Water-based curable composition for producing coating comprising phosphors

Abstract

To provide a water-based curable composition for production of a coating having an antimicrobial property.SOLUTION: A water-based curable composition for the production of a coating having an antimicrobial property, comprises: at least one film-forming polymer; optionally, at least one additive; optionally, at least one curing agent; and at least one up-conversion phosphor comprising a rare earth atom.SELECTED DRAWING: Figure 1.1

Description

[Technical Field]

[0001] The present invention relates to aqueous curable compositions for producing coatings having antimicrobial properties, their use, and coatings and articles coated therewith. [Background technology]

[0002] Every day, humans are exposed to a wide variety of microorganisms, including bacteria, fungi, and viruses. Many of these microorganisms are beneficial or even necessary. Nevertheless, there are not only less harmful representatives, but also disease-causing or even deadly bacteria, fungi, and viruses.

[0003] Microorganisms can be transmitted through everyday interactions with other people or through contact with objects used by others. Surfaces are given antibacterial finishes, especially in hygiene-sensitive areas. Areas of use include surfaces of medical equipment and consumer goods, especially 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 husbandry. The spread of pathogenic microorganisms is a major problem today in the care sector and in healthcare, and in places where many people interact in enclosed spaces. A particular current risk is also the increasing occurrence of so-called multidrug-resistant bacteria, which are insensitive to most antibiotics.

[0004] In addition to standard hygiene measures, antimicrobial technologies and materials are utilized to reduce the risk of pathogen spread through contact surfaces. The use of chemical or physical methods can have a significant effect on the microbial reproduction process. Physical methods include, for example, heat, cold, radiation, or ultrasound. Among chemical methods, halogens, metal ions, organic compounds and dyes, as well as certain gases such as ozone, are known.

[0005] Chemical and physical methods are often highly effective in destroying microorganisms, but their effectiveness is short-lived. Chemical methods promote the development of resistance and lead to the destruction of the surface being protected, making them unsuitable for some applications under certain circumstances. However, the greatest drawback, especially with organic chemicals, is their risk or toxicity to humans. Certain substances, such as formaldehyde, which has been used as a disinfectant for many years, are now suspected of causing cancer and being extremely harmful to the environment.

[0006] Antibacterial surfaces can make a crucial contribution to solving these problems. Today's standard processes for generating such antibacterial properties primarily utilize active ingredients incorporated into materials, such as silver particles, copper particles, their metal oxides, or quaternary ammonium compounds. This often involves processing antibacterial metals, metal oxides, or metal oxide mixtures to produce nanoparticles, which are then incorporated into paints, coatings, or polymeric materials. The widespread use of metal particles is questionable, as it is nearly impossible to assess the long-term impact of these heavy metals on humans and the environment.

[0007] For example, U.S. Patent No. 5,929,999 discloses particles finished with a layer containing both antimony tin oxide and manganese oxide. Those skilled in the art know that antibacterial surfaces are created due to the electrochemical properties of metals, which in the presence of moisture develop microscale galvanic cells, resulting in a bactericidal action thanks to microscale electric fields.

[0008] Similarly, it is known that UV radiation can be used in medicine or hygiene, for example, to disinfect water, process gases, air, or surfaces. For example, UV radiation has long been used in drinking water treatment to reduce the number of facultative pathogenic microorganisms in water. This is preferably done using UV-C radiation in the wavelength range between 200 nm and 280 nm. The use of electromagnetic radiation of different wavelengths allows for the identification of different proteins, amino acids / nucleic acids (e.g., DNA or RNA), and differences in peptide bonds between individual acids present in microorganisms, tissues, or cells. The absorption of different wavelengths must be taken into account. For example, DNA / RNA absorbs electromagnetic radiation well in the 200-300 nm wavelength range, especially in the 250-280 nm range, making this radiation range particularly suitable for inactivating or mutating DNA / RNA. Therefore, such irradiation can inactivate pathogenic microorganisms (viruses, bacteria, yeasts, molds, spores, and inter alia). Depending on the duration and intensity of irradiation, mutations can be induced or even the structure of DNA or RNA can be disrupted. Thus, metabolically active cells can be inactivated and / or their proliferation ability can be eliminated. The advantage of UV irradiation is that microorganisms cannot develop resistance to it. However, these physical methods require specific equipment and generally require regular repetition by trained personnel, making their widespread use difficult.

[0009] Furthermore, as well as direct irradiation with electromagnetic radiation from the wavelength range of UV radiation, the use of the "upconversion" effect is also known, which uses phosphor particles that are able to convert electromagnetic radiation with wavelengths beyond UV radiation, in particular visible light or infrared radiation, into electromagnetic radiation with shorter wavelengths, so that the desired effect of emitting radiation can be achieved by individual phosphor particles.

[0010] Patent Document 2 relates to an object that emits in the wavelength range of UV radiation. Phosphor particles are embedded in a near-surface region within the material from which the object is formed, or in a coating on the object. It generally states that the phosphor particles are added directly to a coating formed on the material during processing, and the specific material must have an appropriate consistency or viscosity. Patent Document 2 is silent regarding suitable polymers and additives.

[0011] U.S. Patent Nos. 5,629,999 and 5,729,999 describe phosphors that can be incorporated into polyvinyl chloride, acryloyl butadiene, polyolefins, polycarbonate, polystyrene, or nylon. These phosphors kill pathogenic microorganisms through the phosphor's upconversion properties. These phosphors are prepared at temperatures between 1800 and 2900°C. U.S. Patent Nos. 5,629,999 and 5,729,999 disclose compositions containing said phosphors with alleged antimicrobial activity, but they do not provide evidence of either upconversion properties or microbiological testing. The processes disclosed in these documents do not produce phosphors with upconversion properties, but instead produce amorphous, glass-like products.

[0012] Furthermore, Patent Documents 5 and 6 are silent, for example, regarding the compatibility of components in the coating composition or the properties of the coating surface (e.g., paint surface, etc.). However, the appearance of the coating surface is most important to consumers.

[0013] The requirements for coatings and paints are diverse. In principle, a coating layer or paint coating has two tasks or functions: a protective function and a decorative function. When the term "coating layer" is used below, 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 shiny coating layer is required, and on the other hand, a coating layer is required to ensure chemical and mechanical stability, a certain slip on the coating, or a certain feel. A continuous coating layer is required.

[0014] In contrast to Patent Document 6, unpublished patent applications EP 19202910.6 and PCT / EP2020 / 077798 disclose upconversion phosphors and their preparation. These phosphors are capable of converting radiation from lower-energy, longer-wavelength electromagnetic radiation in the 2000-400 nm range, especially the 800-400 nm range, into higher-energy, shorter-wavelength electromagnetic radiation in the 400-100 nm range, preferably the 300-200 nm range, making them suitable for use as antibacterial phosphors in coating layers.

[0015] For example, the not-yet-published European patent application EP 21157055.1 describes compositions comprising at least one film-forming polymer, at least one upconversion phosphor according to the teachings of EP 19202910.6 and PCT / EP2020 / 077798, optionally at least one additive, and optionally at least one hardener. Coating layers containing these phosphors have been shown to have antibacterial activity without significant impairment of other properties, particularly storage stability.

