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WO2023104224A1 - Antimicrobial hydrophobizing liquid for surface treatment/protection of smooth non-absorbent materials containing methyl silicone resin - Google Patents

Antimicrobial hydrophobizing liquid for surface treatment/protection of smooth non-absorbent materials containing methyl silicone resin Download PDF

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Publication number
WO2023104224A1
WO2023104224A1 PCT/CZ2022/050093 CZ2022050093W WO2023104224A1 WO 2023104224 A1 WO2023104224 A1 WO 2023104224A1 CZ 2022050093 W CZ2022050093 W CZ 2022050093W WO 2023104224 A1 WO2023104224 A1 WO 2023104224A1
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Prior art keywords
antimicrobial
solution
methyl silicone
weight
nanoparticles
Prior art date
Application number
PCT/CZ2022/050093
Other languages
French (fr)
Inventor
Vojtech RUZEK
Petr Louda
Katarzyna Ewa Buczkowska
Original Assignee
Technicka Univerzita V Liberci
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Publication date
Application filed by Technicka Univerzita V Liberci filed Critical Technicka Univerzita V Liberci
Priority to EP22799843.2A priority Critical patent/EP4444787A1/en
Publication of WO2023104224A1 publication Critical patent/WO2023104224A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015—Biocides
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0881—Titanium
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Definitions

  • Nanoparticles of the above-mentioned metals and/or their oxides with antimicrobial properties may be in the form of a colloidal solution.
  • the antimicrobial hydrophobizing liquid may further comprise 0.1 to 60 % by weight of thickening agents, which in a preferred embodiment are formed by cetyl alcohol and/or lanolin.
  • the antimicrobial hydrophobizing liquid contains the addition of ethyl acetate solution in an amount of 0.1 to 60 % by weight of the starting solution of methyl silicone resin or the starting aqueous methyl silicone emulsion.
  • the antimicrobial hydrophobizing liquid according to the invention is based on methyl silicone resin dissolved in xylene and, if necessary, thickened with conventional thickening agents, for example with cetyl alcohol or lanolin. Nanoparticles and/or microparticles of at least one of metals with antimicrobial properties, such as silver, copper, nickel, zinc, titanium, iron and/or their oxides, such as copper oxide, zinc oxide, titanium dioxide, are added to this solution, wherein mutual combinations of the nanoparticles and/or microparticles of these metals and/or their oxides are also possible.
  • An aqueous emulsion can be formed by adding water to a solution of methyl silicone resin in xylene.
  • the antimicrobial hydrophobizing liquid contains a solution of methyl silicone resin dissolved in xylene, with 15 to 70 % by weight of methyl silicone resin in a thickened solution (resin + xylene + thickening agents) or in an unthickened solution.
  • the xylene solution of this resin can be used alone as a hydrophobizing coating, however, in order to add nanoparticles and/or microparticles to the powder, it is advisable to thicken it with cetyl alcohol or lanolin, to limit the sedimentation of nanoparticles and/or microparticles with a content of up to 60 % by weight of a thickening agent.
  • the nanoparticles and/or microparticles of metals and/or their oxides with antimicrobial properties are added to the solution in powder form in an amount of 0.001 to 8 % by weight based on the total weight of the solution for nanoparticles and in an amount of 0.1 to 8 % by weight based on the total weight of the solution for microparticles, whereupon they are thoroughly mixed to ensure that they are evenly dispersed in the solution. This applies to both the unconcentrated and concentrated solution.
  • the mixing method is arbitrary, except for ferromagnetic metals, especially iron and nickel, where magnetic stirrers are not suitable.
  • the liquid After the application of the antimicrobial hydrophobizing liquid to the surface of the treated component, the liquid is able to harden even at normal room temperature.
  • a heat treatment may be carried out, namely by at least drying it at a temperature of at least 50 °C for at least 20 minutes. It is also possible to use firing at higher temperatures if the surfaces of thermally stable materials are being treated.
  • water is added for emulsification in an amount of up to 50 % by weight based on the total weight of the resulting emulsion.
  • This procedure also enables an alternative method to deliver nanoparticles into the resulting liquid, when instead of powdered nanoparticles, an aqueous solution of nanoparticles, a so-called colloidal solution of antimicrobial metals or their oxides, as well as their mutual combination, is used.
