Composition for producing a coating having antibacterial properties

Abstract

To provide a curable composition for production of coatings with an antimicrobial property.SOLUTION: A curable composition contains at least one film-forming polymer, at least one up-conversion phosphor, and optionally at least one additive and one curing agent. The phosphor is selected from the idealized general formula (I), A1-x-y-zB*yB2SiO4:Ln1x,Ln2z, where x=0.0001-0.05, z=0 or z=0.0001 to 0.3, and y=x+z; A is selected from Mg, Ca, Sr and Ba; B is selected from Li, Na, K, Rb and Cs; B* is selected from Li, Na and K; Ln1 is selected from praseodymium (Pr), erbium (Er), and neodymium (Nd); and Ln2 is optionally selected from gadolinium (Gd).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a curable composition for producing an antibacterial coating, its use, a coating produced from the composition, and a product coated with the coating.

Background Art

[0002] Humans are exposed to millions of microorganisms such as bacteria, fungi, and viruses every day. Many of these microorganisms are useful or even essential. Nevertheless, in addition to these representative microorganisms with low harmfulness, there are also bacteria, fungi, and viruses that cause diseases or even lead to death.

[0003] Microorganisms can be transmitted through daily contact with others and contact with items used by others. Especially in hygienically sensitive places, the surfaces are given an antibacterial finish. Specific fields of use are the surfaces of medical devices and consumables in hospitals and outpatient health and welfare facilities. In addition to these, there are surfaces in the public sphere, the food and beverage sector, and animal breeding. The spread of pathogenic microorganisms is currently a major problem in the nursing sector, medicine, and places where many people are active in closed spaces. The current specific risk is the increasing occurrence of so-called multi-drug resistant bacteria that are resistant to standard antibiotics.

[0004] In addition to standard hygiene measures, antibacterial technologies and antibacterial materials are used to reduce the risk of pathogen diffusion through contact surfaces. The use of chemical substances and physical methods can have a significant impact on the microbial reproduction process. Physical methods include, for example, heat, cold air, radiation, or ultrasonic waves. Among chemical methods, halogens, metal ions, organic compounds, organic dyes, and toxic gases are known.

[0005] Chemical and physical methods are, in most cases, very effective in destroying microorganisms, but their effects are short-lived, promote the development of resistance, and can lead to the destruction of the surface to be protected, making them unsuitable for application in some cases. However, the biggest drawback, especially in the case of chemical organic substances, is the danger or toxicity to the human body. Certain substances such as formaldehyde, which has been used as a disinfectant for many years, are now suspected of causing cancer or being very harmful to the environment.

[0006] Surfaces with antibacterial properties can potentially make an important contribution to solving these problems. In today's standard methods for obtaining such antibacterial properties, mainly active ingredients incorporated into the material, such as silver particles, copper particles, their metal oxides, or quaternary ammonium compounds, are utilized. This often involves the process of treating antibacterial metals, antibacterial metal oxides, or antibacterial metal oxide mixtures to generate nanoparticles, and then mixing them into paints, coatings, or polymer materials. There are doubts about the widespread use of metal particles because it is almost impossible to evaluate the long-term effects of these heavy metals on humans and the environment.

[0007] For example, Patent Document 1 discloses particles finished with a layer containing both antimony tin oxide and manganese oxide. A person skilled in the art would notice that in the absence of moisture, a microscale galvanic cell is developed, and due to the electrochemical properties of the metal that produces a bactericidal effect by a microscale electric field, the antibacterial surface is generated.

[0008] Similarly, for example, it is known that UV irradiation can be used in medicine and hygiene to disinfect water, gas, or surfaces. For example, UV irradiation has long been used in drinking water treatment to reduce the number of pathogenic microorganisms in water. This is preferably done using UV-C irradiation in the wavelength range of 100 nm to 280 nm. When using electromagnetic radiation of different wavelengths, it is necessary to consider the different absorption effects of various proteins, amino acids / nucleic acids (e.g., DNA) present in microorganisms, tissues, or cells, and the peptide bonds between individual acids. For example, DNA absorbs electromagnetic radiation in the wavelength range of 200 nm to 300 nm well, especially at 250 nm to 280 nm, so this radiation is particularly suitable for DNA. Therefore, such irradiation can inactivate pathogenic microorganisms (especially viruses, bacteria, yeasts, molds). Depending on the duration and intensity of the irradiation, the DNA structure can be destroyed. Therefore, it is possible to inactivate metabolically active cells and / or cause them to lose their replication ability. The advantage of ultraviolet irradiation is that microorganisms do not have resistance to ultraviolet light.

[0009] Furthermore, in addition to the direct irradiation of electromagnetic radiation from the ultraviolet wavelength range, it is also known to utilize the so-called upconversion effect. This is to use phosphor particles that can convert electromagnetic radiation with a longer wavelength than ultraviolet light (especially visible light or infrared light) into electromagnetic radiation with a shorter wavelength in such a way that the emission of radiation with the desired effect can be achieved by individual phosphor particles.

[0010] Patent Document 2 relates to an emitter of electromagnetic radiation in the ultraviolet wavelength range. The phosphor particles are embedded in the emitter in a region near the surface of the material forming the emitter or in the coating of the emitter. Generally stated are the direct addition of phosphor particles to the coating formed on the material during processing and the need for specific active ingredients to have an appropriate consistency or viscosity. Patent Document 2 does not describe suitable polymers and additives.

[0011] Patent Documents 3 and 4 describe phosphors that can be incorporated into polyvinyl chloride, acryloyl butadiene, olefins, polycarbonates, styrenes, or nylons, and these phosphors kill pathogenic microorganisms by the upconversion properties of the phosphors. These are phosphors prepared at temperatures of 1,800°C to 2,900°C. Further, Patent Document 3 discloses a liquid composition containing polyurethane, an acrylate polymer, and a filler, and optionally a crosslinking agent. Patent Document 3 deals with the antibacterial action of the phosphor, but does not explain the compatibility of the components in the coating composition or the properties of the coating surface (e.g., paint surface). However, the appearance of the coating surface is of utmost importance to consumers.

[0012] Patent Documents 3 and 4 disclose compositions containing the above-mentioned phosphors that are claimed to have antibacterial action, but no evidence of upconversion properties or microbiological studies are shown. The disclosed methods produce amorphous and glassy products rather than phosphors having upconversion properties.

[0013] The requirements for paints and coatings are diverse. In principle, paints or coatings have two tasks or functions (i.e., a protective function and a decorative function). Hereinafter, when it is necessary to simply mention the term "coating", both types of coatings are intended. They decorate, protect, and preserve materials such as wood, metal, or plastic. Therefore, on the one hand, a bright and glossy paint layer is required, and on the other hand, a continuous coating layer is required to ensure chemical and mechanical resistance, specific coating surface slipperiness, or specific tactility.

Prior Art Documents

Patent Documents

[0014]

Patent Document 1

Patent Document 2

[0015] Therefore, the problem to be solved by the present invention is to provide a curable composition of the first-defined type, and by using said composition, it is possible to produce a coating that provides long-term protection against microorganisms without significantly impairing other properties (especially storage stability).

