ITFI20120131A1 - COMPOSITION AND WATERPROOFING TREATMENT - Google Patents

COMPOSITION AND WATERPROOFING TREATMENT Download PDF

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ITFI20120131A1
ITFI20120131A1 IT000131A ITFI20120131A ITFI20120131A1 IT FI20120131 A1 ITFI20120131 A1 IT FI20120131A1 IT 000131 A IT000131 A IT 000131A IT FI20120131 A ITFI20120131 A IT FI20120131A IT FI20120131 A1 ITFI20120131 A1 IT FI20120131A1
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Italy
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composition according
monomers
fluorinated polymers
fluoroalkene
fluoroalkyl
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IT000131A
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Italian (it)
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Alessio Benelli
Simona Benelli
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Benelli S R L
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Priority to IT000131A priority Critical patent/ITFI20120131A1/en
Publication of ITFI20120131A1 publication Critical patent/ITFI20120131A1/en

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    • 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
    • C04B41/46—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 organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4838—Halogenated polymers
    • C04B41/4842—Fluorine-containing polymers
    • C04B41/4846—Perfluoro-compounds
    • 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
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/83—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium

Description

Descrizione Description

“COMPOSIZIONE E TRATTAMENTO IMPERMEABILIZZANTE†⠀ œCOMPOSITION AND WATERPROOF TREATMENTâ €

SETTORE DELL’INVENZIONE SECTOR OF INVENTION

La presente invenzione riguarda una composizione ed il suo uso per impermeabilizzare un materiale edile di rivestimento per edilizia in particolare materiale edile poroso come mattoni, piastrelle in cotto, e simili. The present invention relates to a composition and its use for waterproofing a building facing building material, in particular porous building material such as bricks, terracotta tiles, and the like.

ANTEFATTO DELL’INVENZIONE BACKGROUND OF THE INVENTION

Il trattamento di materiale edile di rivestimento per edilizia à ̈ necessario per conferire alle pavimentazioni, ed in genere ai rivestimenti a piastrella e simili, caratteristiche di resistenza all’acqua e anti macchia, ed in particolare agli agenti atmosferici nel caso di rivestimenti per esterno. The treatment of building covering material for building is necessary to give the flooring, and in general to the tile coverings and the like, characteristics of resistance to water and anti-stain, and in particular to atmospheric agents in the case of outdoor coverings. .

Attualmente, i sistemi per il rivestimento risultano generalmente non del tutto soddisfacenti per durata e persistenza dell’efficacia impermeabilizzante. Currently, coating systems are generally not entirely satisfactory in terms of duration and persistence of the waterproofing effectiveness.

In particolare à ̈ sentita l’esigenza di una composizione e di un metodo per impermeabilizzare materiale edile poroso come le piastrelle in cotto ed i mattoni a base di argilla da rivestimento. Per piastrelle in cotto si intendono materiali da rivestimento a base di argilla con percentuali di silicio. In particular, the need is felt for a composition and a method for waterproofing porous building material such as terracotta tiles and clay-based bricks for facing. Terracotta tiles are clay-based covering materials with percentages of silicon.

Un obiettivo della presente invenzione à ̈ fornire una composizione che conferisca buone caratteristiche idro-, oleorepellenti ai materiali trattati e un metodo semplice, economico, ecocompatibile, resistente ai lavaggi, per impermeabilizzare i materiali trattati senza alterarne le caratteristiche estetiche originali. An objective of the present invention is to provide a composition that confers good hydro-, oil-repellent characteristics to the treated materials and a simple, economical, eco-compatible, washing-resistant method for waterproofing the treated materials without altering their original aesthetic characteristics.

SOMMARIO DELL’INVENZIONE SUMMARY OF THE INVENTION

La presente invenzione riguarda un metodo per impermeabilizzare un materiale edile poroso, ad esempio materiale a base di argilla,: The present invention relates to a method for waterproofing a porous building material, for example clay-based material:

a. bagnatura del materiale edile, ad esempio per immersione, con una composizione impermeabilizzante in forma di dispersione acquosa ad una concentrazione del 5-40%, comprendente monomeri, polimeri fluorurati aventi una catena fluoroalchilica o fluoroalchenica C6-C21, paraffine con un punto di fusione compreso tra 0 e 80 °C e zirconil derivati; to. wetting of the building material, for example by immersion, with a waterproofing composition in the form of an aqueous dispersion at a concentration of 5-40%, comprising monomers, fluorinated polymers having a fluoroalkyl or fluoroalkene chain C6-C21, paraffins with a melting point including between 0 and 80 ° C and zirconyl derivatives;

b. asciugatura del materiale edile, b. drying of the building material,

c. eventualmente in contemporanea alla fase di asciugatura, riscaldamento superficiale del materiale edile ad una temperatura maggiore di 40 °C per un tempo indicativamente superiore ad un minuto. c. possibly at the same time as the drying phase, surface heating of the building material at a temperature higher than 40 ° C for a time indicatively greater than one minute.