  • the nanoparticle size again ranges from 5 to 1000 nm and their concentration in an aqueous solution ranges from 0.01 to 20 g/l.
  • the resulting emulsion must be homogenized.
  • the nanoparticles and microparticles further stabilize the emulsion, and emulsification prevents their sedimentation.
  • the liquids with microparticles can be mixed (homogenized) again before use, especially if sedimentation of microparticles occurs.
  • a mixture of Ce to C14 hydrocarbons may also be added to the mixture to further improve the water-repellent properties of the resulting liquid.
  • Microparticles, nanoparticles, hydrocarbons, as well as ethyl acetate can be used alone or in mutual combination.
  • the liquid thus prepared must be mixed thoroughly before use, as the microparticles sediment quickly, but their significant aggregation does not occur.
  • Suitable methods of application of this antimicrobial hydrophobizing liquid are coating or spraying, wherein it is suitable to use it for applications where abrasion is not expected, nor are expected other risks of mechanical damage due to the worse tribological properties of the given microparticles and where equipment is available to mix the liquid before use, whether continuously or once just before use.
  • methyl silicone resin in xylene 5 % by weight of cetyl alcohol and lanolin were added in a 1/1 ratio relative to the stock solution of methyl silicone resin and 2 % by weight of copper microparticles up to 10 pm in size relative to the stock solution of methyl silicone resin in xylene.
  • the solution was mixed thoroughly to ensure uniform dispersion of the microparticles in the solution.
  • liquid prepared in this manner should be thoroughly mixed before use, even though in this example the sedimentation of microparticles is slower than in example 1 .
  • the application can be carried out by spraying or coating, the liquid being usable for applications where abrasion or other risks of mechanical damage due to the inferior tribological properties of the microparticles are not expected and where equipment is available to mix the liquid before use, either continuously or once just before utilization.
  • An antimicrobial hydrophobizing liquid is formed from a solution of methyl silicone resin in xylene with a proportion of 50 % by weight and a colloidal silver solution in which the silver particle sizes range from 5 to 100 nm, with a mass concentration of silver of 50 mg/l.
  • the proportion of the aqueous colloidal solution in the total weight of the liquid was 10 % by weight, the proportion of methyl silicone resin in the resulting solution was therefore 45 % by weight.
  • the emulsion is subsequently homogenized.
  • the nanoparticles do not sediment in the thus prepared liquid and the coating or spray has a higher abrasion resistance and is therefore suitable for applications where this resistance is needed.
  • An antimicrobial hydrophobizing liquid is formed from a solution of methyl silicone resin in xylene with a proportion of 50 % by weight and water, the proportion of which je 10 % by weight.
  • the proportion of methyl silicone resin in the emulsion obtained is 45 % by weight.
  • the liquid is homogenized and 5 % by weight of a thickening agent is added to it.
  • the liquid is modified by the addition of 1 % by weight of silver microparticles up to 20 pm in size and by the addition of hydrocarbons with a Ce to C14 content at a concentration of 1 ml/l of the aqueous emulsion of methyl silicone resin. Then the emulsion is homogenized.
  • the addition of hydrocarbons serves to improve the tribological properties of the coating or spray, and silver nanoparticles are highly antimicrobial.
  • the liquid prepared in this manner is suitable, for example, for applications with high requirements for resistance to microbial contamination.
  • An antimicrobial hydrophobizing liquid is formed from a solution of methyl silicone resin in xylene with a proportion of 50 % by weight and water the proportion of which is 10 % by weight.
  • the proportion of methyl silicone resin in the emulsion obtained is 45 % by weight.
  • the liquid is homogenized and 3 % by weight of a thickening agent is added to it.
  • the liquid is modified by adding 0.1 % by weight of silver nanoparticles up to 100 pm in size.
  • a solution of ethyl acetate is also added in an amount of 50 % by weight of the aqueous emulsion and the emulsion is homogenized.
  • Silver nanoparticles exhibit antimicrobial properties even at a minimum concentration and ethyl acetate is used to improve the useful properties of the coating or spray.