[0016] Therefore, this problem is a curable composition for producing a coating having antibacterial properties, - at least one film-forming polymer, - at least one upconversion phosphor, - optionally, at least one additive, - optionally, at least one curing agent, comprising, The problem is solved by providing a curable composition in which the phosphor is selected from the following ideal general formula (I). A 1-x-y-z B* y B2SiO4:Ln 1 x, Ln 2 z, (I) (wherein x = 0.0001 to 0.05, z = 0 or z = 0.0001 to 0.3, and y = x + z, A is selected from Mg, Ca, Sr, and Ba, B is selected from Li, Na, K, Rb, and Cs, B* is selected from Li, Na, and K, B is the same as B*, or not the same as B*, and B and B* are preferably not the same, Ln 1 is selected from praseodymium (Pr), erbium (Er), and neodymium (Nd), Ln 2 is optionally selected from gadolinium (Gd).)

[0017] Surprisingly, it has been found that coatings having antibacterial action and not impairing the surface profile can be produced using the compositions of the present invention.

[0018] The phosphor is preferably doped with praseodymium used in the composition according to the present invention.

[0019] In the composition according to the present invention, the phosphor is preferably doped with praseodymium and codoped with gadolinium.

[0020] The phosphor is preferably a solidified melt of a crystalline silicate containing at least one alkali metal ion and at least one alkaline earth metal ion, or a solidified melt of a crystalline silicate containing at least one alkali metal ion and at least one alkaline earth metal ion and doped with a lanthanoid ion.

[0021] In the composition according to the present invention, the phosphor is preferably selected from the following ideal general formula (Ia). A 1-x-y-z B* y B2SiO4:Pr x, Gd z, (Ia) (In the formula, A is Mg, Ca, Sr, Ba, and B is Li, Na, K, Rb, Cs, x = 0.0001 to 0.05, z = 0 or z = 0.0001 to 0.3, and y = x + z, B* is selected from Li, Na, and K and balances the charge of the silicate, B is the same as B*, or is not the same as B*, and B and B* are preferably not the same.)

[0022] In the composition according to the present invention, the phosphor is preferably selected from the following general formula (II). (Ca 1-a Sr a ) 1-2b Ln b Na b Li2SiO4 (II) (wherein a = 0.0001 to 1, preferably 0.0001 to 0.1, b = 0.0001 to 1, preferably 0.0001 to 0.1, Ln is a lanthanoid ion selected from praseodymium, gadolinium, erbium, neodymium, and is a lanthanoid ion for co-doping at least one of these, preferably gadolinium.)

[0023] It should be noted that the phosphor required for the present invention is disclosed in European Patent Application No. 19202910.6, which is a previous European patent application before publication.

[0024] When the phosphor is irradiated with low-energy electromagnetic radiation having a long wavelength in the range of 2,000 nm to 400 nm, particularly 800 nm to 400 nm, it emits high-energy electromagnetic radiation having a short wavelength in the range of 400 nm to 100 nm, preferably 300 nm to 200 nm, and the maximum irradiation intensity of the high-energy electromagnetic radiation having the short wavelength is at least 1·10 3 counts / (mm 2 ·s), preferably higher than 1·10 4 counts / (mm 2 ·s), more preferably higher than 1·10 5 counts / (mm 2 ·s). The emission spectrum is excited by a laser (particularly a laser with an output of 75 mW at 445 nm and / or an output of 150 mW at 488 nm).

[0025] The phosphor of formula (II) is preferably It has XRPD signals in the ranges of 23° 2Θ to 27° 2Θ and 34° 2Θ to 39.5° 2Θ, and the signals are measured by Bragg-Brentano geometry and Cu-Kα radiation. Details of the test method are described in European Patent Application No. 19202910.6 before publication.

[0026] European Patent Application No. EP19202910.6 before publication deals with the preparation of phosphors, in particular phosphors of formula (I), formula (Ia) and formula (II). It describes a method having the following steps. -i) A step of preparing at least one lanthanoid salt selected from lanthanoid nitrates, lanthanoid carbonates, lanthanoid carboxylates, preferably lanthanoid acetates, lanthanoid sulfates, lanthanoid oxides, more preferably Pr6O 11 and / or Gd2O3, wherein the lanthanoid ions in the lanthanoid oxide or lanthanoid salt are selected from praseodymium, gadolinium, erbium, neodymium, and are used for co-doping at least two of them, -ii) A step of preparing silicic acid, preferably a silicate, more preferably an alkali metal salt of a silicate, -iii) A step of preparing at least one alkaline earth metal salt and at least one alkali metal salt, preferably an alkali metal silicate selected from lithium salts or lithium compounds and optionally selected from sodium salts and potassium salts (preferably an alkali metal silicate selected from lithium salts, i.e., lithium silicate), -a) A step of mixing i), ii) and iii) by grinding to obtain a mixture, or -b) Mixing i), ii) and iii) in an aprotic organic polar / non-polar solvent to obtain a mixture, and firing the mixture of b) at 600 °C to 1,000 °C (step 1a) to remove the organic components, preferably firing at 600 °C to 1,000 °C for at least 1 hour, preferably 2 hours or more, in a normal (air) atmosphere to obtain a fired mixture, Firing the mixture of -a) or the fired mixture of b) (preferably firing the mixture of -a) or the fired mixture of b) in air at a temperature lower than the melting temperature of the silicate material), and in order to crystallize the silicate material, (preferably in a further firing step (i.e., a firing step carried out at a temperature of 50°C to 200°C for at least 3 hours, preferably in air at a temperature lower than the melting temperature of the silicate-based material) (step 1b)), performing at least partial crystallization (preferably performing at least partial crystallization at a temperature of 800°C to 900°C, more preferably at about 850°C, for at least 3 hours, preferably for at least 12 hours, preferably in air). - In a further firing step, raising the temperature (preferably above 800°C and up to a temperature 50°C to 200°C lower than the melting point of the material (e.g., 850°C)) (step 2), and reducing the lanthanoid to Ln 3+ ions in a reducing atmosphere for at least 3 hours, more preferably for at least 6 hours. - Preferably, after cooling the material, obtaining a silicate-based lanthanoid ion-doped material. A more detailed embodiment of this method can be found in European Patent Application No. 19202910.6.

[0027] Surprisingly, it has been found that the phosphors according to European Patent Application No. 19202910.6 have the necessary upconversion properties that are factors in antibacterial action. In other words, these phosphors can convert electromagnetic radiation with a longer wavelength (especially visible light or infrared light) to electromagnetic radiation with a shorter wavelength than ultraviolet light, particularly in regions where, for example, the DNA of microorganisms can be destroyed. Therefore, these phosphors have very good compatibility with the compositions according to the present invention.

[0028] The preparation of the phosphor according to the present invention can also be considered as follows: The starting materials used are CaCO3 (Alfa Aesar, 99.5%), Li2CO3 (Alfa Aesar, 99%), SiO2 (Aerosil 200, manufactured by Evonik), Pr6O 11(Treibacher, 99.99%) and Na2CO3 (Merck, 99.9%). A stoichiometric mixture of these compounds is mixed in acetone for 30 minutes. Once the acetone has completely evaporated at room temperature, the mixture is transferred to a crucible. The mixture is fired twice. The first firing is carried out in a melting furnace at 850 °C for 12 hours while supplying air, and the second firing is carried out at 850 °C for 6 hours under 95 / 5 N2 / H2. Thereafter, the final product is ground in an agate mortar.

