Aqueous curable composition for producing coatings containing 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 an aqueous curable composition for producing a coating having antibacterial properties, its use, and a coating produced therefrom and an article coated therewith.

Background Art

[0002] Humans are exposed to a wide variety of microorganisms such as bacteria, fungi, and viruses every day. Many of these microorganisms are useful or even necessary. Nevertheless, there are not only harmless representatives but also bacteria, fungi, and viruses that cause diseases or are fatal.

[0003] Microorganisms can be transmitted through daily interactions with other people and contact with articles used by other people. Surfaces are given an antibacterial finish, especially in areas sensitive to hygiene. The fields of use are, in particular, the surfaces of medical devices and consumer goods in hospitals and outpatient health care 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 in today's care sector, medicine, and places where many people socialize in closed spaces. A current particular risk is also the increasing occurrence of so-called multi-drug resistant bacteria that have become insensitive to most antibiotics.

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

[0005] While chemical and physical methods are highly effective in destroying microorganisms in most cases, their effects are short-lived. Chemical methods, however, promote the development of resistance and can lead to the destruction of surfaces that should be protected, making them unsuitable for certain applications under specific circumstances. However, the biggest drawback, especially in the case of chemical organic substances, is their danger or toxicity to humans. Certain substances, such as formaldehyde, which have been used as disinfectants for many years, are now suspected of causing cancer and being highly harmful to the environment.

[0006] Antimicrobial surfaces can make a decisive contribution to solving these problems. Current standard processes for producing such antimicrobial properties primarily utilize active ingredients incorporated into the material, such as silver particles, copper particles, their metal oxides, or quaternary ammonium compounds. This often involves processing antimicrobial metals, metal oxides, or metal oxide mixtures to produce nanoparticles, which are then mixed into paints, coatings, or polymer materials. However, the widespread use of metal particles is questionable because it is nearly impossible to assess the long-term effects of these heavy metals on humans and the environment.

[0007] For example, Patent Document 1 discloses particles finished with layers containing both antimonstin oxide and manganese oxide. Those skilled in the art know that antimicrobial surfaces are produced due to the electrochemical properties of metals, which develop microscale galvanic cells in the presence of moisture, resulting in a bactericidal effect thanks to the microscale electric field.

[0008] Similarly, UV radiation is known to 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 is used to distinguish between different proteins, amino acids / nucleic acids (e.g., DNA or RNA), and peptide bonds between individual acids present in microorganisms, tissues, or cells. Absorption must be taken into consideration. For example, DNA / RNA absorbs electromagnetic radiation well in the wavelength range of 200-300 nm, and especially well at 250-280 nm, making this radiation range particularly suitable for DNA / RNA inactivation or mutation. Therefore, it is possible to inactivate pathogenic microorganisms (viruses, bacteria, yeasts, fungi, spores, and especially (interalia)) with such irradiation. Depending on the duration and intensity of irradiation, mutations may be induced, or even the structure of DNA and RNA may be destroyed. Thus, metabolically active cells can be inactivated and / or their ability to proliferate can be eliminated. An advantage of irradiating with ultraviolet light is that microorganisms cannot develop resistance to it. However, these physical methods require specific equipment and generally need to be repeated regularly by trained personnel, making their widespread use difficult.

[0009] Furthermore, the use of "upconversion" effects is also known, similar to direct irradiation with electromagnetic radiation from the UV wavelength range. This involves using phosphor particles that can convert electromagnetic radiation with wavelengths beyond UV radiation, particularly visible or infrared radiation, into electromagnetic radiation with shorter wavelengths, making it possible to achieve emission of radiation with a desired effect by individual phosphor particles.

[0010] Patent Document 2 relates to an object that emits light in the UV wavelength range. The phosphor particles are embedded in a region near the surface within the material on which the body is formed, or in a coating of the body. Generally, it is stated here that the phosphor particles are added directly to a coating formed on the material during processing, and the specific material needs to have appropriate consistency or viscosity. Patent Document 2 is silent regarding suitable polymers and additives.

[0011] Patent documents 3 and 4 describe phosphors that can be introduced into polyvinyl chloride, acryloyl butadiene, polyolefins, polycarbonates, polystyrene, or nylon. These phosphors kill pathogenic microorganisms by their upconversion properties. These are phosphors prepared at temperatures of 1800-2900°C. Although patent documents 3 and 4 disclose compositions containing the phosphors having claimed antimicrobial activity, they do not show any evidence of upconversion properties or microbiological experiments. The processes disclosed in these documents do not result in phosphors with upconversion properties, but rather in 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). However, the appearance of the coating surface is of paramount importance to consumers.