In un ulteriore aspetto la presente invenzione riguarda un materiale edile da rivestimento trattato con la composizione impermeabilizzante sopra descritta. In a further aspect, the present invention relates to a building covering material treated with the waterproofing composition described above.

In un ulteriore aspetto la presente invenzione riguarda una composizione impermeabilizzante in forma di dispersione acquosa ad una concentrazione del 5-40%, comprendente monomeri, polimeri fluorurati aventi una catena fluoroalchilica o fluoroalchenica C6-C21, paraffine con un punto di fusione compreso tra 0 e 80 °C e zirconil derivati. In a further aspect, the present invention relates to a waterproofing composition in the form of an aqueous dispersion at a concentration of 5-40%, comprising monomers, fluorinated polymers having a fluoroalkyl or fluoroalkene chain C6-C21, paraffins with a melting point between 0 and 80 ° C and zirconyl derivatives.

Sorprendentemente, la composizione impermeabilizzante dell’invenzione conferisce al materiale edile trattato idro-, oleorepellenza e resistenza alle macchie, e consente al materiale edile trattato di mantenere le proprie caratteristiche, quali, per esempio colore e traspirabilità. La composizione impermeabilizzante dell’invenzione à ̈ utilizzata in forma di dispersione acquosa, evitando l’uso di solventi chimici, con i conseguenti problemi di smaltimento, tossicità ambientale, precauzioni particolari per il personale addetto o attrezzature e macchinari particolari. Surprisingly, the waterproofing composition of the invention gives the treated building material water-, oil-repellent and stain resistance, and allows the treated building material to maintain its characteristics, such as, for example, color and breathability. The waterproofing composition of the invention is used in the form of an aqueous dispersion, avoiding the use of chemical solvents, with the consequent problems of disposal, environmental toxicity, special precautions for the staff or special equipment and machinery.

DESCRIZIONE DETTAGLIATA DELL’INVENZIONE DETAILED DESCRIPTION OF THE INVENTION

Tutti i termini utilizzati nella presente domanda, salvo indicazioni contrarie, devono essere compresi nel loro comune significato come conosciuti nell'arte. Altre definizioni più specifiche per alcuni termini, come utilizzati in questa domanda, sono messe in evidenza più avanti e si applicano costantemente per tutta la descrizione e le rivendicazioni, a meno che una diversa definizione fornisca esplicitamente una definizione più ampia. All the terms used in the present application, unless otherwise indicated, must be understood in their common meaning as known in the art. Other more specific definitions for some terms, as used in this question, are highlighted below and apply consistently throughout the description and claims, unless a different definition explicitly provides a broader definition.

Il termine “bagnatura†si riferisce al trattamento del materiale edile mediante immersione in una soluzione, emulsione, dispersione acquosa contenente la composizione dell’invenzione. I termini “catena fluoroalchilica o fluoroalchenica C6-C21†si riferiscono a catene alchiliche o alcheniche, con uno o più doppi legami, lineari, ramificate, cicliche o loro combinazioni, aventi almeno un atomo di H sostituito da un atomo di F, contenenti da 6 a 21 atomi di carbonio, preferibilmente, e da 6 a 14 atomi di carbonio (C6-C14). Esempi includono, senza limitazione, perfluoroesano, perfluoroeptano, perfluoroottano, perfluorononano, perfluorodecano, perfluoroundecano, perfluorododecano, perfluoroesene, perfluoroeptene, perfluoroottene, perfluorononene, perfluorodecene, perfluoro n-ottiletilene, perfluoroottil acrilato, e simili. The term â € œwettingâ € refers to the treatment of the building material by immersion in a solution, emulsion, aqueous dispersion containing the composition of the invention. The terms â € œC6-C21 fluoroalkyl or fluoroalkene chainâ € refer to alkyl or alkenic chains, with one or more double bonds, linear, branched, cyclic or combinations thereof, having at least one H atom replaced by an F atom, containing from 6 to 21 carbon atoms, preferably, and from 6 to 14 carbon atoms (C6-C14). Examples include, but are not limited to, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluorooctene, perfluorononene, perfluorodecene, perfluoro n-octyletylene, perfluorodecene, perfluoro n-octyletylene, perfluorodecene, perfluoro n-octyletylene, perfluorooctyl and perfluoro-like acryl.

