Spray can with a fluorine-, water-, and solvent-free, non-foaming, sprayable filling, process for its manufacture, its use, as well as fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations, and process for their manufacture

Abstract

Spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling, containing (A) Propyltriethoxysilane (PTEOS), (B) dimethyl ether or a mixture of propane, n-butane and isobutane as propellant, (C) at least one clay mineral with an average particle size d 50 from 1 to 30 µm, (D) Corundum with an average particle size d 50 from 1 to 30 µm or a mixture of, based on the mixture, 10 wt.% to 99 wt.% corundum with an average particle size d 50 from 1 to 30 µm and 1 wt.% to 90 wt.% calcium magnesium carbonate and / or magnesium hydroxide with an average particle size d 50 from 1 to 30 µm and (E) at least one acid as catalyst and optionally containing (F) at least one solid, functional, organic, inorganic or organometallic additive with an average particle size d 50 from 1 to 30 µm, Process for their preparation, and their use for the production of fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations with properties protecting against corrosion, weathering, water absorption and flying sparks on porous and non-porous substrates.

Description

Field of the invention

[0001] The present invention relates to a spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling.

[0002] Furthermore, the present invention relates to the production of the spray can.

[0003] Furthermore, the present invention relates to the use of the spray can for producing fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations with properties that protect against corrosion, weathering, water absorption and flying sparks on porous and non-porous substrates.

[0004] Last but not least, the present invention relates to fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations with properties that protect against corrosion, weathering, water absorption and flying sparks on porous and non-porous substrates, which can be produced using a spray can, and to processes for their production. State of the art

[0005] German patent application DE 103 21 799 A1 discloses a coating agent with antigraffiti effect. The coating agent is obtainable by reacting organic silicon compounds of the general formula (I) RSiX 4-n , where R 1 a group having 1 to 20 carbon atoms, X is an alkoxy radical having 1 to 20 carbon atoms or a halogen and n is an integer from 0 to 3, where different radicals X or R 1which may each be the same or different, and / or precondensates obtainable therefrom, wherein at least 50 wt.% of the silicon compounds, based on the total weight of the silicon compounds used, can be represented by the formula R'SiX, in which R 1 and X have the meaning given above, are condensed to polysiloxanes until the ratio of R'SiO(OH) to R'SiO 1,5 -signals measured by NMR spectroscopy in the range of 0.6 to 4, and adding to this polysiloxane mixture compounds of the formula (II) (R'') Si(R'),(OR)( 4-+-u) (II), wherein R'' represents a group having 1 to 20 carbon atoms and containing at least 3 fluorine atoms, u is 1 or 2 and t is 0 or 1, R and R' are the same or different and represent a group having 1 to 20 carbon atoms.

[0006] The disadvantage is that the coating agent contains considerable amounts of organically bound fluorine.

[0007] German patent application DE 102 18 871 A1 discloses a method for impregnating porous mineral substrates such as fiber cement using a spray technique. The method uses a gas-assisted spray unit to apply liquid impregnating agent to the substrate surface in a controlled manner at a rate significantly lower than that required for conventional flood-coating applications. Common and well-known hydrophobic or oleophobic agents based on organofunctional silanes, siloxanes, silicones, silicone resins, or siliconates, which may also contain organically bound fluorine, are used as impregnating agents.

[0008] From the international patent application WO 2009 / 144495 A2, a hydrophobic coating agent is known which contains at least one hydroxyl-terminated siloxane and at least one silane which react with each other during curing.

[0009] An aerosol product based on a silicone elastomer is known from the American patent application US 2018 / 0215947 A1. The silicone elastomer is sprayed from a container using a propellant.

[0010] Weatherproof, fungal, and soil-resistant coatings for wood and masonry are known from the American patent application US 2022 / 0259442 A1. These coatings are produced from sol-gel solutions that may contain a variety of alkoxysilanes, including propyltriethoxysilane (PTEOS), as well as solvents such as water and methanol. No acid catalysts are used for the crosslinking of the alkoxysilanes.

[0011] The coatings may contain functional inorganic additives that impart abrasion-resistant, fire-retardant, electrically conductive, antimicrobial, antibacterial, or fungicidal properties. The particle size of the additives can range from 2 nm to 500 µm. Examples include silver, titanium dioxide, zinc oxide, aluminum oxide, iron oxide, selenium oxide, tellurium oxide, and clay, which may be composed of kaolinite, montmorillonite, illite, or chlorite.