[0013] The requirements for coatings and paints are diverse. In principle, a coating layer or paint coating has two tasks or functions: protective and decorative. When the term "coating layer" is used below, both types of coatings are intended. They decorate, protect, and preserve materials such as wood, metal, and plastic. Therefore, on the one hand, a bright, glossy coat layer is needed, while on the other hand, chemical and mechanical stability, a certain slipperiness on the coating, or a specific feel are required. A continuous court layer is required.

[0014] In contrast to Patent Document 6, the unpublished patent applications EP19202910.6 and PCT / EP2020 / 077798 disclose phosphors demonstrating upconversion and preparation thereof. Such phosphors can convert irradiation with electromagnetic radiation having lower energy and longer wavelengths in the range of 2000-400 nm, particularly in the range of 800-400 nm, into electromagnetic radiation having higher energy and shorter wavelengths in the range of 400-100 nm, preferably in the range of 300-200 nm, and as a result they are suitable for use as antimicrobial phosphors in coating layers.

[0015] For example, the yet-to-be-published European patent application EP21157055.1 describes a composition comprising at least one film-forming polymer, at least one upconversion phosphor as taught in EP19202910.6 and PCT / EP2020 / 077798, optionally at least one additive, and optionally at least one curing agent. Coating layers comprising these phosphors have been shown to have antimicrobial activity without significantly impairing other properties, particularly storage stability.

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

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

[0018] Solvents are used to establish processable consistency in the coating material. Low molecular weight organic liquids that completely dissolve the film-forming agent used are commonly employed.

[0019] Coatings, coating materials, paints, and coating systems are used synonymously in this specification.

[0020] However, solvent-based systems have toxicological and ecological drawbacks. High levels of flammable solvents, which are harmful to health, are undesirable for health, safety, and environmental protection reasons. Furthermore, the use of solvents is increasingly subject to legal regulations. These stem, among other things, from various national and international guidelines (EU Decopaint guidelines) regarding the restriction of VOC (volatile organic compound) emissions from coating materials and the reduction of health risks to processors and users from volatile and semi-volatile compounds (VOCs and SVOCs). Refer to the requirements of the Building Products Health Assessment Committee or the Building Certification by the German Sustainable Building Council (DGNB) or Leadership in Energy & Environmental Design (LEED).

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

[0022] [Patent Document 1] International Publication No. 2019 / 197076 [Patent Document 2] German Patent Application Publication No. 10 2015 102 427 [Patent Document 3] U.S. Patent Application Publication No. 2009 / 0130169 [Patent Document 4] International Publication No. 2009 / 064845A2 Specification [Patent Document 5] U.S. Patent Application Publication 2009 / 0130169, Specification A1 [Patent Document 6] International Publication No. 2009 / 0644845A2 Specification [Overview of the project] [Problems that the invention aims to solve]

[0023] Therefore, it is desirable to provide the type of aqueous curable composition described in the introduction, which can be used to manufacture aqueous coatings that provide protection against microorganisms, and the antimicrobial action should be carried out via a physical pathway. Thus, the curable composition is not subject to the Biocides Regulation (Regulation (EU) No. 528 / 2012 of the Council of 22 May 2012 in the current text of the European Parliament and 2019), which is highly advantageous as it eliminates the need for approval periods and costs. [Means for solving the problem]

[0024] Based on the teachings of European Patent Applications EP19202910.6, PCT / EP2020 / 077798 and EP21157055.1, the present invention provides an aqueous curable composition for the manufacture of coatings having antimicrobial properties, comprising: - At least one film-forming polymer, - At least one optional additive, -Optionally, at least one curing agent, - At least one upconversion 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, or B is B * is not the same as, preferably B and B * 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), where the phosphor as a result of the post-treatment contains at least one material having a band gap exceeding 6 electron volts (eV) and being stable against hydrolysis.)

[0025] Phosphors prepared according to the teachings of European patent application EP19202910.6, PCT / EP2020 / 077798, and EP21157055.1 have been found not to exhibit upconversion when suspended in water.

[0026] Without wishing to be bound by theory, it is assumed that certain elements of the phosphor enter the solution, and thus the crystal lattice structure of the phosphor is destroyed to such an extent that the phosphor no longer exhibits upconversion. Therefore, the physical antibacterial action may be lost.