[0016] However, it was also found that phosphors prepared by processes according to EP19202910.6 and PCT / EP2020 / 077798 are not particularly suitable for water-based coating systems.

[0017] The prior art discloses solvent-based, water-based, and solvent-free coating materials.

[0018] Solvents are used to establish a workable consistency for the coating material. Low molecular weight organic liquids in which the film formers used are completely soluble are commonly used.

[0019] Coating, coating material, paint, and coating system are used synonymously herein.

[0020] However, solventborne systems have toxicological and ecological disadvantages. Their high content of flammable solvents, which are harmful to health, is undesirable for health and safety and environmental protection reasons. Furthermore, the use of solvents is increasingly subject to legal restrictions. These arise, among other things, from various national and international guidelines (EU Decopaint guidelines) on limiting VOC (volatile organic compounds) emissions from coating materials and on reducing the health risks from volatile and semi-volatile compounds (VOCs and SVOCs) for processors and users (Ausschuss fur die gesundheitliche Bewertung von Bauprodukten = AgBB [German] (See also the requirements for certification of buildings by the German Sustainable Building Council (DGNB) [German Commission for the Health-Related Assessment of Building Products] or the Deutsche Gesellschaft fur Nachhaltiges Bauen eV (DGNB) [German Sustainable Building Council] or Leadership in Energy & Environmental Design (LEED).

[0021] Therefore, water-based paints and coatings are used industrially on a large scale. [Prior art documents] [Patent documents]

[0022] [Patent Document 1] International Publication No. 2019 / 197076 [Patent Document 2] DE 10 2015 102 427 [Patent Document 3] US Patent Application Publication No. 2009 / 0130169 [Patent Document 4] International Publication No. 2009 / 064845A2 [Patent Document 5] US Patent Application Publication No. 2009 / 0130169 A1 [Patent Document 6] International Publication No. 2009 / 0644845A2 Summary of the Invention [Problem to be solved by the invention]

[0023] It is therefore desirable to provide an aqueous curable composition of the type mentioned in the introduction, which can be used to produce aqueous coatings that provide protection against microorganisms, the antimicrobial action being via a physical route. The curable composition is therefore not subject to the Biocides Regulation (Regulation (EU) No. 528 / 2012 of the European Parliament and of the Council of 22 May 2012 in its current text for 2019), which very advantageously entails the elimination of approval times and costs. [Means for solving the problem]

[0024] Based on the teachings of European patent applications EP 19202910.6, PCT / EP2020 / 077798 and EP 21157055.1, the present invention provides an aqueous curable composition for the production of a coating having antimicrobial properties, comprising: at least one film-forming polymer, optionally at least one additive, optionally at least one hardener, at least one up-conversion phosphor of general formula (I) A 1-x-y-z B * y B2SiO4:Ln 1 x ,Ln 2 z , (I) (where x=0.0001~0.0500, z=0.0000 or z=0.0001 to 0.3000, where y = x + z, A is selected from the group consisting of Mg, Ca, Sr, and Ba; B is selected from the group consisting of Li, Na, K, Rb, and Cs; B* is selected from the group consisting of Li, Na, and K, where B is B * is the same as B or B is B * Not the same as B and B, preferably * is not the same, Ln 1 is selected from the group consisting of praseodymium (Pr), erbium (Er), and neodymium (Nd); Ln 2 is selected from gadolinium (Gd), wherein the post-treatment phosphor comprises at least one material having a band gap greater than 6 electron volts (eV) and being hydrolytically stable.

[0025] It has been found that phosphors prepared according to the teachings of European Patent Applications EP 19202910.6, PCT / EP2020 / 077798, and EP 21157055.1 no longer exhibit upconversion when suspended in water.

[0026] Without wishing to be bound by theory, it is hypothesized that certain elements of the phosphor go into solution, and thus the crystal lattice structure of the phosphor is disrupted to the extent that the phosphor no longer exhibits upconversion, and therefore the physical antibacterial activity may be lost.

[0027] Using the presently post-treated phosphors according to the invention, it has surprisingly been possible to create a diffusion barrier such that the aqueous curable compositions according to the invention can be used to produce antimicrobial coatings. Surprisingly, the phosphors have been found to be capable of converting the wavelengths required for antimicrobial action and, moreover, to be hydrolytically stable.

[0028] Uncoated, unpost-treated, and unencapsulated are understood to be synonymous herein, and the same applies equally to the terms coated, post-treated, and encapsulated.

[0029] Here, the band gap of the preferred material can affect the diffusion barrier: for example, preferred materials allow UV-C radiation (200-280 nm) to pass through unattenuated.

[0030] The material preferably has a bandgap of 12 electron volts (eV) or less.

[0031] Preferably, the material is selected from the group consisting of inorganic oxides, silicates, borates, phosphates, or mixtures thereof.

[0032] The material is preferably SiO2, α-Al2O3, MgO, MgAl2O4, Ca polyphosphate, Sr polyphosphate, Ca or Sr pyrophosphate (Ca 1-x Sr x )3P2O7 (x=0.0 to 1.0), or a mixture thereof.

[0033] Preferably, the material is formed on the phosphor as a result of post-treatment with the starting material.

[0034] Preferred starting materials for the aftertreatment are tetraalkyl orthosilicates in which the alkyl groups, which may be the same or different at each occurrence, have 1 to 10 carbon atoms, preferably the alkyl groups, which may be the same or different at each occurrence, have 1 to 4 carbon atoms, in particular tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetraisopropyl orthosilicate and tetrabutyl orthosilicate and / or mixtures thereof.

[0035] Particular preference is given to tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetraisopropyl orthosilicate (TiPOS), tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS) and / or mixtures thereof.

[0036] Preferred starting materials are also Al alkoxides, such as, for example, Al methoxide, Al ethoxide, Al propoxide, Al isopropoxide, Al butoxide, or Mg alkoxides, such as, for example, Mg methoxide, Mg ethoxide, Mg propoxide, Mg isopropoxide, Mg butoxide, or Al and Mg alkoxides, such as, for example, Al / Mg methoxide, Al / Mg ethoxide, Al / Mg propoxide, Al / Mg isopropoxide, Al / Mg butoxide, or Ca / Sr nitrate, Ca / Sr acetate and Ca / Sr oxalate, and sodium polyphosphate, or sodium pyrophosphate, or mixtures thereof.

[0037] Preferably, the post-treated phosphor has a crystalline core with a glassy or amorphous coating.

[0038] Preferably, the phosphor prior to post-treatment is prepared with at least one flux.

[0039] The skilled person knows from the prior art a large number of fluxes of all kinds, such as halides, carbonates, sulfates, oxides and borates of ammonium, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lead, lanthanum, lutetium, aluminum, bismuth, boric acid, where applicable, and also their use in the field of metallurgy, for example to accelerate crystal growth or to suppress the formation of foreign phases.

[0040] Therefore, finding a suitable flux was also particularly important.

[0041] Completely surprisingly, it has been found that the preparation of upconversion phosphors in the presence of at least one halogen-containing flux results in upconversion phosphors having a uniform particle size distribution and also having increased luminescence intensity or a greater quantum yield compared to phosphors without added flux or containing a different flux.