  • the liquid prepared in this manner is therefore again suitable for applications with higher requirements for antimicrobial properties.
  • the antimicrobial hydrophobizing liquid according to the invention is intended for the treatment of non-porous materials with a smooth surface, ensuring their hydrophobicity and antimicrobial properties, wherein these properties are achieved even when dried at room temperature. By drying at an elevated temperature, a significantly faster drying time and a slight improvement in surface hydrophobicity can be achieved.

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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to an antimicrobial hydrophobizing liquid for surface treatment/protection of smooth non-absorbent materials containing methyl silicone resin dissolved in xylene. The proportion of methyl silicone resin is in the range of 15 to 70 % by weight in the solution, which further contains nanoparticles and/or microparticles of metals and/or their oxides with antimicrobial properties in an amount of 0.001 to 8 % by weight based on the total weight of the solution pro nanoparticles and in an amount of 0.1 to 8 % by weight based on the total weight of the solution for microparticles, wherein the size of the nanoparticles is in the range of 5 to 1000 nm and the size of the microparticles is in the range of 1 to 50 pm.

Description

Antimicrobial hydrophobizing liquid for surface treatment/protection of smooth non-absorbent materials containing methyl silicone resin
Technical field
The invention relates to an antimicrobial hydrophobizing liquid for surface treatment/protection of smooth non-absorbent materials containing methyl silicone resin dissolved in xylene.
Background art
Non-absorbent materials with a smooth surface are generally at less risk from exposure to moisture than absorbent materials. There is only a danger if the surface is not hydrophobic and the liquid can remain on it, which allows it to contribute to destructive processes, especially corrosion in the case of metals or microbial degradation in the case of other materials during which certain microorganisms can form corrosive compounds, for example, sulfur-oxidizing bacteria can produce biogenic sulfate or sulfuric acid, or fungi and lichens can mechanically erode the surface, to which contributes, among other things, longterm moisture on the surface of materials.
The usual method of protecting materials against corrosion and other destructive phenomena is using a variety of varnishes, coatings or paints which create a layer on the surface of the material and thereby prevent its contact with the external environment, although their properties differ depending on the application. Their properties can also be modified by additives. For example, the addition of metal microparticles or nanoparticles improves the antibacterial properties of the particular coating.
CZ PV 2015-417 discloses a hydrophobizing impregnation liquid with nano-additives for improving the hydrophobic and other useful properties of surfaces, which consists of an aqueous emulsion of methyl silicone resin with a minimum silicone content of 15 % by weight, containing 0.1 to 60 % by weight of a thickening agent in the form of lanolin and/or cetyl alcohol and nanoparticles of zirconium oxide Zr02 in powder form and/or nanoparticles of silicon dioxide SiO2 in powder form and/or nanoparticles of titanium dioxide TiO2 in powder form and/or nanoparticles of aluminium oxide AI2O3 in powder form at a concentration of 0. 01 to 10.0 g/l of the starting aqueous methyl silicone emulsion, wherein the nanoparticles of each oxide used in powder form have a size range of 5 nm to 100 nm and may be used either alone or in combination. The hydrophobic surface treatment will reduce the water absorption of the treated materials, increasing the durability and functionality of the products.
An alternative to varnishes and coatings can be, for example, the application of thin layers of materials with higher chemical resistance, antimicrobial properties or other advantages in comparison with the basic material. An example can be chemical nickel plating or nickel electroplating or applying a thin film by means of plasma-based methods.
The immense importance of antimicrobial treatments which prevent contamination of surfaces by dangerous microorganisms, including bacteria, moulds and viruses, is also becoming apparent nowadays. One of the ways of howto ensure antimicrobial properties is to apply layers of certain metals, especially silver, whose antimicrobial properties are the strongest of metals, or their oxides, or their nanoparticles or microparticles, which ensure antimicrobiality by disrupting the electrostatic potential of cell membranes, by formation of reactive forms of oxygen, such as free radicals or hydrogen peroxide and can also directly damage DNA or cause destructive mutations in these microorganisms.
The object of the invention is to provide hydrophobizing liquid with antimicrobial effects for surface treatment/protection of smooth non-absorbent materials.