[0027] Surprisingly, using the currently post-treated phosphor according to the present invention, it was possible to create a diffusion barrier so that the aqueous curable composition according to the present invention can be used for the production of antibacterial coatings. Unexpectedly, the phosphor has been found to be able to convert the wavelengths necessary for the antibacterial action and to be stable against hydrolysis.

[0028] Those that are not coated, not post-treated, not encapsulated are understood here as synonyms, and the same applies to the terms coated, post-treated, encapsulated.

[0029] Here, the band gap of the preferred material can affect the diffusion barrier. For example, the preferred material allows UV-C radiation (200-280 nm) to pass through without attenuation.

[0030] This material preferably has a band gap of 12 electron volts (eV) or less.

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

[0032] The materials are preferably SiO2, α-Al2O3, MgO, MgAl2O4, Ca polyphosphate, Sr polyphosphate, Ca or Sr pyrophosphate (Ca 1-x Sr x )Selected from the group consisting of 3P2O7 (x=0.0~1.0) or mixtures thereof.

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

[0034] Preferred starting materials for post-treatment are tetraalkyl orthosilicates, where each occurrence has the same or different alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetraisopropyl orthosilicate, and tetrabutyl orthosilicate and / or mixtures thereof.

[0035] Tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetraisopropyl orthosilicate (TiPOS), tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS), and / or mixtures thereof are of particular preference.

[0036] Preferred starting materials also include, for example, Al alkoxides such as Al methoxide, Al ethoxide, Al propoxide, Al isopropoxide, and Al butoxide; or Mg alkoxides such as, for example, Mg methoxide, Mg ethoxide, Mg propoxide, Mg isopropoxide, and Mg butoxide; or Al and Mg alkoxides such as Al / Mg methoxide, Al / Mg ethoxide, Al / Mg propoxide, Al / Mg isopropoxide, and 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 before post-treatment is prepared with at least one flux.

[0039] Those skilled in the art are familiar with a wide variety of fluxes from the prior art, including, where applicable, ammonium, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lead, lanthanum, lutetium, aluminum, bismuth, boric acid halides, carbonates, sulfates, oxides, and borates. They are also familiar with their applications in the field of metallurgy, for example, to accelerate crystal growth or to suppress the formation of foreign phases.

[0040] Therefore, finding the appropriate flux was also of particular importance.

[0041] To our great surprise, the preparation of upconversion phosphors in the presence of at least one halogen-containing flux was found to result in upconversion phosphors having a more uniform particle size distribution and increased emission intensity or greater quantum yield compared to phosphors without flux or with different fluxes.

[0042] The process of treating a product with flux is also called fluxing, meaning the product is treated with flux.

[0043] The example shows 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 more easily.

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

[0045] The emission intensity of upconversion phosphors could also be achieved through a simple technical implementation of synthesis.

[0046] Therefore, a further subject of the present invention is the process of preparing these upconversion phosphors and the upconversion phosphors obtained thereby.

[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, upconversion phosphors prepared using halides from this group have been found to have higher emission intensities than other fluxes.

[0048] The halogenated compound is preferably a fluoride or 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 phosphor is preferably doped with praseodymium used in the composition according to the present invention.

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

[0054] It is preferable that the phosphor is at least partially crystalline. Therefore, it is preferable that the phosphor is partially or completely crystalline. Therefore, it is preferable that the phosphor is at least not completely amorphous. Therefore, it is preferable that the phosphor is not an amorphous solidified molten material (glass).

[0055] The phosphor is preferably 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 present invention, the phosphor is preferably selected 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 * B is selected from the group consisting of Li, Na, and K. Here, B is B * Is it the same as B? * Not the same as B and B * They are not the same. x = 0.0001 ~ 0.0500; z = 0.0000 or z = 0.0001 to 0.3000. (where y = x + z.)

[0057] B * This is where it functions to balance the charge of the praseodymium or gadolinium substitution.

[0058] Here, 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., A = (Mg a1 Ca a2 Sr a3 Ba a4 ) 0≦a1≦1, 0≦a2≦1, 0≦a3≦1, 0≦a4≦1, where a1+a2+a3+a4=1. Therefore, A is (Ca 0.9 Sr 0.1 ) can sometimes represent this.

[0059] In the composition according to the present invention, the phosphor is preferably selected from compounds of general formula (II). (Ca 1-a Sr a ) 1-2b Ln b Na b Li2SiO4(II) (In the formula, 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, especially 0.0000. b = 0.0001 to 0.5000, preferably 0.0001 to 0.1000, and especially 0.0050 to 0.0500.