[0042] Treatment with flux is also called fluxing, i.e. the product is treated with flux.

[0043] The examples show that the particle size distribution resembles a Gaussian distribution. The particle sizes are more uniform, and as a result, they can be incorporated into the coating matrix substantially more easily.

[0044] The particle size of the phosphors according to the present invention was found to be more uniform as a result of the flux, therefore they can be more easily incorporated into the coating matrix, which may lead to improvements in coating properties such as the appearance, gloss, feel and touch of the coating surface.

[0045] The emission intensity of the upconversion phosphor was also achieved by a simple technical implementation of the synthesis.

[0046] A further subject of the present invention is therefore a process for the preparation of these upconversion phosphors, and the upconversion phosphors thereby obtained.

[0047] Preferably, the halogen-containing flux used is at least one substance from the group consisting of ammonium halides, alkali metal halides, alkaline earth metal halides, and lanthanide halides. Surprisingly, it has been found that upconversion phosphors prepared using halides from this group have higher emission intensities than other fluxes.

[0048] The halide is preferably a fluoride or a chloride.

[0049] The alkali metal is preferably potassium, sodium or lithium.

[0050] The lanthanide is preferably praseodymium.

[0051] The alkaline earth metal is preferably calcium or strontium.

[0052] The phosphors used in the compositions according to the invention are preferably doped with praseodymium.

[0053] In the composition according to the invention, the phosphor is preferably doped with praseodymium and co-doped with gadolinium.

[0054] Preferably, the phosphor is at least partially crystalline. Therefore, it is preferred that the phosphor is partially or completely crystalline. Therefore, it is preferred that the phosphor is at least not completely amorphous. Therefore, it is preferred that the phosphor is not an amorphous solidified melt (glass).

[0055] The phosphor preferably consists of a crystalline silicate or a crystalline silicate doped with lanthanide ions, and contains at least one alkali metal ion and at least one alkaline earth metal ion.

[0056] In the composition according to the invention, the phosphor is preferably chosen from compounds of general formula (Ia): A 1-x-y-z B * y B2SiO4:Pr x ,Gd z , (Ia) (wherein A is selected from the group consisting of Mg, Ca, Sr, and Ba. B is selected from the group consisting of Li, Na, K, Rb, and Cs. B * is selected from the group consisting of Li, Na, and K, where B is B * is the same as B or B is B * Not the same as B and B, preferably * are not the same. x = 0.0001 ~ 0.0500; z=0.0000 or z=0.0001~0.3000, where y = x+z.

[0057] B * functions here to balance the charge of the praseodymium or gadolinium substitution.

[0058] where A is a single element of the group consisting of Mg, Ca, Sr, and Ba, or a combination of two or more elements of this group, i.e., for example, A = (Mg a1 Ca a2 Sr a3 Ba a4 ) where 0≦a1≦1, 0≦a2≦1, 0≦a3≦1, 0≦a4≦1, but a1+a2+a3+a4=1. Therefore, A is (Ca 0.9 Sr 0.1 ) may be used.

[0059] In the composition according to the invention, the phosphor is preferably chosen from compounds of general formula (II): (Ca 1-a Sr a ) 1-2b Ln b Na b Li2SiO4(II) wherein Ln is selected from the group consisting of praseodymium, gadolinium, erbium, neodymium, preferably praseodymium; a=0.0000 to 1.0000, preferably 0.0000 to 0.1000, particularly 0.0000; b=0.0001 to 0.5000, preferably 0.0001 to 0.1000, particularly 0.0050 to 0.0500.

[0060] Here, Ln can represent a single element from the group consisting of praseodymium, gadolinium, erbium, and neodymium, or a combination of two elements from this group. For example, Ln = (Ln 1 x Ln 2 y ) where Ln 1 and Ln 2 is selected from the group consisting of praseodymium, gadolinium, erbium, and neodymium, and x and y are as defined in formulas (I) and (Ia).

[0061] Ln 1 is useful for doping. For doping, the use of praseodymium is preferred. Ln 2 is used for optional co-doping. Preference is given to using gadolinium for optional co-doping. Phosphor is preferably not co-doped. In other words, Ln preferably represents a single element from the group consisting of praseodymium, gadolinium, erbium, and neodymium.

[0062] It is more preferred to select the phosphor from the compounds of general formula (IIa). Ca 1-2b Pr b Na b Li2SiO4(IIa) (In the formula, b=0.0001 to 0.5000, preferably 0.0001 to 0.1, particularly 0.005 to 0.0500.)

[0063] The phosphor is Ca 0.98 Pr 0.01 Na 0.01 Li2SiO4 is particularly preferred. Preferably, the upconversion phosphor according to the present invention contains a halogen corresponding to the halide of the flux.

[0064] The phosphor preferably irradiates with electromagnetic radiation having a lower energy and a longer wavelength in the range of 2000 to 400 nm, particularly in the range of 800 to 400 nm, and emits electromagnetic radiation having a higher energy and a shorter wavelength in the range of 400 to 100 nm, preferably in the range of 300 to 200 nm. Furthermore, the maximum emission intensity of the higher energy and shorter wavelength electromagnetic radiation is at least 1×10 3 Counts / (mm 2* s), preferably 1 × 10 4 Counts / (mm 2* s), particularly preferably 1 × 10 5 Counts / (mm 2* s) is preferably higher than s). To determine these indices, the emission is preferably stimulated by a laser, in particular a laser with a power of 75 mW at 445 nm and / or a power of 150 mW at 488 nm.

[0065] The phosphor according to formula (II) preferably has XRPD signals in the ranges of 23°2θ to 27°2θ and 34°2θ to 39.5°2θ, the signals being determined by Bragg-Brentano geometry and Cu-Kα radiation. Details of the measurement method are described in the unpublished European patent applications EP19202910.6 and PCT / EP2020 / 077798.

[0066] The not yet published European patent applications EP19202910.6 and PCT / EP2020 / 077798 are dedicated to the preparation of phosphors, in particular phosphors of formula (I), formula (Ia), and formula (II), and do not mention fluxes and / or starting materials.