I termini “monomeri fluorurati†, “polimeri fluorurati†si riferiscono a monomeri, omopolimeri, copolimeri, compresi per esempio, terpolimeri, tetrapolimeri, e termini superiori, in cui la gran parte dei legami chimici presenti à ̈ di tipo C-F e aventi una catena fluoroalchilica o fluoroalchenica C6-C21, preferibilmente C6-C14. È evidente che i monomeri, polimeri fluorurati possono includere parti che non sono fluorurate. I monomeri, polimeri fluorurati dell’invenzione comprendono monomeri, polimeri perfluorurati. Idrogeno, altri alogeni e altri elementi possono essere presenti in minor quantità. Monomeri, polimeri fluorurati sono noti all’esperto del ramo, ed includono, ma non sono limitati a, composti fluorurati quali C6-C21 alcoli o acidi che hanno reagito con composti chimici appropriati per formare esteri, amidi o polimeri, vinil polimeri, quali acrilati, metacrilati, e simili. Esempi includono, senza limitazione, perfluoroesano, perfluoroeptano, perfluoroottano, perfluorononano, perfluorodecano, perfluoroundecano, perfluorododecano, perfluoroesene, perfluoroeptene, perfluoroottene, perfluorononene, perfluorodecene, perfluoro n-ottiletilene, perfluoroottil acrilato, e simili. The terms â € œfluorinated monomersâ €, â € œfluorinated polymersâ € refer to monomers, homopolymers, copolymers, including for example, terpolymers, tetrapolymers, and higher terms, in which most of the chemical bonds present are of type C-F and having a C6-C21 fluoroalkyl or fluoroalkene chain, preferably C6-C14. It is evident that the monomers, fluorinated polymers can include parts that are not fluorinated. The monomers, fluorinated polymers of the invention include monomers, perfluorinated polymers. Hydrogen, other halogens and other elements may be present in smaller quantities. Monomers, fluorinated polymers are known to those skilled in the art, and include, but are not limited to, fluorinated compounds such as C6-C21 alcohols or acids which have reacted with appropriate chemical compounds to form esters, starches or polymers, vinyl polymers, such as acrylates, methacrylates, and the like. Examples include, but are not limited to, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluorooctene, perfluorononene, perfluorodecene, perfluoro n-octyletylene, perfluorodecene, perfluoro n-octyletylene, perfluorodecene, perfluoro n-octyletylene, perfluorooctyl and perfluoro-like acryl.

Preferibilmente i monomeri, polimeri fluorurati sono perfluoroesano, perfluoroesene, perfluoroottene, perfluorodecene, perfluoro n-ottiletilene, perfluoroottil acrilato. Preferably the monomers, fluorinated polymers are perfluorohexane, perfluorohexene, perfluorooctene, perfluorodecene, perfluoro n-octylethylene, perfluorooctyl acrylate.

Sono venduti, per esempio, con i nomi commerciali Draig 300<®>(Bozzetto Group), REAPRET® FCT (Bozzetto Group), QUECOPHOB PC 6 (Thor), Unidyne TG-5543 (Daikin) e sono caratterizzati più per le loro proprietà che per la loro composizione chimica. I monomeri, polimeri fluorurati dell’invenzione hanno un punto di fusione compreso tra 30 e 80 °C, preferibilmente 30-60 °C, più preferibilmente 40-50 °C. Sono esenti da composti tossici, quali nonilfenoli (APEO), acido perfluoroottanoico (PFOA) e perfluoroottano sulfonato (PFOS). They are sold, for example, under the trade names Draig 300 <®> (Bozzetto Group), REAPRET® FCT (Bozzetto Group), QUECOPHOB PC 6 (Thor), Unidyne TG-5543 (Daikin) and are characterized more by their properties and for their chemical composition. The monomers, fluorinated polymers of the invention have a melting point between 30 and 80 ° C, preferably 30-60 ° C, more preferably 40-50 ° C. They are free from toxic compounds, such as nonylphenols (APEO), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS).

Preferibilmente, i monomeri e polimeri fluorurati dell’invenzione sono dispersi in una soluzione acquosa (si veda in generale Fluorine-Containing Polymers, Encyclopedia of Polymer Science & Technology, pp.179-203, Interscience, 1967); preferibilmente a diluizioni comprese tra 5-40%; più preferibilmente a diluizioni comprese tra 20-30%; ancor più preferibilmente a diluizioni del 30% in peso. Preferably, the fluorinated monomers and polymers of the invention are dispersed in an aqueous solution (see in general Fluorine-Containing Polymers, Encyclopedia of Polymer Science & Technology, pp.179-203, Interscience, 1967); preferably at dilutions comprised between 5-40%; more preferably at dilutions comprised between 20-30%; even more preferably at dilutions of 30% by weight.

I monomeri, polimeri fluorurati dell’invenzione conferiscono alla soluzione acquosa in cui sono dispersi un pH compreso tra 1 e 6, preferibilmente 2 - 5, ancor più preferibilmente 2.5 Il termine “paraffina†si riferisce a qualunque idrocarburo saturo, comprendendo normali paraffine, paraffine ramificate, iso- paraffine, cicloparaffine, microcere e loro miscele. Le paraffine dell’invenzione hanno un punto di fusione compreso tra 0 e 80 °C, più preferibilmente 20-60 °C, ancor più preferibilmente 50-60 °C. The monomers, fluorinated polymers of the invention give the aqueous solution in which they are dispersed a pH between 1 and 6, preferably 2 - 5, even more preferably 2.5 The term â € œparaffinâ € refers to any saturated hydrocarbon, including normal paraffins , branched paraffins, isoparaffins, cycloparaffins, microcers and their mixtures. The paraffins of the invention have a melting point between 0 and 80 ° C, more preferably 20-60 ° C, even more preferably 50-60 ° C.