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

[0061] Ln 1 It is useful for doping. For doping, the use of praseodymium is preferred. Ln 2 It is used for optional co-doping. For optional co-doping, gadolinium is preferred. 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 even more preferable to select a phosphor from 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, and especially 0.005 to 0.0500.)

[0063] Phosphor is Ca 0.98 Pr 0.01 Na 0.01 It is particularly preferable that the material be Li2SiO4. 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 lower energy and longer wavelengths in the range of 2000 to 400 nm, particularly in the range of 800 to 400 nm, and emits electromagnetic radiation having higher energy and shorter wavelengths in the range of 400 to 100 nm, preferably in the range of 300 to 200 nm. Furthermore, the maximum emission intensity of the electromagnetic radiation having higher energy and shorter wavelengths is at least 1 × 10⁻⁶ 3 Count / (mm) 2* s), preferably 1 × 10 4 Count / (mm) 2* s) is higher than, and particularly preferably 1 × 10 5 Count / (mm) 2* It is preferable that the intensity is higher than s). To determine these indicators, the emission is preferably induced by a laser, particularly a laser having an output of 75 mW at 445 nm and / or 150 mW at 488 nm.

[0065] The phosphors according to equation (II) preferably have XRPD signals in the ranges of 23°2θ to 27°2θ and 34°2θ to 39.5°2θ, and the signals are determined by the Bragg-Brentano geometry and Cu-Kα radiation. Details of the measurement method are described in European patent applications EP19202910.6 and PCT / EP2020 / 077798, which have not yet been published.

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

[0067] Moving forward from the processes described in these documents, the process according to the present invention includes the following steps. -i) Lanthanide nitrate, lanthanide carbonate, lanthanide carboxylic acid, preferably lanthanide acetate, lanthanide sulfate, lanthanide oxide, more preferably Pr6O 11 Prepare at least one lanthanide salt selected from and / or Gd2O3, where, The lanthanide ions in lanthanide oxides or lanthanide salts are selected from praseodymium, gadolinium, erbium, and neodymium, and in the case of co-doping, at least two of these are selected. -ii) Prepare a silicate, preferably a silicate, particularly preferably an alkali metal salt of a silicate, or silicon dioxide. -iii) Prepare an alkali metal silicate or alkali metal carbonate, which is selected from at least one alkaline earth metal salt and at least one alkali metal salt, preferably lithium salt or lithium compound, and optionally selected from sodium salt and potassium salt, preferably a salt of lithium salt, preferably a salt of lithium carbonate, calcium carbonate and sodium carbonate, -iv) Prepare 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 of i), ii), iii) and optionally iv) by grinding to obtain a mixture, -b) To obtain the mixture, i), ii), and iii) are mixed in an organic polar or nonpolar solvent that is not an aprotic solvent, and the mixture of b) is calcined at 600-1000°C (step 1a) to remove the organic components, and below, to obtain the calcined mixture, it is preferable to calcine at 600-1000°C for at least 1 hour, preferably 2 hours or more, under a standard (air) atmosphere. , - In the firing step, preferably in air, at a temperature lower than the melting temperature of the silicate-based material, the mixture from a) or the firing mixture from b) is fired to at least partial crystallization, preferably in a further firing step (step 1b) at a temperature 50-200°C lower than the melting temperature of the silicate-based material for at least 3 hours, preferably in air to crystallize the silicate-based material, preferably at a temperature of 800-900°C, particularly preferably at about 850°C, for at least 3 hours, preferably at least 12 hours, preferably in air. -In a further firing step with increased 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, under a reducing atmosphere, thereby removing the lanthanides Ln 3+ Reduced to ions, - A silicate-based lanthanide ion-doped material is obtained, preferably after the material has been cooled. - To obtain a material having a band gap greater than 6.0 electron volts (eV) on the doped material, at least one starting material and a silicate-based lanthanide ion-doped material are post-treated.

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

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

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

[0071] The upconversion phosphor prepared in this manner can then preferably be subjected to post-treatment with the above-mentioned starting materials.

[0072] There are many possibilities for post-processing the phosphor to obtain a glassy or amorphous coating consisting of a substantially crystalline core and the aforementioned materials.

[0073] Proceeding from the above process for preparing phosphor, the post-treatment according to the present invention preferably includes the following steps: -Phosphorus is dispersed in an anhydrous medium, preferably the anhydrous medium contains an alcohol such as ethanol, methanol, propanol, butanol, isopropanol, isobutyl alcohol, or amyl alcohol. -Add departure materials, -In an alkaline region, preferably by Stober synthesis, a different sol-gel process, or homogeneous precipitation with urea, urotropin, or another hydroxide ion donor, the sol-gel process is carried out. -Optionally, you can add more starting materials, - Deagglomeration is performed, preferably by ultrasonic waves or stirring with the pulverized material, or by microfluidization. - Remove the anhydrous medium, - Dry the phosphorus.