[0012] The known sol-gel solutions can be applied by spraying, atomizing, squeegeeing, padding, foaming, rolling, dipping, soaking, or inkjet printing. Whether spraying can be performed using aerosol cans is not disclosed.

[0013] However, for coating materials to be sprayed to produce functional coatings using aerosol cans, their fillings must exhibit a series of very specific, coordinated chemical and physical properties. For example, the filling ingredients must not attack the spray can during transport, prolonged storage, or heating; they must not react chemically with one another, and in particular, they must not emit gases; and they must not separate. Should they do separate somewhat, the filling should be able to be homogenized again simply by shaking. The solid ingredients must be small enough not to clog the spray nozzles. On the other hand, they must not be so small that they agglomerate or aggregate. The filling must not foam during spraying, as this would result in unusable coatings. Last but not least, the propellants required for spraying with aerosol cans must be non-toxic.

[0014] However, the American patent application does not provide the skilled person with any indication as to how such a property profile can be realized. Object of the present invention

[0015] The object of the present invention was to provide a spray can with a water- and solvent-free, non-foaming, sprayable filling which allows the production of abrasion-resistant anti-graffiti coatings and functional coatings and impregnations with properties protecting against corrosion, weathering and water absorption as well as against flying sparks on porous and non-porous substrates, in particular on metals, wood, stones, minerals, glasses, concrete, asphalt, plaster tongues, plastics and / or composite materials made of at least two of these materials.

[0016] The fillings must exhibit a series of very specific, coordinated chemical and physical properties. For example, the filling components should not attack the spray can during transport, prolonged storage, or when heated, and they should not react chemically with one another, in particular, they should not emit gases, and they should not separate. If they do separate somewhat, the fillings should be able to be homogenized again simply by shaking. The solid components should be small enough that they do not clog the spray nozzles. On the other hand, they should not be so small that they agglomerate or aggregate. The filling should not foam during spraying, as this would result in unusable coatings and impregnations. Last but not least, the propellants required for spraying with aerosol cans should be non-toxic.In particular, the liquid components of the filling, which form the matrix of the coatings produced from it, should disperse the solid components excellently.

[0017] The resulting functional coatings should have excellent property profiles that are particularly advantageous for the respective application. The inventive solution

[0018] Accordingly, the spray can according to the invention was found according to independent patent claim 1. Advantageous embodiments of the spray can according to the invention are the subject of dependent patent claims 2 to 6.

[0019] Furthermore, the process according to the invention for producing the spray can according to the invention was found according to independent claim 7.

[0020] Furthermore, the inventive use of the spray can according to the invention was found according to independent claim 8. An advantageous embodiment of the inventive use is the subject of dependent patent claim 10.

[0021] Furthermore, the inventive method for producing fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations with properties that protect against weathering, corrosion, water absorption, and flying sparks was found according to independent claim 10. Advantageous embodiments of the inventive method are the subject of dependent claims 11 and 12.

[0022] Last but not least, the coatings according to the invention were found according to independent claim 13. Advantages of the inventive solution

[0023] In view of the prior art, it was surprising and unforeseeable for the person skilled in the art that the object of the present invention could be achieved by means of the spray can according to the invention, the method according to the invention for its production and its use according to the invention, as well as by means of the method according to the invention for producing coatings and impregnations and the coatings and impregnations according to the invention.

[0024] Using the spray cans according to the invention, fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations with properties that protect against corrosion, weathering, water absorption and flying sparks can be produced on porous and non-porous substrates, in particular on metals, wood, stones, minerals, glasses, concrete, asphalt, plaster tongues, plastics and / or composite materials made of at least two of these materials, with excellent property profiles that are particularly advantageous for the respective intended use.

[0025] The fillings of the spray cans according to the invention advantageously exhibit a series of very specific, coordinated chemical and physical properties. For example, the ingredients or components of the fillings do not attack the spray cans during transport, prolonged storage, or when heated. They also do not react chemically with one another and, in particular, they do not evolve gases, thus preventing undesirable overpressure. Furthermore, they do not separate. If they do separate somewhat, the filling can be homogenized again by simply shaking. The solid components are small enough that, on the one hand, they do not clog the spray nozzles. On the other hand, they are not so small that they agglomerate or aggregate, or are released as nanoparticles that are harmful to the environment and human health.The filling does not foam during spraying, thus always producing the functional coatings according to the invention with the desired property profiles. Last but not least, the propellants required for spraying are non-toxic, and the liquid components of the filling, which form the matrix of the coatings according to the invention produced from them, are excellent at dispersing the solid components.