Qualunque zirconil derivato noto all’esperto del ramo, può essere usato nella presente invenzione. Zirconil derivati comprendono, per esempio, zirconio ossido, zirconio idrossido, zirconio solfato, zirconio silicato; sali di zirconio, per esempio, zirconio nitrato, zirconio disolfato, zirconio fosfato, sali di zirconio con acidi grassi contenenti nella loro catena 2-21 atomi di carbonio, per esempio zirconio stearato; alogenuri di zirconio, per esempio zirconio cloruro, zirconio fluoruro, zirconio tetrafluoruro; esteri di zirconio, per esempio, zirconio acetato, zirconio tetraacetato, zirconio propionato, zirconio butilato, zirconio valerato, zirconio esanato, zirconio eptanato, zirconio octoato, zirconio stearato; zirconio alcossidi, per esempio zirconio tetrapropossido, zirconio tetrabutossido; alchil zirconati e zirconati polimerici con gruppi alchilici aventi 2-21 atomi di carbonio nella catena; e simili. Any zirconyl derivative known to the person skilled in the art can be used in the present invention. Zirconyl derivatives include, for example, zirconium oxide, zirconium hydroxide, zirconium sulfate, zirconium silicate; zirconium salts, for example, zirconium nitrate, zirconium disulfate, zirconium phosphate, zirconium salts with fatty acids containing in their chain 2-21 carbon atoms, for example zirconium stearate; zirconium halides, for example zirconium chloride, zirconium fluoride, zirconium tetrafluoride; zirconium esters, for example, zirconium acetate, zirconium tetraacetate, zirconium propionate, zirconium butylate, zirconium valerate, zirconium hexanate, zirconium heptanate, zirconium octoate, zirconium stearate; zirconium alkoxides, for example zirconium tetrapropoxide, zirconium tetrabutoxide; alkyl zirconates and polymeric zirconates with alkyl groups having 2-21 carbon atoms in the chain; and similar.

Gli zirconil derivati hanno la funzione di fissare la paraffina. Qualunque metallo derivato noto all’esperto del ramo per fissare la paraffina, può essere usato nella presente invenzione. The zirconyl derivatives have the function of fixing the paraffin. Any derivative metal known to one skilled in the art to fix paraffin can be used in the present invention.

Preferibilmente paraffine e zirconil derivato/derivati sono preventivamente dispersi in una soluzione acquosa, diluiti in modo opportuno a secondo dell’esigenza, preferibilmente a diluizioni comprese tra 5-40%; più preferibilmente a diluizioni comprese tra 20-30%; ancor più preferibilmente a diluizioni del 30% in peso. La dispersione acquosa di paraffine e zirconil derivato/derivati possiede un pH compreso tra 1 e 5, preferibilmente 2 - 5, ancor più preferibilmente 2.5 - 4.0. La concentrazione totale di zirconio metallico in tale dispersione à ̈ compresa tra 0.01-3%, preferibilmente 0.1-1%, ancor più preferibilmente 0.15-0.18%. Miscele di questo tipo sono presenti in commercio, per esempio con il nome commerciale Draig NSZ<®>, Draig Z<®>(Bozzetto Group), Contraqua PZ (Thor). Preferably, paraffins and zirconyl derivatives / derivatives are previously dispersed in an aqueous solution, diluted appropriately according to requirements, preferably at dilutions ranging from 5-40%; more preferably at dilutions comprised between 20-30%; even more preferably at dilutions of 30% by weight. The aqueous dispersion of paraffins and zirconyl derivatives / derivatives has a pH between 1 and 5, preferably 2 - 5, even more preferably 2.5 - 4.0. The total concentration of metallic zirconium in this dispersion is comprised between 0.01-3%, preferably 0.1-1%, even more preferably 0.15-0.18%. Mixtures of this type are commercially available, for example under the trade name Draig NSZ <®>, Draig Z <®> (Bozzetto Group), Contraqua PZ (Thor).