[0029] A further problem to be solved by the invention is the selection of a film-forming polymer that can be used in a curable composition having antibacterial properties. In principle, all film-forming polymers known from the prior art are useful.

[0030] The film-forming polymer preferably has a functional group, preferably an acidic hydrogen that reacts with an isocyanate-containing curing agent and is catalyzed by a catalyst if necessary.

[0031] Advantageously, the film-forming polymer is selected from the group consisting of hydroxy-functional acrylate polymers, hydroxy-functional polyester polymers, and / or hydroxy-functional polyether polymers, hydroxy-functional cellulose derivatives, amino-functional aspartic acid polymers or amino-functional polyester polymers, and reacts with an isocyanate-containing curing agent.

[0032] The film-forming polymer preferably has low resonance.

[0033] One skilled in the art will notice the physical interactions on the surface. Depending on the material and its surface, many effects occur on the surface with respect to the incident light. The incident light is partially absorbed, partially reflected, and scattered depending on the material surface. The light may also be absorbed first and then emitted again. In the case of opaque, translucent, or transparent materials, the light can pass through the body (transmittance). In some cases, the light may also be polarized or diffracted at the surface. Among objects, there are those that emit light (backlit displays, LED segments, displays) and those that fluoresce or phosphoresce with light of different colors (afterglow).

[0034] "Low resonance" in the context of this specification means that the absorbability, reflectivity, reflectance, and scatterability of the film-forming polymer are low. In contrast, the transmittance is preferably significant.

[0035] The reason is that, surprisingly, the film-forming polymer according to the present invention with low resonance transmits more low-energy electromagnetic radiation having a long wavelength in the range of 2,000 nm to 400 nm, particularly 800 nm to 400 nm, and as a result, can emit more high-energy electromagnetic radiation having a short wavelength in the range of 400 nm to 100 nm, preferably 300 nm to 200 nm. Therefore, the film-forming polymer according to the present invention with low resonance has an improved antibacterial effect.

[0036] It has been found that the higher the transmittance, the higher the emission amount, which is important for the antibacterial effect.

[0037] The transmittance of the film-forming polymer is preferably at least 75%, more preferably at least 80%, and particularly preferably at least 85% when measured at a wavelength of 260 nm.

[0038] The transmittance of the film-forming polymer, when measured at a wavelength of 500 nm, is preferably at least 75%, more preferably at least 80%, and particularly preferably at least 85%. It should be noted that, as an example, the transmittance can be defined at different wavelengths (see Figure 1). In the present invention, a wavelength of 260 nm is selected as an example of the emission wavelength, and a wavelength of 500 nm is selected as an example of the excitation wavelength. These first affect upconversion and second have a significant impact on the antibacterial action.

[0039] For example, when the transmittance measured at a wavelength of 260 nm is 100%, the same amount of radiation is converted and emitted. In other words, there is no loss due to absorption, scattering, etc. When the transmittance measured at a wavelength of 260 nm is 80%, presumably 20% is not transmitted, probably due to absorption, reflection, reflectivity, and / or scattering. Therefore, only 80% of the radiation at a wavelength of 260 nm can be emitted.

[0040] This important discovery is significant in the selection of the film-forming polymer. For example, polymers with a transmittance of 0% are not suitable for the curable composition according to the present invention. They do not transmit any low-energy electromagnetic radiation of high wavelengths, and thus the luminophores present in the composition cannot convert this electromagnetic radiation into high-energy electromagnetic radiation of short wavelengths and emit it. This is a requirement for the antibacterial action.

[0041] Preferably, the composition according to the present invention has a transmittance of at least 75%, preferably at least 80%, more preferably at least 85% when measured at 260 nm.

[0042] Preferably, the composition according to the present invention has a transmittance of at least 75%, preferably at least 80%, more preferably at least 85% when measured at 500 nm.

[0043] The transmittance is preferably measured with a "Specord 200 Plus" twin-beam UV / VIS spectrophotometer manufactured by Analytik Jena. Anholmium oxide filter is used for internal wavelength calibration. Monochromatic light from a deuterium lamp (UV range) or a tungsten halogen lamp (visible range) passes through the sample. The spectral bandwidth is 1.4 nm. The monochromatic light is split into a measurement channel and a reference channel, enabling direct measurement against a reference sample. The radiation passing through the sample is detected and processed by a photodiode.

[0044] It is conceivable to use compositions with a transmittance of less than 70%. They probably also have an antibacterial effect, but the effect is rather moderate.

[0045] The average particle size (d50) of the phosphor, measured in accordance with ISO 13320:2020 and USP 429 using, for example, a LA-950 laser particle size analyzer from Horiba, is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm. In order to efficiently incorporate and / or stabilize the phosphor in the composition according to the present invention, various additives can preferably be added.

[0046] The additives are preferably selected from the group consisting of dispersants, rheology aids, leveling agents, wetting agents, defoamers, and UV stabilizers.

[0047] Surprisingly, it has been found that adding additives to the composition according to the present invention results in a decrease in transmittance.

[0048] Therefore, in a further embodiment where additives are used, the composition according to the present invention preferably has a transmittance of at least 70%, preferably at least 75%, more preferably at least 80% when measured at 260 nm.

[0049] Thus, in a further embodiment where an additive is used, the composition according to the invention preferably has a transmittance of at least 70%, preferably at least 75%, more preferably at least 80% when measured at 500 nm.

[0050] Preferably, the composition according to the invention comprises a curing agent selected from the group consisting of aliphatic or cycloaliphatic isocyanates.

[0051] Examples of isocyanate-containing curing agents are monomeric isocyanates, polymeric isocyanates, and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates because they are less toxic. Examples of polyisocyanates are isocyanurates, uretdiones, and biurets based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). Examples of commercial products are those with the trade name DESMODUR® from Covestro or VESTANAT from Evonik Industries. Known products are DESMODUR® N3400, DESMODUR® N3300, DESMODUR® N3600, DESMODUR® N75, DESMODUR® XP2580, DESMODUR® Z4470, DESMODUR® XP2565, and DESMODUR® VL from Covestro. Other examples are VESTANAT® HAT 2500 LV, VESTANAT® HB 2640 LV, or VESTANAT® T1890E from Evonik Industries. Examples of isocyanate prepolymers are DESMODUR® E XP 2863, DESMODUR® XP 2599, or DESMODUR® XP 2406 from Covestro. Other isocyanate prepolymers known to those skilled in the art may also be used.

[0052] It is conceivable to use a catalyst for hardening. The following catalysts selected from organic Sn(IV), Sn(II), Zn, Bi compounds or tertiary amines may be used. It is preferable to use a catalyst selected from the group consisting of an organotin catalyst, a titanate or zirconate, an organometallic compound of aluminum, iron, calcium, magnesium, zinc or bismuth, a Lewis acid or an organic acid / base, a linear or cyclic amidine, guanidine or an amine, or a mixture thereof.