[0067] Proceeding from the processes described in these documents, the process according to the invention comprises the following steps: -i) lanthanoid nitrates, lanthanoid carbonates, lanthanoid carboxylates, preferably lanthanoid acetates, lanthanoid sulfates, lanthanoid oxides, more preferably PrO 11 and / or Gd2O3, wherein: The lanthanide ions in the lanthanide oxide or salt are selected from praseodymium, gadolinium, erbium, neodymium, or in the case of co-doping, from at least two of these; -ii) providing a silicate, preferably an alkali metal silicate, or silicon dioxide, -iii) providing at least one alkaline earth metal salt and at least one alkali metal salt, preferably an alkali metal silicate or alkali metal carbonate selected from lithium salts or lithium compounds, and optionally selected from sodium and potassium salts, preferably a salt of lithium salt, preferably lithium carbonate, calcium carbonate and sodium carbonate, -iv) optionally providing at least one flux from the group consisting of ammonium halides, preferably ammonium chloride, alkali metal halides, preferably sodium chloride, sodium fluoride, sodium bromide, lithium fluoride, lithium chloride, alkaline earth metal halides, preferably calcium chloride, calcium fluoride, and lanthanide halides, preferably praseodymium fluoride or praseodymium chloride, a) mixing i), ii), iii) and optionally iv) by grinding to obtain a mixture, or - b) Preference is given to mixing i), ii) and iii) in an organic polar or non-polar solvent, which is not an aprotic solvent, to obtain a mixture, and calcining the mixture b) at 600-1000 ° C (step 1a) to remove the organic components, followed by calcination at 600-1000 ° C for at least 1 hour, preferably 2 hours or more, under normal (air) atmosphere, to obtain a calcined mixture. R, - a calcination step, preferably in air, of the mixture from a) or the calcined mixture from b) at a temperature below the melting temperature of the silicate-based material, to effect at least partial crystallization, preferably at a temperature between 50 and 200°C below the melting temperature of the silicate-based material for at least 3 hours, in a further calcination step (step 1b), preferably in air in order to crystallize the silicate-based material, preferably at a temperature between 800 and 900°C, particularly preferably at about 850°C, for at least 3 hours, preferably at least 12 hours, preferably in air, - a further calcination step at elevated temperature, preferably at 800°C and 50-200°C below the melting point of the material (step 2), for example at 850°C for at least 3 hours, particularly preferably at least 6 hours, in a reducing atmosphere, whereby the lanthanides are converted to Ln 3+ reduced to ions, obtaining a silicate-based lanthanide ion-doped material, preferably after cooling the material, - post-treating at least one starting material and a silicate-based lanthanide ion-doped material to obtain a material having a band gap of more than 6.0 electron volts (eV) on the doped material.

[0068] Further detailed embodiments of the process can be gleaned from EP19202910.6 and PCT / EP2020 / 077798, where only the flux is used and then post-treated with the starting material.

[0069] Preferably, the flux can be used in an amount of 0.01 to 3.5% by weight, more preferably 0.5 to 3.5% by weight, particularly preferably 1.0 to 3.5% by weight, based on the total amount of reactants.

[0070] It is also conceivable to prepare the phosphors according to the invention as follows. The starting materials used were CaCO3 (Alfa Aesar, 99.5%), Li2CO3 (Alfa Aesar, 99%), SiO2 (Aerosil 200, Evonik), and Pr6O11 (Treibacher, 99.99%), Na2CO3 (Merck, 99.9%), and CaF2 (Sigma-Aldrich, 99.9%) fluxes. 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 corundum crucible. The mixture is calcined twice: the first calcination is carried out in a melting furnace at 850 °C for 12 hours with air supply, and the second calcination is carried out at 850 °C for 6 hours under 95 / 5 N2 / H2. The final product is then Grinded in an agate mortar.

[0071] The upconversion phosphor thus prepared can then be preferably subjected to a post-treatment with the starting material described above.

[0072] There are many possibilities for post-treating the phosphor to obtain a substantially crystalline core and a glassy or amorphous coat of the material mentioned above.

[0073] Proceeding from the above process for preparing the phosphor, the post-treatment according to the invention preferably comprises the following steps: -phosphorus dispersed in an anhydrous medium, preferably the anhydrous medium comprises an alcohol such as ethanol, methanol, propanol, butanol, isopropanol, isobutyl alcohol or amyl alcohol, -Add starting materials, - carrying out a sol-gel process in the alkaline range, preferably according to the Stober synthesis, a different sol-gel process or homogeneous precipitation with urea, urotropine or another hydroxide ion donor, - optionally adding further starting materials; - deagglomeration, preferably by ultrasound or stirring with grinding bodies or by microfluidization, removing the anhydrous medium, - Allowing the phosphor to dry.

[0074] The starting materials can preferably be applied to the phosphor by dropwise addition or by spraying.

[0075] Deagglomeration may preferably be achieved by using a rotor-stator system, eg a stirrer system, a colloid mill, a homogenizer, or also by spray drying.

[0076] In a preferred embodiment, the post-treatment is carried out using a mixture of tetraethyl orthosilicate (TEOS) and tetramethyl orthosilicate (TMOS).

[0077] It is also conceivable to optimize the post-treatment step by spraying the starting materials onto the phosphor using a fluidized bed, intensive mixers or the Innojet process.

[0078] Surprisingly, it has been found that the phosphors according to EP19202910.6 and PCT / EP2020 / 077798 have the necessary upconversion properties in aqueous media to be responsible for the antibacterial effect after post-treatment according to the present invention. In other words, these phosphors are capable of converting electromagnetic radiation with wavelengths exceeding UV radiation, in particular visible or infrared light, into electromagnetic radiation with shorter wavelengths, in particular in the bands where, for example, the DNA or RNA of microorganisms can be destroyed or mutated. Therefore, these phosphors are very well suited for the compositions according to the present invention.

[0079] The present invention further provides phosphors of formula (I), (Ia), (II) or (IIa), wherein the phosphor has an essentially crystalline core with a glassy or amorphous coating.

[0080] Preferably, the phosphor has a glass-like coating made from a material with a bandgap greater than 6 electron volts (eV).

[0081] Preferably, the phosphor has a glass-like coating made from a material with a bandgap of less than 12 electron volts (eV).

[0082] The phosphor preferably comprises a material selected from the group consisting of inorganic oxides, silicates, borates, phosphates, or mixtures thereof.

[0083] The material is preferably SiO2, α-Al2O3, MgO, MgAl2O4, Ca polyphosphate, Sr polyphosphate, Ca or Sr pyrophosphate (Ca 1-x Sr x )3P2O7 (x = 0.0 to 1.0), or mixtures thereof.

[0084] The phosphor is preferably prepared using at least one of the above fluxes and then post-treated so that the phosphor is hydrolytically stable.

[0085] A further problem addressed by the present invention is the selection of film-forming polymers that can be used in the aqueous curable compositions having antibacterial properties. In principle, all film-forming polymers known from the prior art are useful.

[0086] The film-forming polymer preferably has a functional group, preferably an acidic hydrogen, that is reactive with the isocyanate-containing curing agent, optionally catalyzed by a catalyst.

[0087] "Aqueous" is also understood to mean those curable compositions that are dilutable or soluble in water.

[0088] Advantageously, the film-forming polymer is selected from the group of hydroxy-functional acrylate polymers, hydroxy-functional polyester polymers, and / or hydroxy-functional polyether polymers, hydroxy-functional cellulose derivatives, amino-functional polyester polymers, or mixtures, and is reacted with an isocyanate-containing curing agent.

[0089] Preferably, these film-forming polymers are dissolved or emulsified with the aid of a suitable emulsifier in water. Those skilled in the art will know suitable anionic, cationic and nonionic emulsifiers.

[0090] The film-forming polymer preferably has low resonance.

[0091] Those skilled in the art are aware of physical interactions at surfaces. Depending on the material and its surface, numerous effects occur at the surface onto which light is incident. The incident light is partially absorbed, partially reflected, and scattered by the surface of the material. Light can also be first absorbed and then re-emitted. In the case of opaque, translucent, or transparent materials, light can penetrate the body (transmission). In some cases, light can even be polarized or diffracted at the surface. Some objects can emit light (illuminated displays, LED segments, display screens), fluoresce with different colors of light, or phosphoresce (afterglow).