Il termine “acidi grassi†si riferisce ad acidi monocarbossilici alifatici saturi o insaturi, ramificati o lineari, contenenti da 4 a 32 atomi di carbonio, preferibilmente da 4 a 22 atomi di carbonio, più preferibilmente da 6 a 18 atomi di carbonio. Esempi di acidi grassi includono, senza limitazione, acidi monocarbossilici alifatici saturi, per esempio acido butirrico, valerico, caproico, enantico, caprilico, pelargonico, caprinico, undecanoico, laurico, tridecanoico, miristico, pentadecanoico, palmitico, margarico, isoeptadecanoico, stearico, isostearico, nonadecanoico, arachidico, beenico, tricosanoico, lignocerico, cerotico, montanico, melissico, laceroico, e simili; acidi monocarbossilici alifatici insaturi monoinsaturi, per esempio acido miristoleico, undecilenico, palmitoleico, oleico, petroselinico, eptadecenoico, elaidico, vaccenico, gadoleico, cetoleico, erucico, nervonico; o poliinsaturi, per esempio acido linoleico, linolenico, stearidonico, arachidonico, timnodonico, clupanodonico, cervonico, e simili. Gli acidi grassi possono essere facoltativamente sostituiti. Esempi di acidi grassi sostituiti includono, senza limitazione, acido ricinoleico, idrossistearico, mercaptoundecanoico, metiltetradecanoico, metilpentadecanoico, e simili. Il termine “circa†comprende l’ambito dell’errore sperimentale che può avvenire in una misurazione. The term â € œfatty acidsâ € refers to saturated or unsaturated, branched or linear aliphatic monocarboxylic acids, containing from 4 to 32 carbon atoms, preferably from 4 to 22 carbon atoms, more preferably from 6 to 18 carbon atoms. Examples of fatty acids include, without limitation, saturated aliphatic monocarboxylic acids, for example butyric, valeric, caproic, enanthic, caprylic, pelargonic, caprinic, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, margaric, isoheptadecanoic, stearic, isostearic acids. , nonadecanoic, arachidic, behenic, tricosanoic, lignoceric, cerotic, montanic, melissic, laceroic, and the like; monounsaturated unsaturated aliphatic monocarboxylic acids, for example myristoleic, undecylenic, palmitoleic, oleic, petroselinic, heptadecenoic, elaidic, vaccenic, gadoleic, cetoleic, erucic, nervous acids; or polyunsaturated, for example linoleic, linolenic, stearidonic, arachidonic, timnodonic, clupanodonic, cervonic, and the like. The fatty acids can optionally be substituted. Examples of substituted fatty acids include, without limitation, ricinoleic, hydroxystearic, mercaptoundecanoic, methyltetradecanoic, methylpentadecanoic, and the like. The term "about" encompasses the scope of the experimental error that can occur in a measurement.

La composizione dell’invenzione comprende monomeri, polimeri fluorurati aventi una catena fluoroalchilica o fluoroalchenica C6-C21, paraffine con un punto di fusione compreso tra 0 e 80 °C e zirconil derivati. Altri additivi, quali per esempio, resine, coloranti, profumi, conservanti, battericidi, possono essere aggiunti a tale composizione. La composizione dell’invenzione à ̈ usata in forma di dispersione acquosa ad una concentrazione in peso del 5-40%, miscelando i monomeri, polimeri fluorurati facoltativamente pre-dispersi in acqua e le paraffine e zirconil derivato/derivati facoltativamente pre-dispersi in acqua. La composizione dell’invenzione à ̈ diluita con acqua in modo opportuno a secondo dell’esigenza e/o del materiale edile da trattare. Se necessario, si aggiusta il pH ai valori desiderati. Preferibilmente, la composizione dell’invenzione à ̈ diluita in dispersione acquosa. Tale dispersione à ̈ stabile, soprattutto in fase di stoccaggio e in fase di lavorazione e ha buone proprietà fissanti. Può essere ulteriormente diluita fino al livello desiderato e viene applicata al materiale edile che deve essere trattato con qualunque metodo noto all’esperto del ramo, per esempio, per immersione in un bagno (“bagnatura†), spray, rullatura, spalmatura (che potra' essere fatta a mano con pennello, spray, rullo, etc etc) e trattamento superficiale dopo la posa dei materiali edili. Preferibilmente, il materiale edile da trattare à ̈ immerso nella composizione dell’invenzione fino ad assorbimento completo ed uniforme per circa 1-5 min. La rimozione della dispersione in eccesso à ̈ effettuata con qualunque metodo noto all’esperto del ramo. La dispersione recuperata, può essere interamente riutilizzata per ulteriori cicli di lavorazione. Il materiale edile così trattato risulta impermeabilizzato dopo averlo asciugato completamente anche a temperatura ambiente o al sole e successivo o contemporaneo riscaldamento superficiale. Per impermeabilizzare il materiale edile trattato bastano temperature di riscaldamento maggiori di 40°C e preferibilmente comprese nel range 40-70 °C. The composition of the invention comprises monomers, fluorinated polymers having a C6-C21 fluoroalkyl or fluoroalkene chain, paraffins with a melting point between 0 and 80 ° C and zirconyl derivatives. Other additives, such as, for example, resins, dyes, perfumes, preservatives, bactericides, can be added to this composition. The composition of the invention is used in the form of an aqueous dispersion at a weight concentration of 5-40%, mixing the monomers, optionally pre-dispersed fluorinated polymers in water and the paraffins and optionally pre-dispersed zirconyl derivatives / derivatives in water. The composition of the invention is diluted with water in an appropriate way according to the need and / or the building material to be treated. If necessary, the pH is adjusted to the desired values. Preferably, the composition of the invention is diluted in aqueous dispersion. This dispersion is stable, especially during storage and processing, and has good fixing properties. It can be further diluted to the desired level and is applied to the building material which must be treated with any method known to the skilled in the art, for example, by immersion in a bath (â € œwettingâ €), spray, rolling, spreading ( which can be done by hand with brush, spray, roller, etc etc) and surface treatment after the laying of building materials. Preferably, the building material to be treated is immersed in the composition of the invention until completely and uniformly absorbed for about 1-5 min. The removal of the excess dispersion is carried out by any method known to the skilled in the art. The recovered dispersion can be entirely reused for further processing cycles. The building material treated in this way is waterproofed after having dried it completely even at room temperature or in the sun and subsequent or simultaneous surface heating. To waterproof the treated building material, heating temperatures higher than 40 ° C and preferably in the range 40-70 ° C are sufficient.