Summary of invention
The object of the invention is achieved by a hydrophobizing liquid with antimicrobial effects for surface treatment/protection of non-absorbent surfaces of materials according to the invention, whose principle consists in that the proportion of methyl silicone resin is in the range of 15 to 70 % by weight in the solution which also contains nanoparticles and/or microparticles of metals and/or their oxides with antimicrobial properties in an amount of 0.001 to 8 % by weight based on the total weight of the solution for nanoparticles and in an amount of 0.1 to 8 % by weight based on the total weight of the solution for microparticles, wherein the size of the nanoparticles is in the range of 5 to 1000 nm and the size of the microparticles is in the range of 1 to 50 pm.
Metals and/or their oxides with antimicrobial properties are selected from the group consisting of silver, copper, nickel, zinc, titanium, iron, copper oxide, zinc oxide, titanium dioxide, wherein they can be used either alone or in combination.
Nanoparticles and/or microparticles of the above-mentioned metals and/or their oxides with antimicrobial properties are in powder form.
Nanoparticles of the above-mentioned metals and/or their oxides with antimicrobial properties may be in the form of a colloidal solution.
By adding up to 50 % by weight of water, an aqueous emulsion is formed.
The antimicrobial hydrophobizing liquid may further comprise 0.1 to 60 % by weight of thickening agents, which in a preferred embodiment are formed by cetyl alcohol and/or lanolin.
To improve the tribological properties of the coating, the antimicrobial hydrophobizing liquid contains the addition of hydrocarbons with a C6-C14 content at a concentration of 0.1 - 10 ml/l of the starting solution of methyl silicone resin in xylene or the starting aqueous methyl silicone emulsion, the hydrocarbons being added either alone, or in mutual combination.
To achieve further improvement in the useful properties of the coating, the antimicrobial hydrophobizing liquid contains the addition of ethyl acetate solution in an amount of 0.1 to 60 % by weight of the starting solution of methyl silicone resin or the starting aqueous methyl silicone emulsion.
Examples of embodiment
The antimicrobial hydrophobizing liquid according to the invention is based on methyl silicone resin dissolved in xylene and, if necessary, thickened with conventional thickening agents, for example with cetyl alcohol or lanolin. Nanoparticles and/or microparticles of at least one of metals with antimicrobial properties, such as silver, copper, nickel, zinc, titanium, iron and/or their oxides, such as copper oxide, zinc oxide, titanium dioxide, are added to this solution, wherein mutual combinations of the nanoparticles and/or microparticles of these metals and/or their oxides are also possible. An aqueous emulsion can be formed by adding water to a solution of methyl silicone resin in xylene.
The antimicrobial hydrophobizing liquid contains a solution of methyl silicone resin dissolved in xylene, with 15 to 70 % by weight of methyl silicone resin in a thickened solution (resin + xylene + thickening agents) or in an unthickened solution. The xylene solution of this resin can be used alone as a hydrophobizing coating, however, in order to add nanoparticles and/or microparticles to the powder, it is advisable to thicken it with cetyl alcohol or lanolin, to limit the sedimentation of nanoparticles and/or microparticles with a content of up to 60 % by weight of a thickening agent.
The nanoparticles and/or microparticles of metals and/or their oxides with antimicrobial properties are added to the solution in powder form in an amount of 0.001 to 8 % by weight based on the total weight of the solution for nanoparticles and in an amount of 0.1 to 8 % by weight based on the total weight of the solution for microparticles, whereupon they are thoroughly mixed to ensure that they are evenly dispersed in the solution. This applies to both the unconcentrated and concentrated solution. The mixing method is arbitrary, except for ferromagnetic metals, especially iron and nickel, where magnetic stirrers are not suitable.
The particle size of metals and/or their oxides with antimicrobial properties ranges from 5 to 1000 nm for nanoparticles and from 1 to 50 pm for microparticles.