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

[0075] Deagglutination can preferably be achieved by using a rotor stator system, such as a stirrer system, colloid mill, or homogenizer, or by spray drying.

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

[0077] The post-treatment step can also be optimized by spraying the starting material onto phosphor using a fluidized bed, intensive mixers, or the Innojet process.

[0078] Surprisingly, phosphors prepared according to EP19202910.6 and PCT / EP2020 / 077798 were found to possess the necessary upconversion properties in aqueous media that cause antimicrobial activity after post-treatment according to the present invention. In other words, these phosphors can convert electromagnetic radiation having wavelengths beyond UV radiation, particularly visible or infrared light, into electromagnetic radiation having shorter wavelengths, especially in the band in which, for example, microbial DNA or RNA can be destroyed or mutated. Therefore, these phosphors have very good compatibility with the compositions according to the present invention.

[0079] The present invention further provides a phosphor of formula (I), (Ia), (II), or (IIa), wherein the phosphor has an essential crystalline core having a glass-like or amorphous coating.

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

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

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

[0083] The materials are preferably SiO2, α-Al2O3, MgO, MgAl2O4, Ca polyphosphate, Sr polyphosphate, Ca or Sr pyrophosphate (Ca 1-x Sr x )3P2O7 (x = 0.0~1.0), or selected from the group consisting of mixtures thereof.

[0084] The phosphor is preferably prepared using at least one of the above fluxes, and then post-treated to ensure that the phosphor is hydrolyzable.

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

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

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

[0088] 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 polyester polymers, or mixtures, and reacts with an isocyanate-containing curing agent.

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

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

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

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

[0093] This is because, surprisingly, the film-forming polymer according to the present invention having low resonance has been found to improve antibacterial activity, allowing more electromagnetic radiation with lower energy and higher wavelengths to be transmitted in the range of 2000 nm to 400 nm, particularly in the range of 800 nm to 400 nm, and consequently, allowing more electromagnetic radiation with higher energy and shorter wavelengths to be emitted in the range of 400 nm to 100 nm, preferably in the range of 300 nm to 200 nm, which is transmitted in the range of 800 nm to 400 nm.

[0094] It has been found that the higher the transmittance, the higher the release, which is essential for antibacterial action.

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

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

[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, probably 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 crucial 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 wavelengths, and therefore, phosphors present in the composition cannot convert this electromagnetic radiation into electromagnetic radiation with higher energy and shorter wavelengths to release the one necessary for antibacterial activity.

[0099] Preferably, the composition according to the present invention has a transmittance of at least 75%, preferably at least 80%, and particularly preferably at least 85%, as measured at 260 nm.

[0100] Preferably, the composition according to the present invention has a transmittance of at least 75%, preferably at least 80%, and particularly preferably at least 85%, as measured at 500 nm.

[0101] The transmittance curve is preferably measured using an Analytik Jena "Specord200Plus" twin-beam UV / VIS spectrometer. A holmium 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 range is 1.4 nm. The monochromatic light is split into a measurement channel and a reference channel, and can be measured directly against the 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 transmittance of less than 70%, which may also have antibacterial properties, but their efficiency will be very moderate.

[0103] The phosphors preferably have an average particle size d50 of 0.1 to 50 μm, preferably d50 = 0.1 to 25 μm, and particularly preferably d50 = 0.1 to 5 μm, and are measured according to ISO 13320:2020 and USP 429, for example, with a Horiba LA-950 laser particle size analyzer.

[0104] It is preferable to add various additives to efficiently incorporate and / or stabilize phosphors in the composition according to the present invention.

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

[0106] Surprisingly, it was found that any addition of additives to the composition according to the present invention reduces the transmittance.

[0107] Therefore, in further embodiments in which additives are used, the compositions according to the present invention preferably have a transmittance of at least 70%, preferably at least 75%, and particularly preferably at least 80%, as measured at 260 nm.

[0108] Therefore, in further embodiments in which additives are used, the compositions according to the present invention have a transmittance of preferably at least 70%, preferably at least 75%, and particularly preferably at least 80%, as measured at 500 nm.