[0026] Since the fillers used according to the invention do not migrate from porous substrates, very thin layers can be applied in one spray pass when using the spray can according to the invention. By repeatedly spraying, comparatively thin functional coatings and impregnations according to the invention with excellent properties can be produced.

[0027] A very particular advantage of the fillings and functional coatings used according to the invention is that they are free of fluorine, in particular free of organically bound fluorine. The anti-graffiti coatings according to the invention are stable to organic solvents. Graffiti sprayed onto their surfaces can therefore be easily removed with cleaning agents containing organic solvents. Afterward, the anti-graffiti coatings exhibit no clouding and remain smooth and glossy.

[0028] Further advantages of the invention will become apparent from the following description. Detailed description of the invention

[0029] The spray can according to the invention contains a fluorine-free, water- and solvent-free, non-foaming, sprayable filling which contains at least ((A) Propyltriethoxysilane (PTEOS), (B) dimethyl ether or a mixture of propane, n-butane and isobutane as propellant, (C) at least one two-layer clay mineral with an average particle size d 50 from 1 to 30 µm, (D) Corundum with an average particle size d 50 from 1 to 30 µm or a mixture of, based on the mixture, 10 wt.% to 99 wt.% corundum with an average particle size d 50 from 1 to 30 µm and 1 wt.% to 90 wt.% calcium magnesium carbonate and / or magnesium hydroxide with an average particle size d 50 from 1 to 30 µm and (E) contains at least one acid as a catalyst.

[0030] A preferred filling contains, based on the sum of the proportions of its components A, C, D and E, A. 60 wt% to 80 wt%, in particular 65 wt% to 75 wt%, PTEOS, C. 1 wt.% to 10 wt.%, in particular 2 wt.% to 5 wt.%, of the at least one two-layer clay mineral having an average particle size d 50 from 1 to 30 µm, D. 10 wt.% to 30 wt.%, in particular 15 wt.% to 25 wt.%, corundum with an average particle size d 50 from 1 to 30 µm or a mixture of, based on the mixture, 10 wt.% to 99 wt.%, in particular 20 wt.% to 80 wt.%, corundum with an average particle size d 50 from 1 to 30 µm and 1 wt.% to 90 wt.%, in particular 20 wt.% to 80 wt.%, calcium magnesium carbonate and / or magnesium hydroxide with an average particle size d 50 from 1 to 30 µm and E. 0.5 wt% to 5 wt% of the at least one acid as catalyst.

[0031] Preferably, the at least one two-layer clay mineral C is kaolinite, kaolin, and / or halloysite. Kaolin is used in particular.

[0032] Component D to be used according to the invention necessarily contains corundum. Corundum is present (i) as the sole component D or (ii) together with calcium magnesium carbonate or (iii) together with magnesium hydroxide. Alternatively, (iv) corundum is present together with the mixture of calcium magnesium carbonate and magnesium hydroxide. In this mixture, the weight ratio of calcium magnesium carbonate to magnesium hydroxide is preferably 10:1 to 1:10.

[0033] Preferably, the acid E is selected from the group consisting of phosphoric acid, phosphoric acid monoalkyl and aryl esters, phosphoric acid dialkyl and diaryl esters, and alkyl and aryl sulfonic acids such as p-toluenesulfonic acid. In particular, the acid E is phosphoric acid.

[0034] The filling may further comprise at least one solid, functional, organic, inorganic or organometallic additive F with an average particle size d 50from 1 to 30 µm, selected from the group consisting of polyoxometalates (POM), metal salts, metal oxides, garnets, spinels, ferrites and flame retardants.

[0035] Suitable biocidal polyoxometalates (POM) F are known from German patent DE 10 2020 125 919 B4, paragraphs

[0157] to

[0181] .

[0036] Suitable flame retardant additives F are zinc borates, aluminum hydroxides, ammonium phosphates and antimony oxide.

[0037] The magnesium hydroxide D to be used according to the invention also has a flame-retardant effect.