[0053] The curing catalyst used is an organotin compound, for example, dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin dilaurate, dioctyltin diacetylacetonate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, dioctyltin oxide, preferably dioctyltin dicarboxylate, dioctyltin dilaurate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, dioctyltin oxide, more preferably dioctyltin diacetylacetonate and dioctyltin dilaurate. Further, zinc salts such as zinc octoate, zinc acetylacetonate and zinc-2-ethyl caproate, or tetraalkylammonium compounds such as N,N,N-trimethyl-N-2-hydroxypropylammonium hydroxide, N,N,N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate or choline 2-ethylhexanoate can also be used. It is preferable to use zinc octoate (zinc 2-ethylhexanoate) and tetraalkylammonium compounds, and it is particularly preferable to use zinc octoate.More preferably, a bismuth catalyst (e.g., TIB Kat (TIB, Mannheim) or Borchi® catalyst), a titanate (e.g., titanium(IV) isopropoxide), an iron(III) compound (e.g., iron(III) acetylacetonate), an aluminum compound (e.g., aluminum triisopropoxide, aluminum tri-sec-butoxide, other alkoxides, aluminum acetylacetonate), a calcium compound (e.g., calcium disodium ethylenediaminetetraacetate or calcium diacetylacetonate), or an amine (e.g., triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, N-ethylmorpholine). Also preferred as the catalyst are organic or inorganic Bronsted acids (e.g., acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid or benzoyl chloride), hydrochloric acid, phosphoric acid, and their monoesters and / or diesters (e.g., butyl phosphate, (iso)propyl phosphate, dibutyl phosphate). Guanidine-containing organic and organosilicon compounds are also preferred. Of course, it is also possible to use two or more catalysts in combination. Further, as described in International Publication No. 2005 / 100482, it is also possible to use a photo latent base as the catalyst.

[0054] The curing catalyst is preferably used in an amount of 0.01% to 5.0% by weight, more preferably 0.05% to 4.0% by weight, and particularly preferably 0.1% to 3% by weight based on the total mass of the curable composition.

[0055] In the case of a film-forming polymer that cures by physical drying, the addition of a reactive curing agent is not necessary.

[0056] The composition according to the invention may preferably be used in a 1K (one-component) coating system or a 2K (two-component) coating system, a melamine baking system, or a room temperature or high temperature system.

[0057] Preferably, the coating made from the composition according to the invention has an antibacterial action against bacteria, yeast, mold, algae, parasites and viruses.

[0058] The coating produced according to the invention preferably has an antibacterial action against the following. - Pathogens of nosocomial infections, preferably Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, Escherichia coli, Enterobacter, Corynebacterium diphtheriae, Candida albicans, Rotavirus, Bacteriophage; - Opportunistic pathogenic environmental organisms, preferably Cryptosporidium parvum, Giardia lamblia, amoeba (Acanthamoeba genus, Naegleria genus), Escherichia coli, coliform group, fecal streptococcus, Salmonella genus, Shigella genus, Legionella genus, Pseudomonas aeruginosa, Mycobacterium genus, enterovirus (e.g. poliovirus and hepatitis A virus); - Pathogens in food and beverages, preferably Bacillus cereus, Campylobacter genus, Clostridium botulinum, Clostridium welchii, Cronobacter genus, Escherichia coli, Listeria monocytogenes, Salmonella genus, Staphylococcus aureus, Vibrio genus, Yersinia enterocolitica, Bacteriophage.

[0059] The invention further provides the use of the composition according to the invention for producing a dispersion, a kneaded pigment, an adhesive, a trowel compound, plaster, paint, a coating or printing ink, an inkjet, a kneaded resin, or a pigment concentrate.

[0060] The use of the composition according to the invention for producing a coating having antibacterial properties is preferred.

[0061] A coating having antibacterial action or antibacterial properties means that the coating has an antibacterial surface that restricts or prevents the growth and proliferation of microorganisms.

[0062] Surprisingly, the coatings according to the present invention have been found to have chemical and mechanical stability. Chemical and mechanical stability is particularly important since antibacterial coatings are often used in places where regular disinfection and other hygiene measures are required.

[0063] The present invention also encompasses a method for forming an antibacterial coating on a substrate, (a) at least one film-forming polymer having a functional group that reacts with an isocyanate-containing curing agent and optionally catalyzed by a catalyst, (b) at least one emitter of formula (II), (c) a curing agent containing an isocyanate functional group, and applying a curable film-forming composition comprising the same to the substrate.

[0064] Preferably, the substrate consists of metal, mineral substrates (e.g., concrete, natural rock or glass), cellulose substrates, wood, and mixtures thereof, dimensionally stable polymers and / or thermosets.

[0065] The term "dimensionally stable polymer" is understood to mean, although not definitively, the following polymers: acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polylactic acid (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polystyrene (PS), polyether ether ketone (PEEK), polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE).

[0066] Preferably, a primer composition may be applied to the substrate prior to application of the curable film-forming composition.

[0067] Preferably, the curable composition according to the present invention is used for coating substrates in sanitary facilities and hospitals as well as in the food and beverage industries.

[0068] This may include all installations in the public sector such as schools, nursing homes, commercial kitchens, nurseries, etc.

[0069] A further invention is an article at least partially, preferably completely coated with the curable composition according to the present invention.

[0070] It should be noted that the terms "antibacterial effect", "antibacterial property", "antibacterial action" and "antibacterial characteristic" are used as synonyms.

[0071] What is shown below is only an example used to explain the present invention to those skilled in the art and does not limit any of the subject matters described in the claims.

Brief Description of the Drawings

[0072]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Example

[0073] Method Measurement of transmittance The measured transmittance values were measured using an "Analytik Jena Specord 200 Plus" twin-beam UV / VIS spectrophotometer. A holmium oxide filter was used for internal wavelength calibration. Monochromatic light from a deuterium lamp (UV range) or a tungsten halogen lamp (visible range) was passed through the sample. The spectral bandwidth was 1.4 nm. The monochromatic light was split into a measurement channel and a reference channel, enabling direct measurement against a reference sample. The radiation transmitted through the sample was detected and processed by a photodiode. The measurements were carried out in transmission mode. The measurement range was 190 nm to 1,100 nm, and the step width was 1 nm. The measurement speed was 10 nm / s (corresponding to an integration time of 0.1 s).