[0092] "Low resonance" in the context of the present invention means that the film-forming polymer has low absorption, reflection, remission, and scattering in the UV region or the blue region of 450-500 nm. In contrast, the transmittance should preferably be significant.

[0093] This is because it has surprisingly been found that the film-forming polymers according to the invention having low resonance improve the antibacterial action, allowing more electromagnetic radiation with lower energy and higher wavelengths in the range of 2000 nm to 400 nm, in particular in the range of 800 nm to 400 nm, to be transmitted, and as a result more electromagnetic radiation with higher energy and shorter wavelengths in the range of 400 nm to 100 nm, preferably in the range of 300 nm to 200 nm, to be emitted.

[0094] Higher permeability has been shown to result in higher release, which is essential for antimicrobial activity.

[0095] Preferably, the transmittance of the film-forming polymer, measured at a wavelength of 260 nm, is at least 75%, preferably at least 80%, particularly preferably at least 85%.

[0096] Preferably, the transmittance of the film-forming polymer, measured at a wavelength of 500 nm, is at least 75%, preferably at least 80%, particularly preferably at least 85%. It should be noted here, by way of example, that the transmittance can be defined at different wavelengths (see FIG. 1). For the present invention, a wavelength of 260 nm is chosen as the emitted wavelength and a wavelength of 500 nm as the excitation wavelength, which are responsible for the upconversion on the one hand and the antibacterial effect on the other hand to a large extent.

[0097] For example, in the case of 100% transmittance measured at a wavelength of 260 nm, the same amount of radiation is converted and emitted; that is, there is no loss due to absorption, scattering, etc. In the case of 80% transmittance measured at a wavelength of 260 nm, 20% is not transmitted, presumably due to absorption, reflection, remission, and / or scattering; therefore, only 80% of the radiation at a wavelength of 260 nm can be emitted.

[0098] This important finding is important in the selection of film-forming polymers. For example, polymers with 0% transmittance are unsuitable for the curable compositions according to the present invention. They do not transmit electromagnetic radiation with lower energy and higher wavelength, and therefore the phosphor present in the composition cannot convert this electromagnetic radiation into electromagnetic radiation with higher energy and shorter wavelength and release it, which is necessary for antimicrobial action.

[0099] Preferably, the compositions according to the invention have a transmittance, measured at 260 nm, of at least 75%, preferably at least 80%, particularly preferably at least 85%.

[0100] Preferably, the compositions according to the invention have a transmittance, measured at 500 nm, of at least 75%, preferably at least 80%, particularly preferably at least 85%.

[0101] The transmittance curves are preferably measured with a "Specord200Plus" twin beam UV / VIS spectrometer from Analytik Jena. Internal wavelength calibration uses a holmium oxide filter. Monochromatic light from a deuterium lamp (UV range) or a tungsten halogen lamp (visible range) is passed through the sample. The spectral range is 1.4 nm. The monochromatic light is split into a measurement channel and a reference channel and can be measured directly against a reference sample. The radiation transmitted through the sample is detected by a photodiode. It is processed into an electrical signal.

[0102] It is conceivable to use compositions with a permeability of less than 70%, which may also have antibacterial activity, but with very moderate efficiency.

[0103] The phosphor preferably has an average particle size with d50 of 0.1 to 50 μm, preferably d50 = 0.1 to 25 μm, particularly preferably d50 = 0.1 to 5 μm, as measured in accordance with ISO 13320:2020 and USP 429, e.g. with a Horiba LA-950 laser particle size analyzer.

[0104] In order to efficiently incorporate and / or stabilize the phosphor in the composition according to the invention, it is preferably possible to add various additives.

[0105] The additives are preferably selected from the group of dispersants, rheological aids, leveling agents, wetting agents, antifoaming agents and UV stabilizers.

[0106] Surprisingly, it has been found that the optional addition of additives to the composition according to the invention reduces the transmittance.

[0107] The composition according to the invention in a further embodiment in which an additive is used therefore preferably has a transmittance, measured at 260 nm, of at least 70%, preferably at least 75%, particularly preferably at least 80%.

[0108] Thus, the composition according to the invention in a further embodiment in which an additive is used preferably has a transmittance, measured at 500 nm, of at least 70%, preferably at least 75%, particularly preferably at least 80%.

[0109] Preferably, the composition according to the invention comprises a curing agent selected from the group of aliphatic or cycloaliphatic isocyanates or mixtures thereof.

[0110] Examples of isocyanate-containing curing agents are monomeric isocyanates, polymeric isocyanates, and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates due to their lower toxicity. 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 commercially available products include those sold under the trade names DESMODUR® by Covestro or VESTANAT by Evonik Industries. Known products are DESMODUR® N3400, DESMODUR® N3300, DESMODUR® N3600, DESMODUR® N75, DESMODUR® XP2580, DESMODUR® Z4470, DESMODUR® XP2565, DESMODUR® VL from Covestro. Another example is VESTANAT® HAT2500 L from Evonik Industries. V, VESTANAT® HB 2640 LV, or VESTANAT® T1890E. Examples of isocyanate prepolymers are DESMODUR® EXP 2863, DESMODUR® XP 2599, or DESMODUR® XP 2406 from Covestro. Further isocyanate prepolymers known to those skilled in the art can be used. Particular preference is given to hydrophilized isocyanates such as Bayhydur 3100 from Covestro.

[0111] The curing may be catalyzed by the use of a catalyst selected from organic Sn(IV), Sn(II), Zn, Bi compounds or tertiary amines.

[0112] Preference is given to using a catalyst selected from the group consisting of organotin catalysts, cyclic amidines, guanidines or amines, or mixtures thereof.

[0113] The curing catalyst is preferably used in an amount of 0.01 to 5.0% by weight, preferably 0.05 to 4.0% by weight, particularly preferably 0.1 to 3% by weight, based on the total weight of the curable composition.

[0114] For film-forming polymers that cure by physical drying, the addition of a reactive curing agent is not necessary.

[0115] The compositions according to the invention can preferably be used in 1K (one-component) or 2K (two-component) coating systems, melamine baking systems, or room temperature or high temperature systems.

[0116] Preferably, the coatings produced from the compositions according to the invention have antimicrobial activity against bacteria, yeasts, molds, algae, parasites and viruses.

[0117] The coatings produced according to the invention preferably have antimicrobial activity against: - Pathogens of nosocomial infections, preferably Enterococcus faecium and Staphylococcus aureus Bacteria, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, Escherichia coli, Enterobacter, Corynebacterium diphtheriae, Candida albicans, rotavirus, bacteriophage, - Facultative pathogenic environmental organisms, preferably Cryptosporidium parvum, Jardia laevis amebilla, amoeba (Acanthamoeba spp., Naegleria spp.), coliform bacteria, coliform bacteria, fecal streptococci, Salmonella spp., Shigella spp., Legionella spp., Pseudomonas aeruginosa, Mycobacterium spp., enteric viruses (e.g., polio and hepatitis A viruses), - Pathogens in food and drink, preferably Bacillus cereus, Campylobacter, Clostridium botulinum, Clostridium perfringens, Cronobacter, Escherichia coli, Listeria monocytogenes, Salmonella, Staphylococcus aureus, Vibrio, Yersinia enterocolitica, bacteriophages.