After the application of the antimicrobial hydrophobizing liquid to the surface of the treated component, the liquid is able to harden even at normal room temperature. To achieve faster curing, a heat treatment may be carried out, namely by at least drying it at a temperature of at least 50 °C for at least 20 minutes. It is also possible to use firing at higher temperatures if the surfaces of thermally stable materials are being treated. In the case of preparing an aqueous emulsion of a solution of methyl silicone resin in xylene, water is added for emulsification in an amount of up to 50 % by weight based on the total weight of the resulting emulsion. This procedure also enables an alternative method to deliver nanoparticles into the resulting liquid, when instead of powdered nanoparticles, an aqueous solution of nanoparticles, a so-called colloidal solution of antimicrobial metals or their oxides, as well as their mutual combination, is used. The nanoparticle size again ranges from 5 to 1000 nm and their concentration in an aqueous solution ranges from 0.01 to 20 g/l. The resulting emulsion must be homogenized. The nanoparticles and microparticles further stabilize the emulsion, and emulsification prevents their sedimentation.
The liquids with microparticles, both emulsions and simple solutions, can be mixed (homogenized) again before use, especially if sedimentation of microparticles occurs.
A mixture of Ce to C14 hydrocarbons (hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and tetradecane) may also be added to the mixture to further improve the water-repellent properties of the resulting liquid.
It is also possible to add to the mixture a solution of ethyl acetate in an amount of 0.1 - 60 % by weight based on the weight of the original solution of methyl silicone resin in xylene or the weight of the aqueous methyl silicone emulsion, for improving the useful properties of the resulting liquid.
Microparticles, nanoparticles, hydrocarbons, as well as ethyl acetate can be used alone or in mutual combination.
To verify the feasibility of the composition and properties of the antimicrobial hydrophobizing liquid according to the invention, the below specific examples of liquids according to the invention were implemented, which serve to clarify the invention, not to limit it.
Example 1
To the solution of methyl silicone resin in xylene with a mass concentration of methyl silicone resin of 50 % by weight, copper microparticles with a particle size of up to 10 pm in size with a proportion of 5 % by weight based on the solution of methyl silicone resin in xylene. Subsequently, the solution was thoroughly mixed to ensure uniform dispersion of the particles in the solution.
The liquid thus prepared must be mixed thoroughly before use, as the microparticles sediment quickly, but their significant aggregation does not occur.
Suitable methods of application of this antimicrobial hydrophobizing liquid are coating or spraying, wherein it is suitable to use it for applications where abrasion is not expected, nor are expected other risks of mechanical damage due to the worse tribological properties of the given microparticles and where equipment is available to mix the liquid before use, whether continuously or once just before use.
Example 2
To the solution of methyl silicone resin in xylene according to Example 1 , 5 % by weight of cetyl alcohol and lanolin were added in a 1/1 ratio relative to the stock solution of methyl silicone resin and 2 % by weight of copper microparticles up to 10 pm in size relative to the stock solution of methyl silicone resin in xylene. The solution was mixed thoroughly to ensure uniform dispersion of the microparticles in the solution.
Even the liquid prepared in this manner should be thoroughly mixed before use, even though in this example the sedimentation of microparticles is slower than in example 1 .
The application can be carried out by spraying or coating, the liquid being usable for applications where abrasion or other risks of mechanical damage due to the inferior tribological properties of the microparticles are not expected and where equipment is available to mix the liquid before use, either continuously or once just before utilization.
Example 3
An antimicrobial hydrophobizing liquid is formed from a solution of methyl silicone resin in xylene with a proportion of 50 % by weight and a colloidal silver solution in which the silver particle sizes range from 5 to 100 nm, with a mass concentration of silver of 50 mg/l. The proportion of the aqueous colloidal solution in the total weight of the liquid was 10 % by weight, the proportion of methyl silicone resin in the resulting solution was therefore 45 % by weight. The emulsion is subsequently homogenized.
The nanoparticles do not sediment in the thus prepared liquid and the coating or spray has a higher abrasion resistance and is therefore suitable for applications where this resistance is needed.
Example 4
An antimicrobial hydrophobizing liquid is formed from a solution of methyl silicone resin in xylene with a proportion of 50 % by weight and water, the proportion of which je 10 % by weight. The proportion of methyl silicone resin in the emulsion obtained is 45 % by weight. Subsequently, the liquid is homogenized and 5 % by weight of a thickening agent is added to it. Next, the liquid is modified by the addition of 1 % by weight of silver microparticles up to 20 pm in size and by the addition of hydrocarbons with a Ce to C14 content at a concentration of 1 ml/l of the aqueous emulsion of methyl silicone resin. Then the emulsion is homogenized.