[0074] Equipment Speed mixer, model: FAC 150.1 FVZ, manufactured by Hauschild Engineering Dispermat, equipment type: CV2-SIP, manufactured by Getzmann Reflectometer, equipment type: ZGM 1130, manufactured by Zehntner Testing Instruments Cross-Cut Tester, DIN EN ISO 2409, MTV Messtechnik oHG, Type: CCP Cross-Cut Stencil Set Checkerboard Erichsen Test, Type 202, manufactured by Erichsen MEK Twin Stroke Test, Type: Tester Bezel Type, manufactured by Bruno Pellizzato Rotational Viscometer, manufactured by Anton Paar, Instrument: Viskotherm VT 2 Spectrophotometer for Color Locus Measurement, manufactured by X-Rite, Instrument Type: SP 62 Laboratory Electronic Balance, Sartorius MSE 6202 S 100 DO Hemocytometer (Thoma Count Chamber), manufactured by Brandt Vortex Bath, manufactured by Byk Gardner, GFL 1083 Specord 200 Plus Twin-Beam UV / VIS Spectrophotometer, manufactured by Analytik Jena

[0075] Nutrient Medium CASO Culture Medium, manufactured by Merck KGaA Millipore CASO Nutrient Agar Plate, manufactured by Oxoid

[0076] Disinfectant Bacillol® AF, manufactured by Hartmann [Table 1] [Table 2]

[0077] 1. Selection of Film-Forming Polymer Using the measured transmittance, a film-forming polymer suitable for the composition according to the present invention was selected. 1.1 Preparation of Composition Containing No Phosphor and Additive The polymer matrices P1 to P6 were prepared as follows. P1 and P2 are one-component systems that dry physically. P3 to P6 are two-component systems that cure chemically. The polymers in Table 1 were diluted or dissolved in butyl acetate in the amounts listed in Table 3 (exception: Polyimide P84® NT, used as a stock solution). Subsequently, 20 g of this polymer solution was weighed into a 50 mL plastic cup. The curing agent and / or catalyst was added immediately before application. Next, the polymer matrix was homogenized at 2,000 rpm for 1 minute with a speed mixer. [Table 3]

[0078] 1.2 Coating of the polymer matrix on a quartz plate To obtain a dry layer thickness of 30 μm in the dry state, P1 to P6 were applied to a quartz plate using a suitable spiral coater. These were dried / cured at room temperature (23 °C) for 10 days.

[0079] 1.3 Measurement of transmittance Subsequently, the UV / VIS transmission spectrum was measured. The polymer matrices P1, P4, and P6 exhibit high transmittance in the wavelength ranges of 450 nm to 500 nm (blue light) and 250 nm to 300 nm (UV-C / B light) (Figure 1), and Table 4 shows the transmittance at wavelengths of 260 nm and 500 nm. The transmittance of P1, P4, and P6 exceeds 80% at both wavelengths. Therefore, it is possible to use the film-forming polymers Degalan® 64 / 12 (P1), Dynacoll® AC 3820 (P4), and CAB® 381-2P6 (P6) in the composition according to the invention for producing a coating having antibacterial properties. Polyimide P84® NT of P2 can be used as a comparative polymer because its transmittance at a wavelength of 260 nm is zero. [Table 4]

[0080] 2. Selection of Additives For the optimization of coating properties and the stabilization of the emitter, various additives were tested with the polymer matrix P4, for example, with respect to precipitation in the liquid composition according to the invention. The compatibility with respect to the functional compatibility of the additives as well as the influence on the transmittance was also tested. For this purpose, the UV / VIS transmittance spectra of formulations containing various additives in the polymer matrix P4 were measured. 2.1 Measurement of Transmittance For this purpose, the polymer matrix P4 (20 g) was weighed together with the amount of additive to be tested (see Table 5) and homogenized at 2,000 rpm for 1 minute in a speed mixer. Immediately before application, the curing agent and catalyst were added and the mixture was homogenized again at 2,000 rpm for 1 minute in a speed mixer. These mixtures P4-1 to P4-17 were applied to a quartz glass plate and an aluminum sheet using a spiral applicator and dried / cured at room temperature for 10 days. Their transmittance and coating properties were tested. Referring to the UV / VIS transmittance spectra, the additives TEGO® Dispers 628, TEGO® Dispers 670, TEGO® Dispers 688, SPHERILEX® DP0111, SPHERILEX® DP0112, SPHERILEX® DP0115, AEROSIL® R 972, AEROSIL® 200, BENTONE SD®-2, BENTONESD®-3, and BENTONE® 38 are suitable for the composition according to the invention because they do not significantly reduce the required transmittance with respect to the transmittance of the film-forming polymer either (see Table 2). Their transmittance exceeds 70%. A transmittance of less than 70% was measured for the additives TEGO® Dispers 710, TEGO® Dispers 650, TEGO® Dispers 652, TEGO® Dispers 630, TEGO® Dispers 689, and TEGO® Dispers 1010 (Table 5).

Table 5

[0081] 2.2 Coating property tests of the polymer matrix without a phosphor The liquid polymer matrix was applied to a Bonder 26s 6800 OC sheet with a spiral applicator and dried / cured at 23 °C for 10 days. A final dry layer thickness of 30 μm was obtained. The following coating properties were verified according to standard DIN and ISO standards. · Gloss · König pendulum hardness · Cross-cut test · Erichsen cupping test · MEK twin stroke test · Chemical stability against ketchup, coffee, sulfuric acid (50% aqueous solution), sodium hydroxide solution (10% aqueous solution), and sunscreen. For sunscreen, after applying to the surface of the coating, it was exposed to 60 °C in an oven for 1 hour. For all other chemicals, it was maintained at room temperature for 16 hours before removal, and then the damage to the coating surface was evaluated. · Bacillol twin stroke test: Bacillol® AF is suitable for the rapid disinfection of alcohol-resistant surfaces by the spray / wiping method. The coating properties were tested for the polymer matrices P3 - P6 (Table 6). The polymer matrices P4 and P6 were found to meet typical coating properties. Therefore, these can be used in subsequent tests.

Table 6

[0082] 3. Antibacterial effect test 3.1 Selection of phosphor The following phosphors were used. ·Lu2CaAl4SiO 12 :Pr 3+ 、Gd 3+ 、Prepared according to Example 6 of European Patent Application No. 19202897.5 before publication ·CaLi2SiO4:Pr 3+ 、Na + (1%), Prepared according to Example 1 of European Patent Application No. 19202910.6 before publication ·CaLi2SiO4, Prepared according to Example 1 of European Patent Application No. 19202910.6 before publication without using praseodymium ·Li4P2O7, Prepared by the following method: 1.8473 g (25.0000 mmol) of Li2O3 and 2.8756 g (25.000 mmol) of NH4H2PO4 were mixed in acetone in an agate mortar. This prepared mixture was calcined at 500 °C for 6 hours in a normal (air) atmosphere. The calcination was further carried out at 650 °C for 12 hours in a normal (air) atmosphere to obtain a product. ·BaY2SI3O 10 :Pr 3+ 、Prepared by the following method: 2.1273 g (10.7800 mmol) of BaCO3, 1.9828 g (33.0000 mmol) of SiO2, 2.4839 g (11.0000 mmol) and 0.0187 g (0.0183 mmol) of Pr6O 11 and were mixed in acetone in an agate mortar. This prepared mixture was calcined at 1,400 °C for 6 hours in a CO atmosphere to obtain a product. ·Ca3Sc2Si3O 12 :Pr 3+ 、Na + (1%), Prepared by the following method: 1.8119 g (18.1030 mmol) of CaCO3 and 0.0104 g (0.0102 mmol) of Pr6O 110.8428 g (6.1110 mmol) of Sc2O3 and 0.0032 g (0.0306 mmol) of Na2CO3 were dissolved in hot concentrated nitric acid. The solution was concentrated to obtain nitrates. Water was added to the nitrates while continuously stirring. 1.1043 g (18.3790 mmol) of SiO2 was mixed with 20 mL of water and placed in an ultrasonic bath to separate aggregates. This dispersion was added to the above water / nitrate solution and mixed. 11.1314 g (121.1300 mmol) of C4H 11 NO3 was added thereto. The solution was concentrated. The reaction product was dried at 150 °C. Next, the reaction product was calcined in a muffle furnace at 1,000 °C for 2 hours under a normal (air) atmosphere. A further calcination step was carried out at 1,300 °C for 4 hours under a production gas (N2 / H2; 95% / 5%) to obtain a product. · The phosphor was prepared according to International Publication No. WO 2009 / 064845 A2: 3.3349 g (33.3200 mmol) of CaCO3, 2.5123 g (34.0000 mmol) of Li2CO3, 0.1479 g (0.3400 mmol) of Pr(NO3)3·6H2O, and 0.0180 g (0.1700 mmol) of Na2CO3 were mixed with hexane in an agate mortar. Na2CO3 was added to compensate for the charge of Ca 2+ / Pr 3+ . This mixture was calcined at 700 °C for 2 hours while supplying air to remove organic components. Subsequently, the calcination was carried out at 1,100 °C (or higher) for 12 hours. As a result, an amorphous glassy product firmly adhered to the crucible was formed. The amorphous product could not be peeled off from the Al2O3 crucible. Therefore, the phosphor according to International Publication No. WO 2009 / 06 4 845 A2 is inappropriate for the composition according to the present invention. This could not be used for subsequent research.