[0118] It has been found that the incorporation of the upconversion phosphor according to the present invention is significantly improved. The terms upconversion phosphor and phosphor are used synonymously.

[0119] The present invention further provides the use of a composition according to the invention for the preparation of a dispersion, millbase, adhesive, trowell compound, rendering, paint, coating or printing ink, inkjet, grind resin or pigment concentrate. Preference is given to the use of the composition according to the invention for the production of coatings with antibacterial properties.

[0120] Here, a coating having antimicrobial activity or properties means that the coating has an antimicrobial surface that limits or prevents the growth and proliferation of microorganisms. Surprisingly, it has also been found that the coatings according to the invention have chemical and mechanical stability, which is particularly important since antimicrobial coatings are frequently used in areas where regular disinfection and additional hygiene measures are required.

[0121] The present invention also includes a process for forming an antimicrobial coating on a substrate, comprising applying a curable film-forming composition to the substrate; a. at least one film-forming polymer containing functional groups reactive with an isocyanate-containing curing agent, optionally catalyzed by a catalyst; b. at least one phosphor of formula (II), c. a curing agent containing an isocyanate functional group; and Includes.

[0122] Preferably, the substrate is metal, a mineral substrate (eg, concrete, natural rock or glass), a cellulosic substrate, wood and hybrids thereof, a dimensionally stable plastic and / or a thermoset resin. The term "dimensionally stable plastics" is understood to mean, but is not exhaustive of, 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).

[0123] Preferably, the primer composition can be applied to the substrate before applying the curable film-forming composition. Preferably, the curable compositions according to the present invention are used for coating substrates in sanitary facilities and hospitals, and in the food and beverage industry.

[0124] This includes all settings in the public sphere, such as schools, nursing homes, industrial kitchens and nurseries. A further invention is an article at least partially, preferably completely coated with a curable composition according to the invention.

[0125] It should be noted that the terms "antimicrobial effect," "antimicrobial efficacy," "antimicrobial activity," and "antimicrobial properties" are used synonymously herein. It should be noted that the articles according to the present invention preferably have antibacterial activity even without the release of antibacterial active ingredients if the coating contains specific phosphors as claimed in the patent application. In this way, the route by which microorganisms are killed is physical. Therefore, such materials are not subject to biocide regulations (Regulation (EU) No. 528 / 2012 of the European Parliament and of the Council of 22 May 2012, current text of 2019). [Brief explanation of the drawings]

[0126] [Figure 1.1] Figure 1.1 shows the X-ray powder diffractogram (X-ray diffraction pattern) of the phosphor from Example 1 (top figure) compared to the reference phosphor (bottom normalized X-ray powder diffractogram). This demonstrates that the desired phosphor was prepared. Figure 1.1 also demonstrates the instability of the untreated phosphor in water. [Figure 1.2] Figure 1.2 shows the X-ray powder diffraction diagram (X-ray diffraction pattern) of the phosphor from Example 1 (above), which was suspended in water. The phosphor was found to have changed; certain elements appear to have leached out of the crystal lattice structure. Figure 1.2 illustrates the instability of the phosphor without post-treatment in water. [Figure 1.3] Figure 1.3 shows the X-ray powder diffractogram (X-ray diffraction pattern) of the phosphor of Example 1.1 (top figure) compared to a reference phosphor (bottom normalized X-ray powder diffractogram), demonstrating that the desired phosphor was prepared. [Figure 1.4] Figure 1.4 shows the X-ray powder diffraction diagram (X-ray diffraction pattern) of the phosphor from Example 1.1 (above), which was suspended in water. The phosphor was found to be unchanged. [Figure 1.5] Figure 1.5 shows the conductivity of aftertreated and non-aftertreated phosphors that had been previously suspended in water. It is clear that the aftertreated phosphor exhibited virtually no conductivity. Therefore, the phosphors according to the present invention are stable to hydrolysis. [Figure 1.6] Figure 1.6 shows the emission spectrum (dashed line) of Example 1.1 compared to the comparative phosphor of Example 1. The measurement was taken before the phosphor was suspended in water. The spectra clearly show that the intensity of both phosphor samples is within the wavelength range of interest. The phosphor according to the present invention loses very little intensity as a result of post-processing. [Figure 1.7]Figure 1.7 shows the emission spectra of Example 1.1 (dashed line) compared to the comparative phosphor of Example 1 after they have been suspended in water. It is clear that the non-post-treated phosphor no longer exhibits upconversion, which means that the physical antibacterial effect is gone. The phosphors according to the invention can be used in aqueous compositions according to the invention, which can be used to produce coatings with antibacterial effect. [Figure 2.1] Figure 2.1 shows the X-ray powder diffractogram (X-ray diffraction pattern) of the phosphor of Example 2 (top figure) compared to the reference phosphor (bottom normalized X-ray powder diffractogram), demonstrating that the desired phosphor was prepared. [Figure 2.2] Figure 2.2 shows the conductivity of the post-treated and non-post-treated phosphors according to Example 2, which were previously suspended in water. It is clear that the post-treated phosphor exhibited virtually no conductivity. The phosphors according to the invention are therefore stable to hydrolysis. [Figure 3.1] Figure 3.1 shows the conductivity of the post-treated phosphor according to Example 3 and the non-post-treated phosphor according to Example 1, which were previously suspended in water. It is clear that neither phosphor is stable to hydrolysis. The material Y2O3 is clearly unsuitable for establishing a diffusion barrier. [Figure 3.2] Figure 3.2 shows the emission spectrum of Example 3 before the phosphor was suspended in water. The phosphor exhibited the desired wavelength range. [Figure 3.3] Figure 3.3 shows the emission spectrum of Example 3 after the phosphor was suspended in water. The phosphor lost all of its intensity. [Figure 3.4] Figure 3.4 shows an SEM image of Example 3. Small irregular spots can be seen on the particle surface. These are assumed to be Y2O3 particles on top of it. [Figure 3.5] Figure 3.5 shows an SEM image of Example 1.1. The phosphor surface is smoother than that of Example 3. [Figure 3.6] Figure 3.6 shows an SEM image of uncoated phosphor. Only a section (black frame) is considered. It can be seen that no coating can be discerned on the particle surface, except for speckle-like fragments of phosphor (see black frame). [Figure 3.7] Figure 3.7 shows the SEM image of Example 1.1. Here, too, only a section is considered (black frame). Marked elevations can be identified on the surface. This can be attributed to the glass-like SiO2 coating (see black frame).

[0127] The following are examples that serve only to elucidate the invention to one skilled in the art and do not constitute any limitation on all of the claimed subject matter. [method]

[0128] Scanning electron microscopy was performed using a Zeiss EVO MA 10 scanning electron microscope. The microscope was operated with a LaB6 cathode and an accelerating voltage of 10 kV at 2 pA. Prior to measurements, the sample chamber was filled with approximately 5 * 10 -9 The pressure was evacuated to a value of mbar. The topography contrast was evaluated by detecting secondary electrons. The maximum resolution was 10 nm.