[0038] Examples of suitable metal salts, metal oxides, garnets, spinels and ferrites are calcium sulfate, strontium sulfate, barium sulfate, calcium phosphate, scandium oxide, yttrium oxide, titanium dioxide, zirconium dioxide, yttrium-stabilized zirconium dioxide, hafnium dioxide, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, zinc oxide, oxides of the lanthanides, preferably lanthanum oxide and cerium oxide, in particular cerium oxide, oxides of the actinides, magnesium oxide, calcium oxide, strontium oxide, barium oxide, aluminum oxide, zinc-dosed aluminum oxide, gallium oxide, indium oxide, germanium oxide, tin oxide, antimony oxide, bismuth oxide, zeolites, mixed oxides of at least two of the mentioned oxides such as antimony-tin oxide and indium-tin oxide, Fe3O4, CoFe2O4, NiFe2O4, MnFe2O4, SrFe2O4, BaFe2O4, CuFe2O4, Y3Fe5O 12 , CrO2, MnO, Mn3O4, Mn2O, FeO, Fe2O3, NiO, Cr2O3, CoO, Co3O4, BaFe 12 O 19 , (Bi, La,Tb)(Fe,Mn,DyPr)O3, Ba3Co2Fe 24 O 41 , Y3Fe5O 12 , NiZnFe2O4, Cu 0,2 Mg0,4 Zn 0,4 Fe2O4, Fe3O4(Cu,Ni,Zn)Fe2O4, TbMn2O5, PbNi 1 / 33 Nb 2 / 3 TiO3-CuNiZn, BaTiO3-NiZnFe2O4, doped BaTiO3, doped SrTiO3, (Ba,Sr)TiO3, Pb(Zr,Ti)O3, SrBi2Ta2O9, PbNi 1 / 3 Nb 2 / 3 TiO3-PbTio3, PbMg 1 / 3 Nb 2 / 3 TiO3-PbTiO3, lanthanum-modified and lanthanum-strontium-modified Pb(Zr,Ti)O3, Pb(Zr x Ti 1-x )O3, where x is greater than or equal to 1, PbHfO3, PbZrO3, Pb(Zr,Ti)O3, PbLa(Zr,Sn,Ti)O3, PbNb(ZrSnTi)O3, Pb 1-x La x (Zr y Ti 1-y ) (1-x) / 4 O3, where x is greater than or equal to 1 and y is greater than or equal to 1, NaNbO3, (K,Na)(Nb,Ta)O3, KNbO3, BaZrO3, Na 0,23 K 0,25 Bi 0,5 TiO3, Ag(Ta,Nb)O3 and Na 0,5 Bi 0,5 TiO3-K 0,5 Bi 0,5 TiO3-BaTiO3;

[0039] The content of the at least one solid, functional, organic, inorganic or organometallic additive F in the fillings can vary very widely and depends primarily on its function in the functional coatings according to the invention.

[0040] In particular, the particularly preferred filling contains, based on the sum of its components A, C, D, E and F - 1 wt.% to 99 wt.%, preferably 1 wt.% to 90 wt.% and more preferably 1 wt.% to 80 wt.% of components A, C, D and E and - 30 wt.% to 1 wt.%, preferably 25 wt.% to 1 wt.% and more preferably 20 wt.% to 1 wt.% of the at least one component F.

[0041] According to the invention, the spray can according to the invention with the fluorine-, water- and solvent-free, non-foaming, sprayable filling is produced by at least (I) the components A, C, D and E or A, C, D, E and F are mixed together and the resulting mixture is homogenised and (II) the homogenized mixture is pressed into a spray can pre-filled with propellant B or alternatively (III) the propellant B is injected into a spray can pre-filled with the homogenised mixture A, C, D and E or A, C, D, E and F.

[0042] In addition, the fluorine-, water-, and solvent-free, non-foaming, sprayable filling may contain an inorganic rheology-controlling additive. Fumed silica, especially Aerosil, is preferred.

[0043] According to the invention, the spray can according to the invention is used for producing the fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations according to the invention with protection against corrosion and water absorption as well as against flying sparks, on porous and non-porous substrates.

[0044] Porous and non-porous substrates contain or consist of metals, wood, stone, minerals, ceramics, glass, concrete, asphalt, plaster, plastics, and / or composite materials made of at least two of these materials. Porous and non-porous substrates can include, for example, the interior and exterior surfaces of buildings, factories, means of transport, bridges, roads, paths, and squares of any kind.