[0083] 3.2 Antibacterial effect test of the phosphor First, the antibacterial effect of the phosphor itself was tested. The effectiveness of the phosphor against Gram-positive test bacteria and Gram-negative test bacteria was tested. The test was carried out using Bacillus subtilis, which is used in the UV-based biodosimetry test of [Standard W294 "UV Equipment for Disinfection in Water Supply"] of DVGW (German Gas and Water Technology Science Association). Since it is a Gram-positive spore-forming bacterium and is particularly insensitive to ultraviolet light, it is suitable for the worst-case example when testing the antibacterial effect of ultraviolet light. Furthermore, in order to show the antibacterial effect against Gram-negative bacteria, the antibacterial effect was tested with Escherichia coli. Escherichia coli is a Gram-negative aerobic bacterium that mainly occurs in the human intestinal tract, so it is a typical indicator of fecal contamination. When other tissues are contaminated with Escherichia coli, as a result, infectious diseases such as urinary tract infections frequently occur.

[0084] 3.2.1 Agar Medium Test The agar medium test was used to verify the antibacterial effect of the phosphor against the test bacteria Bacillus subtilis and Escherichia coli. For the test, the bacterial suspension of the test bacteria was inoculated confluently onto solid ordinary agar medium. The phosphor sample was applied to the inoculated ordinary medium (Figure 2). The medium was cultured under appropriate growth conditions. After culturing the medium, the growth inhibition characteristics were evaluated from the formation of a zone where colonies did not grow concentrically around the phosphor accumulated on the ordinary medium and its periphery. The test bacteria used were spizizenii (DSM 347, ATCC 6633), which is a subspecies of Bacillus subtilis, and Escherichia coli (DSM 1116; ATCC 9637). The test bacteria were used in a suspension with a final concentration of 10 7 cells / mL. The bacterial suspension was generated by diluting the preculture of each bacterial strain. The dilution was carried out with sterile deionized water. The preculture of the test bacteria was generated in sterile casein peptone-soybean peptone (CASO) broth. The preculture of Bacillus subtilis was cultured at 30 °C for 16 ± 1 hours with constant stirring in a vortex bath. The preculture of Escherichia coli was cultured at 36 °C with constant stirring at 350 rpm in a heat-insulated Erlenmeyer flask equipped with a magnetic stirrer bar. The cell titer of the preculture was measured by microscopic examination using a hemocytometer (Thoma counting chamber). In the agar medium test, in order to ensure a confluent coating of ordinary agar, 10 7A bacterial suspension (1.0 mL) of cells / mL was uniformly distributed on a sterilized CASO agar medium. Before applying the phosphor in the center, the applied bacterial suspension was equilibrated on a normal agar medium at room temperature (22 ± 2 °C) for 300 ± 30 seconds. Further, as a minus and plus comparison, calcium carbonate and copper oxide were also applied to the center of the normal medium, respectively. It is known that copper oxide has a growth inhibitory effect, while calcium carbonate has no growth inhibitory effect. The normal medium was cultured at room temperature for 24 ± 1 hours under constant illumination. The same preparation was further cultured in the dark. As a result of culturing under illumination and in the dark, if there is a growth inhibitory effect only under illumination, the upconversion characteristics of the phosphor are shown. For all samples and comparative examples, three tests were performed regardless of the presence or absence of illumination during the 24 ± 1 hour culture period. The phosphor and the phosphorescent particles are used as synonyms.

[0085] 3.2.2 Results of the agar medium test The growth inhibitory effect of the phosphor on bacteria was visually detected after culturing at room temperature for 24 ± 1 hours (Table 7). If a concentric zone where bacterial colonies have not grown occurs around the accumulated phosphorescent particles or comparative particles and their periphery on the normal agar medium, there is a growth inhibitory effect. If the growth of bacterial colonies is detected in the normal agar medium around the accumulated phosphorescent particles or reference particles and their periphery, there is no growth inhibitory effect. After culturing at room temperature for 24 ± 1 hours under illumination, the growth inhibitory effect of the phosphor CaLi2SiO4:Pr 3+ , Na + (1%) on Bacillus subtilis and Escherichia coli could be detected. No growth inhibitory effect could be detected around other phosphors (Table 7). For all phosphors, the growth of bacterial colonies under dark culture conditions could not be detected around the accumulated phosphorescent particles and their periphery. These results show that the phosphor CaLi2SiO4:Pr 3+ , Na +It clearly shows that the reason for the antibacterial effect of (1%) is the physical effect of UV emission in the photoexcited state. In the dark state, upconversion does not occur, so the antibacterial effect of the phosphor was not detected in the dark state. Furthermore, it can be seen that the phosphor CaLi2SiO4 did not show a growth inhibitory effect on the test bacteria. Therefore, it can be concluded that doping the phosphor with praseodymium is advantageous for the physical effectiveness of the upconversion of the phosphor without being bound by theory. The comparative example using calcium carbonate did not show a zone where bacterial growth was inhibited, either in the illuminated state or in the dark state. In contrast, the comparative example using copper oxide showed concentric zones where bacterial colonies did not grow, both in the illuminated state and in the dark state. Furthermore, the phosphor showed no pure bacterial contamination at all. The results show that the phosphor CaLi2SiO4:Pr 3+ , Na + (1%) is suitable for the curable composition according to the present invention.