[0129] Powder XRD: X-ray powder diffractograms of the samples were recorded using a Panalytical X'Pert PRO MPD diffractometer operating in Bragg-Brentano geometry, using Cu-Kα radiation and a line-scan CCD detector. The integration time was 20 s and the step size was 0.017° 2Θ.

[0130] Emission spectra were recorded using an Edinburgh Instruments FLS920 spectrometer equipped with a Coherent 488 nm continuous-wave OBIS laser and a Hamamatsu (R2658P) Peltier-cooled (-20 °C) single-photon counting photomultiplier tube. Bandpass filters were used to suppress nth-order reflections caused by the monochromator.

[0131] The conductivity was determined using a Knick 703 laboratory conductivity meter. For this, 0.1 g of sample was dispersed in 200 ml of water at 300 rpm and room temperature. After immersing the measuring electrode in the dispersion, the conductivity was measured for 30 minutes, with measurements recorded every 30 seconds. The sample was then filtered and dried overnight at 150 °C in a drying cabinet for further measurements, such as XRD and luminescence measurements.

[0132] Example 1 Phosphor (Ca 0.94 Pr 0.03 Na 0.03 ) Preparation of Li2SiO4 2.8225 g (28.2 mmol) of CaCO3, 2.2167 g (30.0 mmol) of Li2CO3, 1.8025 g (30.0 mmol) of SiO2, 0.0477 g (0.45 mmol) of Na2CO3, and 0.1781 g (0.9 mmol) of PrF3 were mixed in acetone in an agate mortar. This mixture was calcined in air at 850 °C for 12 hours to remove organic components. Calcination was then carried out in a forming gas atmosphere (5% H2 / 95% N2) at 850 °C for an additional 6 hours, which yielded the desired product. The phosphor was recovered for further analysis.

[0133] Example 1.1 Phosphors according to the invention Phosphor (Ca 0.94 Pr 0.03 Na 0.03 ) Li2SiO4 post-treated with 36 wt% SiO2 based on phosphor 15 g of phosphor was suspended in 300 ml of dried ethanol in an ultrasonic bath for 30 minutes and then decanted to obtain a solid phase. This procedure was performed twice. Next, the phosphor was added to 360 ml of dried ethanol and 0.6 ml of TMOS was added. After 10 minutes in the ultrasonic bath, 45 ml of concentrated NH3 was added with stirring. Next, a TEOS / ETOH mixture consisting of 20 ml of TEOS and 60 ml of ethanol was added dropwise within 1 hour. During this time, the ultrasonic was turned on for 10 seconds every 10 minutes. Next, the dispersion was stirred for 3 hours, with the ultrasonic turned on for 10 seconds every 15 minutes. The solid phase was filtered off and washed with dried ethanol. It was then dried overnight at 200 °C.

[0134] Example 2 Phosphor according to the invention Phosphor (Ca 0.94 Pr 0.03 Na 0.03 ) Li2SiO4 was post-treated with 72 wt% SiO2 based on phosphor. The work-up was carried out as in Example 1.1 using a TEOS / ETOH mixture consisting of 40 ml TEOS and 60 ml ethanol.

[0135] Comparative Example Example 3: Phosphor (Ca) with 5% by weight of Y2O3 based on phosphor 0.94 Pr 0.03 Na 0.03 ) Post-treatment of Li2SiO4 1g of (Ca 0.94 Pr 0.03 Na 0.03 ) Li2SiO4 was mixed with 0.05g of Y2O3 in an agate bowl.

[0136] Application Examples The procedure is similar to that of the example in EP 21157055.1. The method, equipment and materials were the same as those in EP 21157055.1. Only the (post-treated) phosphor according to the present invention was substituted.

[0137] Antibacterial effect test Aqueous curable compositions were prepared according to Tables 1 and 2. 50g of glass beads were added to each composition, and the mixture was milled in a speed mixer at 2000 rpm for 5 minutes. After filtering out the glass beads, each composition was coated onto a high-gloss rolled aluminum panel and crosslinked to form a film with a dry film thickness of 50µm. The substrate was then coated with a coating whose surface was expected to have antibacterial activity, while the control had no expected antibacterial activity. Comparative Examples CE1 and CE2 contained no phosphor.

[0138] [Table 1] Silikopur 8081 is an aqueous silicone-modified polyurethane dispersion from Evonik for air drying.

[0139] [Table 2] The transfer method was carried out as in EP21157055.1. It was found that the coatings C1-1, C1-2 and C2-1, C2-2 according to the present invention have antibacterial properties.

Claims

1. 1. An aqueous curable composition for producing a coating having antimicrobial properties, comprising at least one film-forming polymer; Optionally, at least one additive; optionally at least one curing agent; at least one up-conversion phosphor of general formula (I), Equipped with The aqueous curable composition is characterized in that the phosphor has a coating applied by a post-treatment that includes at least one material selected from the group consisting of an inorganic oxide, a silicate, a borate, a phosphate, or a mixture thereof, and the material has a band gap greater than 6.0 electron volts (eV). A １－ｘ－ｙ－ｚ B ＊ ｙ B ２ SiO ４ :Ln １ ｘ 、Ln ２ ｚ 、 (I) (In the formula, x=0.0001~0.0500; z = 0.0000 or z = 0.0001 to 0.3000, where y = x + z; A is selected from the group consisting of Mg, Ca, Sr, and Ba; B is selected from the group consisting of Li, Na, K, Rb, and Cs; B ＊ is selected from the group consisting of Li, Na, and K, where B is B ＊ Is it the same as B? ＊ is not the same as Ln １ is selected from the group consisting of praseodymium (Pr), erbium (Er), and neodymium (Nd); Ln ２ is selected from gadolinium (Gd).

2. 10. The composition of claim 1, wherein the material has a band gap of at most 12 electron volts (eV).

3. The material is SiO ２ , α-Al ２ O ３ , MgO, MgAl ２ O ４ , Ca polyphosphate, Sr polyphosphate, Ca or Sr pyrophosphate (Ca １－ｘ Sr ｘ ) ３ P ２ O ７ (x = 0.0 to 1.0), or a mixture thereof.

4. 2. The composition of claim 1, wherein said material is formed on said phosphor as a result of post-treatment with a starting material.

5. 2. The composition of claim 1, wherein the starting material is a composition selected from the group of tetraalkyl orthosilicates, wherein the alkyl groups at each occurrence are the same or different and have 1 to 10 carbon atoms.

6. 2. The composition according to claim 1, characterized in that the starting materials are selected from tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetraisopropyl orthosilicate and tetrabutyl orthosilicate and / or mixtures thereof.

7. 10. The composition of claim 1, wherein the phosphor after post-treatment has a crystalline core with a glassy or amorphous coating.

8. 10. The composition of claim 1, wherein the phosphor material prior to post-treatment is prepared with at least one flux.

9. 2. The composition according to claim 1, characterized in that the flux used is at least one substance from the group of ammonium halides, alkali metal halides, alkaline earth metal halides and lanthanide halides.

10. 2. The composition of claim 1, wherein the halide is fluoride, bromide, or chloride.

11. 2. The composition of claim 1, wherein the alkali metal is potassium, sodium or lithium.

12. 2. The composition of claim 1, wherein the lanthanide is praseodymium.

13. 2. The composition of claim 1, wherein the alkaline earth metal is calcium or strontium.