[0045] The fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations according to the invention with properties that protect against corrosion, water absorption, and flying sparks are produced by spraying the fluorine-, water-, and solvent-free, non-foaming, sprayable fillers contained in the spray cans according to the invention at least once onto a porous or non-porous substrate and allowing them to cure in air. The spraying process can be repeated several times. Care must be taken to ensure that the applied layers cure between each spraying process.

[0046] Another particular advantage of the fluorine-free, abrasion-resistant, functional coatings and impregnations according to the invention is that they prevent the weathering of stones such as sandstone, which is particularly important for listed buildings, historical ruins and monuments.

[0047] Another particular advantage of the fluorine-free, abrasion-resistant, functional coatings and impregnations according to the invention is that they protect porous and non-porous, flammable substrates, especially those made of wood and plastics such as polystyrene and polyurethane foam, from flying sparks and thus prevent the outbreak of fires. Flying sparks are a common cause of fires on construction sites, in craft businesses, and in factory halls where welding, cutting, and grinding work are frequently carried out.

[0048] Preferably, the fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations according to the invention have a thickness of 10 µm to 60 µm.

[0049] The major advantages of the procedures described above are that no solvents, in particular no solvents harmful to health and the climate, are emitted, so that no shrinkage of the fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations according to the invention caused by a loss of mass, nor any cracking occurs.

[0050] The present invention is further illustrated by the following examples. These examples serve to illustrate the invention and do not limit it. Example 1The production of a spray can according to the invention with a corundum-containing filling and its use1.1 The production of the spray can according to the invention

[0051] A homogeneous mixture of, based on the total amount of the mixture, 70 wt.% PTEOS, 23 wt.% corundum with a particle size d 50of 25 µm, 3 wt.% kaolin with an average particle size d 50 of 28 µm, 2 wt.% of a solvent-free silicone surfactant, 0.5 wt.% fumed silicon dioxide, and 1.5 wt.% phosphoric acid, and pressed into a spray can prefilled with dimethyl ether and fitted with a mixing ball. The result is the spray can according to the invention with the internal pressure required for spraying. 1.2 The production of an anti-graffiti coating according to the invention

[0052] The inventive spray can 1.1 is shaken prior to use, ensuring thorough mixing and homogenization of all components with the aid of the mixing ball. The filling is then sprayed onto a white plastered house wall in several spray passes for testing purposes. The applied layer is air-dried. The result is a uniform, scratch-resistant, abrasion-resistant, fluorine-free, transparent, 50 µm thick anti-graffiti coating according to the invention.

[0053] Using a spray can, the word "ANTIGRAFFITI" is sprayed onto the coating using black paint. After the black paint has dried and hardened, it is left to age for a further 24 hours. Even after that, the black graffiti can be completely removed with a mixture of spirit and acetone and a cleaning cloth without damaging the anti-graffiti coating. This test is repeated several times, without the inventive anti-graffiti coating losing its excellent properties. It remains smooth, shiny, and free of cloudiness even after repeated cleaning. 1.3 The production of an impregnation according to the invention that protects against weathering, corrosion and water absorption

[0054] The spray can 1.1 according to the invention is shaken before use, so that the mixing ball ensures intensive mixing and homogenization of all components. The filling is then sprayed onto a 1 kg concrete block in several spray passes for testing purposes and allowed to cure.

[0055] After the impregnation has cured, the impregnated concrete block is sprayed with water. The water beads up and rolls off the impregnated surface. For comparison, a 1 kg, unimpregnated concrete block is sprayed with water. The water does not roll off, but is absorbed by the material.

[0056] The impregnated and non-impregnated concrete blocks are stored in water baths and their respective weight gain in grams is measured after the periods of time specified in Table 1. Table 1: Water absorption by the impregnated and non-impregnated concrete block Weight gain (g) after 1h 2h 3h 10h Impregnated 2 4 5 8 Not impregnated 5 8 9 12

[0057] The results show the good protective effect of the impregnation according to the invention on concrete.

[0058] The inventive spray can 1.1 is shaken before use, ensuring thorough mixing and homogenization of all components with the aid of the mixing ball. The filling is then sprayed onto a 0.5 kg red sandstone in several spray passes for testing purposes and allowed to cure.