Table 7

[0086] 3.3 Test of the antibacterial effect of the composition according to the present invention In 3.2, it was shown that the phosphor CaLi2SiO4:Pr 3+ , Na + (1%) itself has an antibacterial effect. However, whether this antibacterial effect still accompanies the composition according to the present invention will be confirmed hereafter. Note that the terms "antibacterial effect", "antibacterial property", "antibacterial action" and "antibacterial characteristic" are used as synonyms. To test the antibacterial effect of the composition according to the present invention, three phosphors and film-forming polymer matrices P4, P2 and P6 were used. P2 functions as a comparative example. The phosphor CaLi2SiO4:Pr 3+ , Na + (1%), Lu2CaAl4SiO 12 :Pr3+ , Gd 3+ , and CaLi2SiO4 were used, and CaLi2SiO4:Pr 3+ , Na + (1%) alone functioned as the phosphor according to the present invention.

[0087] 3.3.1 Preparation of curable compositions The curable compositions Z4-2 and Z6-2 according to the present invention, and Comparative Examples VZ4-1, VZ4-3, VZ2-1, VZ2-2, VZ2-3, VZ6-1 and VZ6-3 were prepared according to the details in Table 8. 50 g of glass beads were added to each composition, and the mixture was ground at 2,000 rpm for 5 minutes with a speed mixer. After filtering off the glass beads, each composition was applied to a polymer film and crosslinked to form a film. Then, if coated on a substrate, the coating surface should have an antibacterial effect. The formulation of the compositions is apparent from Table 8.

[0088] 3.3.2 Transfer method The test bacterium used was again spizizenii (DSM 347, ATCC 6633), a subspecies of Bacillus subtilis. 1 mL of a Bacillus subtilis suspension with a final concentration of 10 7 cells / mL was uniformly distributed on a sterilized CASO agar medium in order to ensure a confluent coating of the normal agar medium. The applied bacterial suspension was equilibrated on the normal agar medium at room temperature (22 ± 2°C) for 300 ± 30 seconds. The bacterial suspension was produced by diluting the preculture of each bacterial strain. Dilution was performed with sterilized deionized water. The preculture of the test bacterium was produced in sterilized CASO broth. The preculture of Bacillus subtilis was cultured at 30°C for 16 ± 1 hours with constant stirring in a vortex bath. The cell titer of the preculture was measured by microscopic examination using a hemocytometer (Thoma counting chamber). The aim of the transfer method is to simulate the antibacterial action of the coated surface under conditions that are actually close on a dry abiotic surface. For this purpose, the coating obtained as described above was cut into pieces of 2.5 cm × 4 cm in size and pressed against an ordinary agar medium inoculated confluently with Bacillus subtilis at a specified weight of 90 ± 1 g for 60 ± 5 seconds. By this process, semi-dry bacteria were transferred onto the surface of the coating. Subsequently, the substrate was placed in an empty Petri dish with the coated and inoculated side facing up and cultured under illumination at room temperature for 0 hours, 1 hour, 2 hours, 3 hours, and 6 hours. To test the antibacterial effect due to the upconversion effect, the substrate with the coated and inoculated side was cultured in the dark at room temperature for 0 hours, 1 hour, 2 hours, 3 hours, and 6 hours. The selected comparative examples were again calcium carbonate (no growth inhibitory effect) and copper oxide (with growth inhibitory effect). For all samples and comparative examples, three tests were conducted regardless of the presence or absence of illumination during the culture period. The antibacterial effect after an appropriate culture time is detected by measuring the culturability by the contact test (Figure 3). To test the culturability of Bacillus subtilis, after culturing for 0 hours, 1 hour, 2 hours, 3 hours, and 6 hours, the coated and inoculated side of the substrate was pressed against a sterilized ordinary agar medium at a specified weight of 90 ± 1 g for 60 ± 5 seconds. Next, the ordinary agar medium was cultured at 30 °C for 24 ± 1 hours under static conditions. The formed bacterial colonies were visually and qualitatively evaluated.

Table 8

[0089] 3.3.3 Results of the transfer method By reducing the culturability of Bacillus subtilis, the growth inhibitory effect can be checked by the transfer method. The culturability of the adhered bacteria on the coating surfaces of Z4-2 and Z6-2 showed that the growth clearly decreased as the culture time increased (Figure 4). The phosphor CaLi2SiO4:Pr in the curable composition according to the present invention 3+ , Na +(1%) significantly reduces the culturing ability of Bacillus subtilis compared to blank samples or samples cultured in the dark. This reduction could be measured under constant illumination even after 1 hour of culturing. The culturing ability continued to decline under constant illumination up to 6 hours of culturing time. The composition cultured in the dark did not show a decline in culturing ability during the 6-hour culturing. A representative image of Z4-2 is shown in Figure 4. Since the number of culturable bacteria does not change over 6 hours, it can be explained that the antibacterial effect of the phosphor exists only under illumination conditions. Therefore, the upconversion effect also exists. The comparative phosphor Lu2CaAl4SiO 12 :Pr 3+ , Gd 3+ and CaLi2SiO4 did not show an antibacterial effect in any of the comparative compositions, whether in the illuminated or dark state (Table 9). In the case of the comparative composition VZ2-2, no antibacterial effect of the tested phosphors was detected (Table 9). From this, it can be inferred that the polymer Polyimide P84 (registered trademark) NT is not a film-forming polymer suitable for the curable composition according to the present invention, in contrast to the polymers Dynacoll (registered trademark) AC 3820 and polymer CAB (trademark) 381-2. In the comparison with calcium carbonate, no decline in the culturing ability of Bacillus subtilis could be detected, whether in the illuminated or dark state. When copper oxide was added, a clear decline in culturing ability could be detected in both the dark and illuminated states. Furthermore, the polymer matrix did not show pure contamination. Figure 5 also shows that the phosphor CaLi2SiO4 has no antibacterial effect at all.

Table 9

[0090] 4. Physical properties of the composition according to the present invention An important property of the curable composition is storage stability. The conclusion regarding storage stability can be derived from the viscosity measurement and the characterization of the precipitate (such as homogenization and slurry formation) of the curable composition Z4-2 according to the present invention shown in Table 8, without using a curing agent or a catalyst. Hereinafter, it is referred to as Z4-2*. The phosphor CaLi2SiO4:Pr 3+ , Na + (1%) was used.

[0091] Viscosity The viscosity of Z4-2* without a curing agent and a catalyst and containing each additive was measured using a cone and plate rotational viscometer. The viscosity difference from the initial value immediately after mixing was confirmed at 40 °C after 1 week and 2 weeks (Table 10). All the compositions containing additives showed improved stability with respect to the viscosity during storage at 40 °C as compared with the composition without additives. The stability with respect to the viscosity during storage at 40 °C was improved by the composition Z4-2* and Tego® Dispers 688. Even if the initial viscosity slightly decreased, good storage stability was ensured.

[0092] Precipitation and homogenization Furthermore, the formation of precipitate was confirmed after 1 week and 2 weeks at 40 °C (Table 11). Evaluation criteria: Precipitate [%] = height of precipitate [cm] compared to the total height [cm] of the wet coating Homogenization = light and heavy, the mixture was stirred with a spatula. As can be seen from Table 11, the compositions Z4-2* and Tego® Dispers 688, and Z4-2* and Tego® Dispers 670 showed very good results regarding the precipitation of particles. Measurable precipitation of particles did not occur within 2 weeks at 40 °C. In the case of Z4-2* and Tego® Dispers 628, the particles could be easily homogenized again after 1 week, but this was not the case for the composition without additives.