14. 2. The composition of claim 1, wherein said phosphor is doped with praseodymium.

15. 2. The composition of claim 1, wherein said phosphor is doped with praseodymium and co-doped with gadolinium.

16. 2. The composition of claim 1, wherein the phosphor is a crystalline silicate or a crystalline silicate doped with lanthanide ions, and contains at least one alkali metal ion and at least one alkaline earth metal ion.

17. 2. The composition of claim 1, wherein said phosphor is at least partially crystalline.

18. 2. The composition according to claim 1, wherein said phosphor is selected from compounds of general formula (Ia): A １－ｘ－ｙ－ｚ B ＊ ｙ B ２ SiO ４ :Pr ｘ 、Gd ｚ 、 (Ia) wherein A is selected from the group consisting of Mg, Ca, Sr, and Ba; B is selected from the group consisting of Li, Na, K, Rb, and Cs; B ＊ is selected from the group consisting of Li, Na, and K, where B is B ＊ or B is not the same as B*, x=0.0001~0.0500; z = 0.0000 or z = 0.0001 to 0.3000, where y = x + z.

19. 2. The composition according to claim 1, characterized in that the phosphor is selected from compounds of general formula (II). (1 １－ａ Sr ａ ) １－２ｂ Ln ｂ Na ｂ Li ２ SiO ４ (II) wherein Ln is selected from the group consisting of praseodymium, gadolinium, erbium, and neodymium; a = 0.0000 to 1.0000, b = 0.0001 to 0.5000.) 20. The composition according to claim 1, wherein the phosphor is selected from compounds of the general formula (IIa). Ca １－２ｂ Pr ｂ Na ｂ Li ２ SiO ４ (IIa) (Wherein, b = 0.0001 to 0.5000.)

21. The phosphor is Ca ０．９８ Pr ０．０１ Na ０．０１ Li ２ SiO ４ or Ca ０．９４ Pr ０．０３ Na ０．０３ Li ２ SiO ４ The composition according to claim 1, characterized in that

22. 2. The composition of claim 1, wherein said phosphor contains a halogen corresponding to the halide of the flux.

23. The phosphor, when irradiated with electromagnetic radiation having a lower energy and a longer wavelength in the range of 2000 to 400 nm, emits electromagnetic radiation having a higher energy and a shorter wavelength in the range of 400 to 100 nm, wherein the maximum emission intensity of the electromagnetic radiation having the higher energy and the shorter wavelength is at least 1×10 ３ Counts / (mm ２ 2. The composition of claim 1, wherein the composition has a strength higher than that of the composition of claim 1.

24. 2. The composition of claim 1, wherein the phosphor according to formula (II) has XRPD reflections in the ranges from 23° 2Θ to 27° 2Θ and from 34° 2Θ to 39.5° 2Θ.

25. 10. The composition of claim 1, wherein the film-forming polymer contains functional groups that are reactive with an isocyanate-containing curing agent or catalyst.

26. 2. The composition according to claim 1, characterized in that the film-forming polymer is selected from the group 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 polyester polymers reacted with isocyanate-containing curing agents.

27. 10. The composition of claim 1, wherein the film-forming polymer has a transmittance of at least 75% by twin beam UV / VIS spectrometer.

28. 10. The composition of claim 1, characterized by a transmittance of at least 70% by twin beam UV / VIS spectrometer.

29. The phosphor has an average particle size d50 of 0.1 to 50 μm, as measured in accordance with ISO 13320: 2020 and USP 429. The composition of claim 1.

30. 2. The composition of claim 1, wherein the additive is selected from the group consisting of dispersants, rheological aids, leveling agents, wetting agents, antifoaming agents and UV stabilizers.

31. 2. The composition of claim 1, wherein the curing agent is selected from the group of aliphatic and cycloaliphatic isocyanates.

32. 10. The composition of claim 1, wherein the coating produced therefrom has antimicrobial activity against bacteria, yeasts, molds, algae, parasites, spores or viruses.

33. The coatings produced therefrom are - causative agents of nosocomial infections, -pathogenic environmental organisms, -Pathogens in food and drink, The composition according to claim 1, characterized in that it has an antibacterial effect against

34. 10. Use of the composition according to claim 1 for the preparation of a dispersion, millbase, adhesive, trowell compound, rendering, paint, coating or printing ink, inkjet, grinding resin or pigment concentrate.

35. 10. Use of the composition according to claim 1 for the preparation of a coating having antibacterial properties.

36. 10. Use of the composition according to claim 1 for coating substrates in sanitary facilities and hospitals and in the food and beverage industry.

37. 10. An article at least partially coated with the curable composition of claim 1.

38. A phosphor selected from the group consisting of compounds of general formula (I), compounds of general formula (Ia), compounds of general formula (II) and compounds of general formula (IIa), having an essentially crystalline core with a glassy coat, the glassy coat comprising a material selected from the group consisting of inorganic oxides, silicates, borates, phosphates or mixtures thereof, the material having a band gap greater than 6.0 electron volts (eV). General formula (I): A 1-xy-z B * y B 2 SiO 4 :Ln 1 x , Ln 2 z , (I) (In the formula, x=0.0001~0.0500; z = 0.0000 or z = 0.0001 to 0.3000, where y = x + z; A is selected from the group consisting of Mg, Ca, Sr, and Ba; B is selected from the group consisting of Li, Na, K, Rb, and Cs; B* is selected from the group consisting of Li, Na, and K, where B is the same as B* or B is not the same as B*; Ln 1 is selected from the group consisting of praseodymium (Pr), erbium (Er), and neodymium (Nd); Ln 2 is selected from gadolinium (Gd). General formula (Ia): A 1-xy-z B * y B 2 SiO 4 : Pr x , Gd z , (Ia) wherein A is selected from the group consisting of Mg, Ca, Sr, and Ba; B is selected from the group consisting of Li, Na, K, Rb, and Cs; B* is selected from the group consisting of Li, Na, and K, where B is the same as B* or B is not the same as B*; x=0.0001~0.0500; z = 0.0000 or z = 0.0001 to 0.3000, where y = x + z. General formula (II): (Ca 1-a Sr a ) 1-2b Ln b Na b Li 2 SiO 4 (II) wherein Ln is selected from the group consisting of praseodymium, gadolinium, erbium, and neodymium; a = 0.0000 to 1.0000, b = 0.0001 to 0.5000.) General formula (IIa): Ca 1-2b Pr b Na b Li 2 SiO 4 (IIa) (Wherein, b = 0.0001 to 0.5000.)

39. 39. The phosphor of claim 38, wherein the glassy coat is made of a material having a bandgap greater than 6.0 electron volts (eV).

40. 40. The phosphor of claim 39, wherein the glassy coat is made of a material having a band gap of less than 12.0 electron volts (eV).

41. The material is SiO ２ , α-Al ２ O ３ , MgO, MgAl ２ O ４ , Ca polyphosphate, Sr polyphosphate, Ca or Sr pyrophosphate (Ca １－ｘ Sr ｘ ) ３ P ２ O ７ (x=0.0 to 1.0), or a mixture thereof.

42. 39. The phosphor of claim 38, wherein the crystalline core is produced with the flux of claim 8.

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