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

[0110] Examples of isocyanate-containing curing agents include monomer isocyanates, polymer isocyanates, and isocyanate prepolymers. Polyisocyanates are preferred over monomer isocyanates due to their lower toxicity. Examples of polyisocyanates include isocyanurates, uretdiones, and biuret based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). Examples of commercially available products include Covestro's DESMODUR® or Evonik Industries' VESTANAT. Known products include Covestro's DESMODUR® N3400, DESMODUR® N3300, DESMODUR® N3600, DESMODUR® N75, DESMODUR® XP2580, DESMODUR® Z4470, DESMODUR® XP2565, and DESMODUR® VL. Other examples include Evonik Industries' VESTANAT® HAT2500 L. Examples include V, VESTANAT® HB 2640 LV, or VESTANAT® T1890E. Examples of isocyanate prepolymers are Covestro's DESMODUR® EXP 2863, DESMODUR® XP 2599, or DESMODUR® XP 2406. Further isocyanate prepolymers known to those skilled in the art may be used. Hydrophilic isocyanates such as Covestro's Bayhydur 3100 are particularly preferred.

[0111] A catalyst may be used for curing. Catalysts selected from organic Sn(IV), Sn(II), Zn, Bi compounds, or tertiary amines can be used.

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

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

[0114] In the case of film-forming polymers that harden through physical drying, the addition of a reactive curing agent is not necessary.

[0115] The compositions according to the present 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.

[0116] Preferably, a coating produced from the composition according to the present invention has antimicrobial activity against bacteria, yeast, mold, algae, parasites, and viruses.

[0117] A coating manufactured according to the present invention preferably has antibacterial activity against the following: - Pathogens of nosocomia infections, preferably Enterococcus faecium and Staphylococcus aureus Bacteria, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, Escherichia coli, Enterobacter, Corynebacterium diphtheriae, Candida albicans, Rotavirus, Bacteriophages, - Facultative pathogenic environmental organisms, preferably Cryptosporidium parvum, Giardia la Mubria, amoeba (Acanthamoeba, Naegleria), coliform bacteria, coliform bacteria, fecal streptococcus, Salmonella, Shigella, Legionella species, Pseudomonas aerugin, Mycobacterium, enterovirus (e.g., polio and hepatitis A virus), - Pathogens in food and beverages, preferably Bacillus cereus, Campylobacter, Clostridium botulinum, Clostridium perfringens, Chronobacter, Escherichia coli, Listeria monocytogenes, Salmonella, Staphylococcus aureus, Vibrio, Yersinia enterocolitica, and bacteriophages.

[0118] It was found that the integration of the upconversion phosphor according to the present invention has been significantly improved. Upconversion phosphor and phosphor are used as synonyms.

[0119] The present invention further provides the use of compositions according to the present invention for the production of dispersions, mill bases, adhesives, trowel compounds, renderings, paints, coatings or printing inks, inkjet printers, pulverized resins or pigment concentrates. The use of the composition according to the present invention for the manufacture of coatings having antimicrobial properties is preferred.

[0120] Here, a coating having antimicrobial properties means that the coating has an antimicrobial surface that restricts or prevents the growth and proliferation of microorganisms. Surprisingly, it was also found that the coating according to the present invention possesses chemical and mechanical stability. Chemical and mechanical stability is particularly important because antimicrobial coatings are frequently used in areas where regular disinfection and further hygiene measures are required.

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

[0122] Preferably, the substrate is a metal, a mineral substrate (e.g., concrete, natural rock, or glass), a cellulose substrate, wood or hybrids thereof, a dimensionally stable plastic, and / or a thermosetting resin. The term "dimensionally stable plastics" is not exhaustive, but is understood to mean 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), and polyethylene (PE).

[0123] Preferably, the primer composition can be applied to the substrate before applying the curable film-forming composition. 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 industry.

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

[0125] Please note that the terms "antibacterial effect," "antibacterial action," and "antibacterial properties" are used here as synonyms. It should be noted here that articles according to the present invention preferably have antimicrobial activity without the release of antimicrobial active ingredients if the coating contains certain phosphors as described in the claims. Thus, the pathway by which microorganisms are killed is physical. Therefore, such materials are not subject to biocide regulations (Regulation (EU) No 528 / 2012 of the Council of 22 May 2012, in the current text of the European Parliament and 2019). [Brief explanation of the drawing]