Table 10

Table 11

Claims

1. A curable composition for producing a coating having antibacterial properties, - at least one film-forming polymer, - at least one upconversion phosphor, - optionally, at least one additive, - optionally, at least one curing agent, comprising a curable composition in which the phosphor is selected from the following ideal general formula (I). A 1-x-y-z B* y B 2 SiO 4 : Ln 1 x, Ln 2 z, (I) (In the formula, x = 0.0001 to 0.05, z = 0 or z = 0.0001 to 0.3, and y = x + z, A is selected from Mg, Ca, Sr, and Ba, B is selected from Li, Na, K, Rb, and Cs, B* is selected from Li, Na, and K, B is the same as B* or different from B*, Ln 1 is selected from praseodymium (Pr), erbium (Er), and neodymium (Nd), Ln 2 is selected from gadolinium (Gd) as required.)

2. The composition according to claim 1, characterized in that the phosphor is doped with praseodymium.

3. The composition according to claim 1 or claim 2, characterized in that the phosphor is doped with praseodymium and codoped with gadolinium.

4. The phosphor is a solidified melt of a crystalline silicate containing at least one alkali metal ion and at least one alkaline earth metal ion, or a solidified melt of a crystalline silicate containing at least one alkali metal ion and at least one alkaline earth metal ion and doped with a lanthanoid ion, The composition according to any one of claims 1 to 3, characterized in that the crystalline silicate is doped with praseodymium and optionally codoped with gadolinium.

5. The composition according to any one of claims 1 to 4, characterized in that the phosphor is selected from the following ideal general formula (Ia). A 1-x-y-z B* y B 2 SiO 4 : Pr x, Gd z, (Ia) (In the formula, A is Mg, Ca, Sr, Ba, and B is Li, Na, K, Rb, Cs, x = 0.0001 to 0.05, z = 0 or z = 0.0001 to 0.3, and y = x + z, B* is selected from Li, Na, and K, which balance the charge of the silicate, B is the same as B* or different from B*.)

6. The composition according to any one of claims 1 to 5, characterized in that the phosphor is selected from the following general formula (II). (Ca 1-a Sr a ) 1-2b Ln b Na b Li 2 SiO 4 (II) (wherein, a = 0.0001 to 1, b = 0.0001 to 1, Ln is a lanthanoid ion selected from praseodymium, gadolinium, erbium, and neodymium, and is at least one of these.)

7. When the phosphor is irradiated with low-energy electromagnetic radiation having a long wavelength in the range of 2,000 nm to 400 nm, particularly 800 nm to 400 nm, it emits high-energy electromagnetic radiation having a short wavelength in the range of 400 nm to 100 nm. The maximum irradiation intensity of the high-energy electromagnetic radiation having the short wavelength is at least 1·10 3 counts / (mm 2 ·s), characterized in that it is the composition according to any one of claims 1 to 6.

8. The composition according to any one of claims 1 to 7, wherein the phosphor according to formula (II) has XRPD signals in the ranges of 23° 2Θ to 27° 2Θ and 34° 2Θ to 39.5° 2Θ.

9. The composition according to any one of claims 1 to 8, wherein the film-forming polymer contains a functional group that reacts with an isocyanate-containing curing agent or catalyst.

10. The composition according to any one of claims 1 to 9, wherein the film-forming polymer is selected from the group consisting of a hydroxy-functional acrylate polymer, a hydroxy-functional polyester polymer, and / or a hydroxy-functional polyether polymer, a hydroxy-functional cellulose derivative, an amino-functional aspartic acid polymer, or an amino-functional polyester polymer, and reacts with an isocyanate-containing curing agent.

11. The composition according to any one of claims 1 to 10, wherein the film-forming polymer has low resonance.

12. The composition according to any one of claims 1 to 11, wherein the transmittance of the film-forming polymer measured by a twin-beam UV / VIS spectrophotometer is at least 75%.

13. The composition according to any one of claims 1 to 12, wherein the transmittance of the film-forming polymer measured by a twin-beam UV / VIS spectrophotometer is at least 70%.

14. The composition according to any one of claims 1 to 13, wherein the average particle size (d50) of the phosphor measured in accordance with ISO 13320:2020 and USP 429 is 0.1 μm to 100 μm.

15. The composition according to any one of claims 1 to 14, characterized in that the additive is selected from the group consisting of a dispersant, a rheology aid, a leveling agent, a wetting agent, an antifoaming agent, and a UV stabilizer.

16. The composition according to any one of claims 1 to 15, characterized in that the curing agent is selected from the group consisting of aliphatic and cycloaliphatic isocyanates.

17. The composition according to any one of claims 1 to 16, characterized in that the coating formed from the composition has an antibacterial action against bacteria, yeasts, molds, algae, parasites, and viruses.

18. The coating formed from the composition is - at least one nosocomial infection pathogen of Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, Escherichia coli, Enterobacter, Corynebacterium diphtheriae, Candida albicans, Rotavirus, Bacteriophage, - at least one pathogenic environmental organism of Cryptosporidium parvum, Giardia lamblia, Ameba, Acanthamoeba, Naegleria, Escherichia coli, Coliform group, Fecal streptococcus, Salmonella, Shigella, Legionella, Pseudomonas aeruginosa, Mycobacterium, Enterovirus, Poliovirus and Hepatitis A virus, - at least one pathogen in food and beverage of Bacillus cereus, Campylobacter, Clostridium botulinum, Clostridium welchii, Cronobacter, Escherichia coli, Listeria monocytogenes, Salmonella, Staphylococcus aureus, Vibrio, Yersinia enterocolitica, Bacteriophage, The composition according to any one of claims 1 to 17, characterized in that it has an antibacterial action against.

19. Use of the composition according to any one of claims 1 to 18 for preparing a dispersion, a kneaded pigment, an adhesive, a trowel compound, plaster, paint, coating or printing ink, an inkjet, a kneaded resin, or a pigment concentrate.

20. Use of the composition according to any one of claims 1 to 18 for preparing a coating having antibacterial properties.

21. Use of the composition according to any one of claims 1 to 18 for coating substrates in the sanitary facilities and hospitals as well as in the food and beverage industries.

22. A method of forming an antibacterial coating on a substrate, (a) at least one film-forming polymer having a functional group that reacts with an isocyanate-containing curing agent and optionally catalyzed by a catalyst; (b) at least one phosphor of the following general formula (II); (Ca 1-a Sr a ) 1-2b Ln b Na b Li 2 SiO 4 (II) (wherein a = 0.0001 to 1, b = 0.0001 to 1, Ln is a lanthanoid ion selected from praseodymium, gadolinium, erbium, neodymium, and is at least one of these). (c) a curing agent containing an isocyanate functional group; A method comprising the step of applying a curable film-forming composition containing the same to the substrate.

23. The method according to claim 22, wherein the substrate is made of metal, mineral substrate, cellulose substrate, wood, and mixtures thereof, dimensionally stable plastics and / or thermosetting materials.

24. The method according to claim 22 or claim 23, wherein a primer composition is applied to the substrate before applying the curable film-forming composition.

25. A product, characterized in that it is at least partially coated with the curable composition according to any one of claims 1 to 18.

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