The addition of hydrocarbons serves to improve the tribological properties of the coating or spray, and silver nanoparticles are highly antimicrobial. The liquid prepared in this manner is suitable, for example, for applications with high requirements for resistance to microbial contamination.
Example 5
An antimicrobial hydrophobizing liquid is formed from a solution of methyl silicone resin in xylene with a proportion of 50 % by weight and water the proportion of which is 10 % by weight. The proportion of methyl silicone resin in the emulsion obtained is 45 % by weight. Subsequently, the liquid is homogenized and 3 % by weight of a thickening agent is added to it. Next, the liquid is modified by adding 0.1 % by weight of silver nanoparticles up to 100 pm in size. To the thus obtained aqueous emulsion, a solution of ethyl acetate is also added in an amount of 50 % by weight of the aqueous emulsion and the emulsion is homogenized.
Silver nanoparticles exhibit antimicrobial properties even at a minimum concentration and ethyl acetate is used to improve the useful properties of the coating or spray. The liquid prepared in this manner is therefore again suitable for applications with higher requirements for antimicrobial properties.
Industrial applicability
The antimicrobial hydrophobizing liquid according to the invention is intended for the treatment of non-porous materials with a smooth surface, ensuring their hydrophobicity and antimicrobial properties, wherein these properties are achieved even when dried at room temperature. By drying at an elevated temperature, a significantly faster drying time and a slight improvement in surface hydrophobicity can be achieved.

Claims

9 PATENT CLAIMS
1. An antimicrobial hydrophobizing liquid for surface treatment/protection of smooth non-absorbent materials containing methyl silicone resin dissolved in xylene, characterized in that the proportion of methyl silicone resin is in the range of 15 to 70 % by weight in the solution which further contains nanoparticles and/or microparticles of metals and/or their oxides with antimicrobial properties in an amount of 0.001 to 8 % by weight based on the total weight of the solution for nanoparticles and in an amount of 0.1 to 8 % by weight based on the total weight of the solution for microparticles, wherein the size of the nanoparticles is in the range of 5 to 1000 nm and the size of the microparticles is in the range of 1 to 50 pm.
2. The antimicrobial hydrophobizing liquid according to claim 1 , characterized in that the metals and/or their oxides with antimicrobial properties are selected from the group consisting of silver, copper, nickel, zinc, titanium, iron, copper oxide, zinc oxide, titanium dioxide, either alone or in combination.
3. The antimicrobial hydrophobizing liquid according to claim 2, characterized in that the nanoparticles and/or microparticles of metals and/or their oxides with antimicrobial properties are in powder form.
4. The antimicrobial hydrophobizing liquid according to claim 2, characterized in that the nanoparticles of metals and/or their oxides with antimicrobial properties are in the form of a colloidal solution.
5. The antimicrobial hydrophobizing liquid according to any of claims 1 to
4, characterized in that it further contains up to 50 % by weight of water, thereby forming an aqueous emulsion.
6. The antimicrobial hydrophobizing liquid according to any of claims 1 to
5, characterized in that it further contains 0.1 to 60 % by weight of a thickening agent.
7. The antimicrobial hydrophobizing liquid according to claim 6, characterized in that the thickening agent consists of cetyl alcohol and/or lanolin.
8. The antimicrobial hydrophobizing liquid according to any of claims 1 to 7, characterized in that it further contains hydrocarbons with a Ce - C14 content at a concentration of 0.1 - 10 ml/l of the starting solution of methyl silicone resin in xylene or of the starting aqueous methyl silicone emulsion, either alone, or in mutual combination.
9. The antimicrobial hydrophobizing liquid according to any of claims 1 to 7, characterized in that it further contains an ethyl acetate solution in an amount of 0.1 to 60 % by weight based on the weight of the starting solution of methyl silicone resin or of the starting aqueous methyl silicone emulsion.
PCT/CZ2022/050093 2021-12-09 2022-09-16 Antimicrobial hydrophobizing liquid for surface treatment/protection of smooth non-absorbent materials containing methyl silicone resin WO2023104224A1 (en)

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