La bagnatura con la composizione dell’invenzione può avvenire in diverse fasi di lavorazione di un materiale edile preferibilmente dopo eventuali fasi cottura in forno a temperatura elevata. The wetting with the composition of the invention can take place in different stages of processing a building material, preferably after any stages of firing in an oven at a high temperature.

Preferibilmente, la composizione dell’invenzione à ̈ diluita fino ad avere una concentrazione in peso del 20-50%, più preferibilmente 25-45%, ancor più preferibilmente 35-40%. Preferably, the composition of the invention is diluted until it has a weight concentration of 20-50%, more preferably 25-45%, even more preferably 35-40%.

Il processo della presente invenzione consente di impermeabilizzare un materiale edile in modo uniforme, omogeneo, estremamente semplice e rapido, in condizioni molto blande, senza ricorrere a temperature elevate. L’utilizzo di temperature blande necessarie per attivare la composizione impermeabilizzante dell’invenzione contribuisce a lasciare inalterate le caratteristiche proprie del materiale edile trattato e contribuisce ad abbattere i costi di produzione. The process of the present invention allows waterproofing a building material in a uniform, homogeneous, extremely simple and rapid way, in very mild conditions, without resorting to high temperatures. The use of mild temperatures necessary to activate the waterproofing composition of the invention helps to leave the characteristics of the building material treated unaltered and helps to reduce production costs.

Il processo dell’invenzione avviene in soluzione acquosa, evitando quindi l’uso di solventi, solventi tossici, o solventi ambientalmente inaccettabili, che richiederebbero sempre uno smaltimento. Il processo della presente invenzione non richiede nessuna attrezzatura, nessun macchinario particolare, nessun macchinario chiuso. Le sostanze utilizzate non sono tossiche, non creano irritazione e sono facilmente smaltibili. The process of the invention takes place in an aqueous solution, thus avoiding the use of solvents, toxic solvents, or environmentally unacceptable solvents, which would always require disposal. The process of the present invention requires no equipment, no particular machinery, no closed machinery. The substances used are not toxic, do not create irritation and are easily disposed of.

In un ulteriore aspetto, la presente invenzione riguarda i materiali trattati con la composizione impermeabilizzante dell’invenzione, quali mattoni a base di argilla, piastrelle in cotto e simili. Il processo della presente invenzione consente di impermeabilizzare un materiale edile senza alterare le sue caratteristiche: i colori rimangono inalterati, sono resistenti alla luce, non sbiadiscono; materiali bianchi o chiari non ingialliscono, le caratteristiche meccaniche permangono immutate. In a further aspect, the present invention relates to the materials treated with the waterproofing composition of the invention, such as clay-based bricks, terracotta tiles and the like. The process of the present invention makes it possible to waterproof a building material without altering its characteristics: the colors remain unaltered, they are resistant to light, they do not fade; white or light materials do not yellow, the mechanical characteristics remain unchanged.

La composizione impermeabilizzante dell’invenzione copre in modo omogeneo il materiale edile trattato e può essere applicata sul materiale edile grezzo o sul prodotto finito, ottenendo sempre ottimi livelli di impermeabilizzazione. The waterproofing composition of the invention homogeneously covers the treated building material and can be applied on the raw building material or on the finished product, always obtaining excellent waterproofing levels.

L’impermeabilizzazione permane anche dopo ripetuti lavaggi ad esempio per esposizione a pioggia ,. In caso di lavaggio del materiale edile, per la “riattivazione†della composizione impermeabilizzante à ̈ sufficiente l’asciugatura naturale o un ulteriore riscaldamento superficiale The waterproofing remains even after repeated washing, for example due to exposure to rain,. In case of washing of the building material, natural drying or further surface heating is sufficient for the â € œreactivationâ € of the waterproofing composition.

Il materiale edile trattato presenta ottime caratteristiche idro- oleorepellenti, ed à ̈ resistente alle macchie The treated building material has excellent water and oil repellent characteristics, and is resistant to stains

Sebbene la presente invenzione sia stata descritta nei suoi aspetti caratteristici, modifiche ed equivalenti che sono evidenti all’esperto del ramo sono incluse nella presente invenzione. Di seguito, la presente invenzione sarà illustrata per mezzo di alcuni esempi, che non devono essere visti come limitanti la portata dell'invenzione. Although the present invention has been described in its characteristic aspects, modifications and equivalents which are apparent to one skilled in the art are included in the present invention. Hereinafter, the present invention will be illustrated by means of some examples, which are not to be seen as limiting the scope of the invention.