[0126] [Figure 1.1] Figure 1.1 shows the X-ray powder diffraction pattern of the phosphor of Example 1 (top figure) compared with the reference phosphor (lower normalized X-ray powder diffraction pattern). This demonstrates that the desired phosphor was prepared. Figure 1.1 shows the instability of the phosphor that has not been post-treated in water. [Figure 1.2] Figure 1.2 shows the X-ray powder diffraction pattern of the phosphor from Example 1 (upper figure). Here, it is suspended in water. It was found that the phosphor has changed. It is thought that specific elements have leached out from the crystal lattice structure. Figure 1.2 shows the instability of phosphor that has not been post-treated in water. [Figure 1.3] Figure 1.3 shows the X-ray powder diffraction pattern of the phosphor of Example 1.1 (top figure) compared with the reference phosphor (lower normalized X-ray powder diffraction pattern). This demonstrates that the desired phosphor was prepared. [Figure 1.4] Figure 1.4 shows the X-ray powder diffraction pattern (X-ray diffraction diagram) of phosphor in Example 1.1 (upper figure). Here, it is suspended in water. It was found that the phosphor remained unchanged. [Figure 1.5] Figure 1.5 shows the conductivity of aftertreated and non-aftertreated phosphors that were previously suspended in water. It is clear that the aftertreated phosphors exhibited virtually no conductivity. Therefore, the phosphors according to the present invention are stable against 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 performed before the phosphor was suspended in water. The spectra clearly show that the intensity of both phosphor samples is within the desired wavelength range. The phosphor according to the present invention loses almost no intensity as a result of post-processing. [Figure 1.7]Figure 1.7 shows the emission spectrum 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 untreated phosphor no longer shows upconversion, which means that it has lost its physical antimicrobial activity. The phosphor according to the present invention can be used in aqueous compositions according to the present invention, which can be used to produce coatings having antimicrobial activity. [Figure 2.1] Figure 2.1 shows the X-ray powder diffraction pattern of the phosphor of Example 2 (top figure) compared with the reference phosphor (lower normalized X-ray powder diffraction pattern). This demonstrates that the desired phosphor was prepared. [Figure 2.2] Figure 2.2 shows the conductivity of post-treated and untreated phosphors according to Example 2, which were pre-suspended in water. It is clear that the post-treated phosphors exhibited substantially no conductivity. Therefore, the phosphors according to the present invention are stable against hydrolysis. [Figure 3.1] Figure 3.1 shows the conductivity of post-treated phosphors from Example 3 and untreated phosphors from Example 1, both of which were pre-suspended in water. It is clear that neither phosphor is stable against hydrolysis. 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 the SEM image of Example 3. Small, irregular spots are visible on the particle surface. These are presumed to be Y2O3 particles on top of them. [Figure 3.5] Figure 3.5 shows the SEM image of Example 1.1. The phosphor surface is smoother than the surface of Example 3. [Figure 3.6] Figure 3.6 shows an SEM image of uncoated phosphor. Only sections (black frames) are considered. It can be seen that no coating is identifiable on the particle surface, except for the mottled fragments of phosphor (see black frames). [Figure 3.7] Figure 3.7 shows the SEM image of Example 1.1. Here again, only the sections are considered (black frame). The marked elevations are identifiable on the surface. This may be due to a glass-like SiO2 coating (see black frame).

[0127] The following examples are solely for the purpose of illustrating the invention to those skilled in the art and do not constitute any limitation in any way to all of the claimed subject matter. [method]

[0128] Scanning electron microscopy was performed using a Zeiss EVO MA 10 scanning electron microscope. The scanning electron microscope was operated with a LaB6 cathode and an accelerating voltage of 10 kV at 2 pA. Before measurement, the sample chamber was approximately 5 * 10 -9 The values ​​were exhausted to mbar. Topography contrast was evaluated by detecting secondary electrons. The maximum resolution was 10 nm.

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

[0130] The emission spectrum was 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. A bandpass filter was used to suppress nth-order reflections caused by the monochromator.

[0131] The conductivity was determined using a Knick 703 laboratory conductivity meter. For this purpose, 0.1 g of the 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, and the measurements were recorded every 30 seconds. After this, the sample was 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. The calcination was then carried out for a further 6 hours at 850°C in a foaming gas atmosphere (5% H2 / 95% N2), thereby obtaining the desired product. The phosphorus was recovered for further measurement.