[0059] After the impregnation has cured, the impregnated red sandstone is sprayed with water. The water beads up and rolls off the impregnated surface. For comparison, a 0.5 kg piece of unimpregnated red sandstone is sprayed with water. The water does not roll off, but is absorbed by the material.

[0060] The impregnated and non-impregnated sandstone are stored in water baths and their respective weight gain in grams is measured after the time periods given in Table 2. Table 2: Water absorption by the impregnated and non-impregnated red sandstone Weight gain (g) after 0,5h 1h 5h Impregnated 1,7 2,4 4 Not impregnated 7,8 11,6 16,4

[0061] The results show the very good protective effect of the impregnation according to the invention on red sandstone. Example 2The production of a spray can according to the invention with a corundum-containing filling and its use

[0062] Example 1 is repeated, except that a mixture of propane, n-butane, and isobutane (AERON® from ScharrCPC) is used as the propellant instead of dimethyl ether. The same advantageous results are achieved. Example 3The production of a spray can with a filling containing corundum and calcium magnesium carbonate and its use3.1 The production of the spray can according to the invention

[0063] A homogeneous mixture of, based on the total amount of the mixture, 70 wt.% PTEOS, 11 wt.% corundum with a particle size d 50 of 25 µm, 12 wt.% calcium magnesium carbonate with a particle size d 50 of 18 µm, 3 wt.% kaolin with an average particle size d 50 of 28 µm, 2 wt.% of a solvent-free silicone surfactant, 0.5 wt.% fumed silicon dioxide, and 1.5 wt.% phosphoric acid, and pressed into a spray can prefilled with dimethyl ether and fitted with a mixing ball. The result is the spray can according to the invention with the internal pressure required for spraying. 3.2 The production of a coating according to the invention that protects against flying sparks

[0064] The inventive spray can 3.1 is shaken before use, ensuring thorough mixing and homogenization of all components with the aid of the mixing ball. The filling is then sprayed onto a smooth wooden board in several spray passes for testing purposes. The applied layer is air-dried. The result is a uniform, scratch-resistant, abrasion-resistant, fluorine-free, transparent, 50 µm thick coating according to the invention. Part of the wooden board remains uncoated.

[0065] The pointed flame of a gas burner is directed directly onto the coating according to the invention from a distance of 2 cm for 10 seconds. Although the wood beneath the coating according to the invention chars a small area where the flame hits, it does not ignite because a gray protective layer forms on the wood surface.

[0066] The experiment is repeated with the uncoated wood surface. The wood chars extensively and begins to glow, so the experiment is discontinued. Example 4The production of a spray can with a filling containing corundum and magnesium hydroxide and its use4.1 The production of the spray can according to the invention

[0067] A homogeneous mixture of, based on the total amount of the mixture, 70 wt.% PTEOS, 11 wt.% corundum with a particle size d 50 of 25 µm, 12 wt.% magnesium hydroxide with a particle size d 50 of 18 µm, 3 wt.% kaolin with an average particle size d 50 of 28 µm, 2 wt.% of a solvent-free silicone surfactant, 0.5 wt.% fumed silicon dioxide, and 1.5 wt.% phosphoric acid, and pressed into a spray can prefilled with dimethyl ether and fitted with a mixing ball. The result is the spray can according to the invention with the internal pressure required for spraying. 4.2 The production of a coating according to the invention that protects against flying sparks

[0068] The inventive spray can 4.1 is shaken before use, ensuring thorough mixing and homogenization of all components with the aid of the mixing ball. The filling is then sprayed onto a smooth wooden board in several spray passes for testing purposes. The applied layer is air-dried. The result is a uniform, scratch-resistant, abrasion-resistant, fluorine-free, transparent, 40 µm thick coating according to the invention. Part of the wooden board remains uncoated.

[0069] The pointed flame of a gas burner is directed directly onto the coating according to the invention from a distance of 2 cm for 10 seconds. Although the wood beneath the coating according to the invention chars a small area where the flame hits, it does not ignite because a gray protective layer forms on the wood surface. The flame-retardant effect is thus guaranteed even with the significantly thinner layer thickness.

[0070] The experiment is repeated with the uncoated wood surface. The wood chars extensively and begins to glow, so the experiment is discontinued.