Esempi Examples

Preparazione della miscela C Preparation of the mixture C

Una dispersione di polimeri fluorurati (Draig 300<®>conc., Bozzetto Group) in acqua e una miscela di paraffine e zirconil derivati (Draig NSZ<®>, Bozzetto Group) sono miscelate in rapporto 1:1 a temperatura ambiente e diluite con acqua (miscela di polimeri fluorurati, paraffine e zirconil derivati 13.40% / acqua 86.60%). La miscela così ottenuta può essere stoccata. A dispersion of fluorinated polymers (Draig 300 <®> conc., Bozzetto Group) in water and a mixture of paraffin and zirconyl derivatives (Draig NSZ <®>, Bozzetto Group) are mixed in a 1: 1 ratio at room temperature and diluted with water (mixture of fluorinated polymers, paraffins and zirconyl derivatives 13.40% / water 86.60%). The mixture thus obtained can be stored.

Trattamento del materiale edile Treatment of building material

Si bagna il materiale edile da trattare con la miscela dell’Esempio 1 fino ad assorbimento superficiale ed uniforme (1-5 min). Si elimina eventualmente la miscela acquosa in eccesso. Si asciuga completamente il materiale edile trattato ad esempio al sole, si riscalda superficialmente il materiale edile ad una temperatura maggiore di 40 C preferibilmente di (40-70 °C) per 1-5 min. The building material to be treated is wet with the mixture of Example 1 until superficial and uniform absorption (1-5 min). The excess aqueous mixture is eventually eliminated. The building material treated for example in the sun is completely dried, the building material is heated on the surface to a temperature higher than 40 C, preferably (40-70 ° C) for 1-5 min.

Claims (16)

