 (fr) 2002-05-15

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00956628A Withdrawn EP1204621A1 (fr) 1999-08-05 2000-08-04 Procede de traitement de materiau architectural

Country Status (13)

Country Link
US (1) US6919104B2 (hu)
EP (1) EP1204621A1 (hu)
JP (1) JP2003506307A (hu)
AR (1) AR025039A1 (hu)
AU (1) AU6850700A (hu)
BR (1) BR0012983B1 (hu)
CZ (1) CZ2002442A3 (hu)
FR (1) FR2797262B1 (hu)
HU (1) HUP0203085A2 (hu)
MY (1) MY131809A (hu)
PL (1) PL202747B1 (hu)
TW (1) TWI238153B (hu)
WO (1) WO2001010793A1 (hu)

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AU6850700A (en) 2001-03-05
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CZ2002442A3 (cs) 2003-01-15
PL353136A1 (en) 2003-10-20
FR2797262A1 (fr) 2001-02-09
BR0012983B1 (pt) 2012-07-24
WO2001010793A1 (fr) 2001-02-15
MY131809A (en) 2007-09-28
PL202747B1 (pl) 2009-07-31
AR025039A1 (es) 2002-11-06
BR0012983A (pt) 2002-04-23
FR2797262B1 (fr) 2001-12-07
JP2003506307A (ja) 2003-02-18
TWI238153B (en) 2005-08-21
US20020182334A1 (en) 2002-12-05

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