Claims

[1] Spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling, containing (A) Propyltriethoxysilane (PTEOS), (B) dimethyl ether or a mixture of propane, n-butane and isobutane as propellant, (C) at least one two-layer clay mineral with an average particle size d 50 from 1 to 30 µm, (D) Corundum with an average particle size d 50 from 1 to 30 µm or a mixture of, based on the mixture, 10 wt.% to 99 wt.% corundum with an average particle size d 50 from 1 to 30 µm and 1 wt.% to 90 wt.% calcium magnesium carbonate and / or magnesium hydroxide with an average particle size d 50 from 1 to 30 µm and (E) at least one acid as a catalyst. [2] Spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling according to claim 1, characterized bythat the filling further comprises at least one solid, functional, organic, inorganic or organometallic additive (F) with an average particle size d 50 from 1 to 30 µm, selected from the group consisting of polyoxometalates (POM), metal salts, metal oxides, garnets, spinels, ferrites and flame retardants. [3] Spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling according to claim 1 or 2, characterized by that at least one two-layer clay mineral (C) is kaolinite, kaolin and / or halloysite. [4] Spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling according to one of claims 1 to 3, characterized by that the acid (E) is selected from the group consisting of phosphoric acid, phosphoric acid monoalkyl and aryl esters, phosphoric acid dialkyl and diaryl esters and alkyl and aryl sulfonic acids. [5] Spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling according to one of claims 1 to 4, characterized by that the filling, in each case based on the sum of the proportions of its components (A), (C), (D) and (E), (A) 60 wt% to 80 wt% PTEOS, (C) 1 wt.% to 10 wt.% of at least one two-layer clay mineral having an average particle size d 50 from 1 to 30 µm, (D) 10 wt.% to 30 wt.% corundum with an average particle size d 50 from 1 to 30 µm or a mixture of, based on the mixture, 10 wt.% to 99 wt.% corundum with an average particle size d 50 from 1 to 30 µm and 1 wt.% to 90 wt.% calcium magnesium carbonate and / or magnesium hydroxide with an average particle size d 50 from 1 to 30 µm and (E) contains 0.5 wt% to 5 wt% phosphoric acid. [6] Spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling according to one of claims 2 to 5, characterized by that the filling, based on the sum of its components (A), (C), (D), (E) and (F), - 1% to 99% by weight of components (A), (C), (D) and (E) and - 99 wt.% to 1 wt.% of the at least one solid, functional, organic, inorganic or organometallic additive (F) with an average particle size d 50 from 1 to 30 µm, selected from the group consisting of polyoxometalates (POM), metal salts, metal oxides, garnets, spinels, ferrites and flame retardants. [7] A process for producing a spray can with a fluorine-, water- and solvent-free, non-foaming, sprayable filling according to one of claims 1 to 6, characterized by that one (I) the components (A), (C), (D) and (E) or (A), (C), (D) (E) and (F) are mixed together and the resulting mixture is homogenised and (II) the homogenized mixture is pressed into a spray can pre-filled with the propellant (B) or alternatively (III) the propellant (B) is pressed into a spray can pre-filled with the homogenized mixture. [8] Use of the spray can according to any one of claims 1 to 6 or the spray can produced according to claim 8 for producing fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations with properties protecting against corrosion, weathering and water absorption as well as against flying sparks on porous and non-porous substrates. [9] Use according to claim 8, characterized bythat the porous and non-porous substrates contain or consist of metals, wood, stones, minerals, ceramics, glasses, concrete, asphalt, plaster tongues, plastics and / or composite materials made up of at least two of these materials. [10] Process for the production of fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations with properties that protect against weathering, corrosion, water absorption and flying sparks characterized by that the fluorine-, water- and solvent-free, non-foaming, sprayable filling contained in at least one spray can according to one of claims 1 to 6 is sprayed at least once onto a porous or non-porous substrate and allowed to harden in the air. [11] A process for producing fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations according to claim 10, characterized bythat the porous or non-porous substrate contains or consists of metals, wood, stones, minerals, glasses, concrete, asphalt, plaster tongues, plastics and / or composite materials made up of at least two of these materials. [12] A process for producing fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations according to claim 10 or 11, characterized by that the coatings have a thickness of 10 µm to 60 µm. [13] Fluorine-free, abrasion-resistant anti-graffiti coatings and functional coatings and impregnations having properties protecting against weathering, corrosion, water absorption and flying sparks, producible by the process according to any one of claims 10 to 12.