Rivendicazioni 1. Composizione impermeabilizzante comprendente monomeri, polimeri fluorurati aventi una catena fluoroalchilica o fluoroalchenica C6-C21, paraffine con un punto di fusione compreso tra 0 e 80 °C e zirconil derivati. Claims 1. Waterproofing composition comprising monomers, fluorinated polymers having a fluoroalkyl or fluoroalkene chain C6-C21, paraffins with a melting point between 0 and 80 ° C and zirconyl derivatives. 2. Composizione, secondo la rivendicazione 1, in forma di dispersione acquosa ad una concentrazione in peso compresa tra 5-40%. 2. Composition according to claim 1, in the form of an aqueous dispersion at a concentration by weight of between 5-40%. 3. Composizione, secondo la rivendicazione 2, in cui la concentrazione della dispersione acquosa à ̈ del 10-15%, preferibilmente 13-14%. 3. Composition according to claim 2, wherein the concentration of the aqueous dispersion is 10-15%, preferably 13-14%. 4. Composizione secondo la rivendicazione 1, in cui i monomeri, polimeri fluorurati hanno una catena fluoroalchilica o fluoroalchenica C6-C7. 4. Composition according to claim 1, wherein the monomers, fluorinated polymers have a C6-C7 fluoroalkyl or fluoroalkene chain. 5. Composizione secondo la rivendicazione 1, in cui i monomeri, polimeri fluorurati hanno una catena fluoroalchilica o fluoroalchenica C8. 5. Composition according to claim 1, wherein the monomers, fluorinated polymers have a C8 fluoroalkyl or fluoroalkene chain. 6. Composizione secondo la rivendicazione 2, in cui i monomeri, polimeri fluorurati hanno una catena fluoroalchilica o fluoroalchenica C6-C7. 6. Composition according to claim 2, wherein the monomers, fluorinated polymers have a C6-C7 fluoroalkyl or fluoroalkene chain. 7. Composizione secondo la rivendicazione 2, in cui i monomeri, polimeri fluorurati hanno una catena fluoroalchilica o fluoroalchenica C8. 7. Composition according to claim 2, wherein the monomers, fluorinated polymers have a C8 fluoroalkyl or fluoroalkene chain. 8. Composizione secondo le rivendicazioni 1-7, in cui i monomeri, polimeri fluorurati sono perfluoroesano, perfluoroeptano, perfluoroottano, perfluorononano, perfluorodecano, perfluoroundecano, perfluorododecano, perfluoroesene, perfluoroeptene, perfluoro nottiletilene, perfluoroottil acrilato, perfluoroottene, perfluorononene, perfluorodecene; più preferibilmente perfluoroesano, perfluoroesene, perfluoroottene, perfluorodecene, perfluoro n-ottiletilene, perfluoroottil acrilato. 8. Composition according to claims 1-7, wherein the monomers, fluorinated polymers are perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluoro noctylethylene, perfluorooctyl acrylate, perfluoroctyl acrylate, perfluoroctyl acrylate, perfluorooctyl acrylate; more preferably perfluorohexane, perfluorohexene, perfluorooctene, perfluorodecene, perfluoro n-octyletylene, perfluorooctyl acrylate. 9. Composizione secondo la rivendicazione 1, in cui i monomeri, polimeri fluorurati hanno un punto di fusione compreso tra 30 e 80 °C, preferibilmente 30-60 °C, più preferibilmente 40-50 °C; sono facoltativamente preventivamente dispersi in una soluzione acquosa a diluizioni in peso comprese tra 5-40%; più preferibilmente 20-30%; ancor più preferibilmente a diluizioni del 30% in peso e conferiscono alla soluzione acquosa in cui sono dispersi un pH compreso tra 1 e 6, preferibilmente 2-5, ancor più preferibilmente 2.5-4.5. 9. Composition according to claim 1, wherein the monomers, fluorinated polymers have a melting point comprised between 30 and 80 ° C, preferably 30-60 ° C, more preferably 40-50 ° C; they are optionally dispersed in advance in an aqueous solution at weight dilutions ranging from 5-40%; more preferably 20-30%; even more preferably at dilutions of 30% by weight and give the aqueous solution in which they are dispersed a pH between 1 and 6, preferably 2-5, even more preferably 2.5-4.5. 10. Composizione secondo la rivendicazione 1, in cui: a. le paraffine hanno un punto di fusione compreso tra 20-60 °C, preferibilmente 50 b. le paraffine e zirconil derivato/derivati sono facoltativamente preventivamente disperse in acqua a diluizioni comprese tra 5-40%; più preferibilmente 20-30%; ancor più preferibilmente a diluizioni del 30% in peso; la dispersione acquosa risultante possiede un pH compreso tra 1 e 5, preferibilmente 2-5, ancor più preferibilmente 2.5-4; la concentrazione totale di zirconio metallico in tale dispersione à ̈ compresa tra 0.1-3%, preferibilmente 0.1-1%, ancor più preferibilmente 0.15-0.18%. 10. Composition according to claim 1, wherein: to. the paraffins have a melting point between 20-60 ° C, preferably 50 b. the paraffins and zirconyl derivatives / derivatives are optionally dispersed in advance in water at dilutions ranging from 5-40%; more preferably 20-30%; even more preferably at dilutions of 30% by weight; the resulting aqueous dispersion has a pH between 1 and 5, preferably 2-5, even more preferably 2.5-4; the total concentration of metallic zirconium in this dispersion is comprised between 0.1-3%, preferably 0.1-1%, even more preferably 0.15-0.18%. 11. Composizione secondo le rivendicazioni 1-10 ulteriormente comprendente additivi, quali resine, coloranti, profumi, conservanti, battericidi. 11. Composition according to claims 1-10 further comprising additives, such as resins, dyes, perfumes, preservatives, bactericides. 12. Metodo per impermeabilizzare un materiale edile poroso da rivestimento comprendente in combinazione una fase di trattamento di bagnatura superficiale del materiale selezionato tra immersione, spalmatura a mano o con pennello o spray o a rullo, etc etc) eseguito eventualmente dopo la posa del materiale, una fase di asciugatura ed una fase di riscaldamento superficiale ad una temperatura maggiore di 40 e preferibilmente nell'intervallo di di 40-70°C per almeno un minuto. 12. Method for waterproofing a porous building material for covering comprising in combination a surface wetting treatment phase of the selected material (immersion, spreading by hand or with a brush or spray or roller, etc etc) possibly carried out after the laying of the material, a drying phase and a surface heating phase at a temperature higher than 40 and preferably in the range of 40-70 ° C for at least one minute. 13. Metodo secondo al rivendicazione 12, in cui detto materiale à ̈ un materiale a base di argilla. 13. A method according to claim 12, wherein said material is a clay-based material. 14. Metodo secondo al rivendicazione 13, in cui detto materiale à ̈ un materiale a base di argilla comprendente silicio. The method according to claim 13, wherein said material is a clay-based material comprising silicon. 15. Uso della composizione secondo la rivendicazione 1 e dei metodi secondo le rivendicazioni 12-14 per il trattamento di materiali edili da rivestimento quali mattoni e piastrelle a base di argilla, materiale edile poroso. 15. Use of the composition according to claim 1 and the methods according to claims 12-14 for the treatment of building facing materials such as clay-based bricks and tiles, porous building material. 16. Materiale edile da rivestimento ottenuto secondo il metodo di una delle rivendicazioni 12-14.16. Coating building material obtained according to the method of one of claims 12-14.
IT000131A 2012-06-22 2012-06-22 COMPOSITION AND WATERPROOFING TREATMENT ITFI20120131A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3486911A (en) * 1967-08-21 1969-12-30 Sun Chemical Corp Textile treating compositions and textiles treated therewith
EP1493761A1 (en) * 2003-07-02 2005-01-05 3M Innovative Properties Company Fluoropolymer of fluorinated short chain acrylates or methacrylates and oil- and water repellent compositions based thereon
WO2006028608A1 (en) * 2004-09-02 2006-03-16 3M Innovative Properties Company Method for treating porous stone using a fluorochemical composition
WO2012085653A1 (en) * 2010-12-23 2012-06-28 Benelli Alessio Waterproofing treatment

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3486911A (en) * 1967-08-21 1969-12-30 Sun Chemical Corp Textile treating compositions and textiles treated therewith
EP1493761A1 (en) * 2003-07-02 2005-01-05 3M Innovative Properties Company Fluoropolymer of fluorinated short chain acrylates or methacrylates and oil- and water repellent compositions based thereon
WO2006028608A1 (en) * 2004-09-02 2006-03-16 3M Innovative Properties Company Method for treating porous stone using a fluorochemical composition
WO2012085653A1 (en) * 2010-12-23 2012-06-28 Benelli Alessio Waterproofing treatment

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