[0133] Example 1.1 Phosphor according to the present invention Phosphor (Ca 0.94 Pr 0.03 Na 0.03 ) Post-treatment of Li2SiO4 with 36 wt% SiO2 based on phosphorus. 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, 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, ultrasound was activated for 10 seconds every 10 minutes. Next, this dispersion was stirred for 3 hours, and ultrasound was activated for 10 seconds every 15 minutes. This 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 present invention Phosphor (Ca 0.94 Pr 0.03 Na 0.03 ) Post-treatment of Li2SiO4 with 72% by weight of SiO2 based on phosphorus. Post-treatment was carried out in the same manner as in Example 1.1 using a TEOS / ETOH mixture consisting of 40 ml of TEOS and 60 ml of ethanol.

[0135] Comparative Example Example 3: Phosphorus (Ca) by 5 wt% Y2O3 based on phosphorus 0.94 Pr 0.03 Na 0.03 ) Post-treatment of Li2SiO4 1g (Network 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 was similar to the example in EP21157055.1. The method, apparatus, and materials were the same as those in EP21157055.1. Only the (post-treated) phosphor according to the present invention was substituted.

[0137] Testing of antibacterial effect Aqueous curable compositions were prepared according to Tables 1 and 2. 50g of glass beads were added to each composition, and the mixtures were ground in a speed mixer at 2000 rpm for 5 minutes. After filtering off the glass beads, each composition was coated onto a high-gloss rolled aluminum panel and crosslinked to form a film with a dry thickness of 50 μm. Next, the coating was placed on the substrate, and its surface should have antibacterial properties, while the control did not exhibit the expected antibacterial properties. Comparative examples CE1 and CE2 did not contain phosphorus.

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

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

Claims

1. An aqueous curable composition for producing an antibacterial coating, comprising at least one film-forming polymer, At least one additive of your choice, At least one curing agent of your choice, At least one upconversion phosphor of general formula (I), Equipped with, The phosphor has a coating comprising at least one inorganic material selected from the group consisting of oxides, silicates, borates, phosphates, or mixtures thereof, which is imparted by post-treatment, and the material is characterized in that it 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? ＊ Not the same as, Ln １ It is selected from the group consisting of praseodymium (Pr), erbium (Er), and neodymium (Nd). Ln ２ (This is selected from gadolinium (Gd).)

2. The composition according to claim 1, characterized in that the material has a band gap of up to 12 electron volts (eV).

3. The aforementioned 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 The composition according to claim 1, wherein x = 0.0 to 1.0, or a mixture thereof.

4. The composition according to claim 1, characterized in that the material is formed on the phosphor as a result of post-treatment with the starting material.

5. The composition according to claim 1, wherein the starting material is selected from the group of tetraalkyl orthosilicates, and each generation has 1 to 10 carbon atoms, the alkyl group being the same or different.

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

7. The composition according to claim 1, characterized in that the post-processed phosphor has a crystalline core with a glassy or amorphous coating.

8. The composition according to claim 1, characterized in that the phosphorus substance before post-treatment is prepared with at least one flux.

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

10. The composition according to claim 1, characterized in that the halogen is a fluoride, bromide, or chloride.

11. The composition according to claim 1, characterized in that the alkali metal is potassium, sodium, or lithium.

12. The composition according to claim 1, characterized in that the lanthanide is praseodymium.

13. The composition according to claim 1, characterized in that the alkaline earth metal is calcium or strontium.

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

15. The composition according to claim 1, characterized in that the phosphor is doped with praseodymium and co-doped with gadolinium.

16. The composition according to claim 1, characterized in that 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. The composition according to claim 1, characterized in that the phosphor is at least partially crystalline.

18. The composition according to claim 1, characterized in that the 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) (In the formula, 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, or is B 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. 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) (In the formula, 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, characterized in that the phosphor is selected from compounds of general formula (IIa). Ca １－２ｂ Pr ｂ Na ｂ Li ２ SiO ４ (IIa) (In the formula, b = 0.0001 to 0.5000.)

21. The aforementioned 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 it is the same as the present.

22. The composition according to claim 1, characterized in that the phosphor contains a halogen corresponding to the halide of the flux.

23. When the phosphor is irradiated with electromagnetic radiation having lower energy and longer wavelengths in the range of 2000 to 400 nm, it emits higher energy and shorter wavelengths in the range of 400 to 100 nm, where the maximum emission intensity of the electromagnetic radiation having higher energy and shorter wavelengths is at least 1 × 10⁻⁶. ３ Count / (mm) ２ The composition according to claim 1, which has a higher strength than *s).

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

25. The composition according to claim 1, characterized in that the film-forming polymer contains a functional group that is reactive with an isocyanate-containing curing agent or catalyst.

26. The composition according to claim 1, characterized in that 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 a polyester polymer that reacts with an isocyanate-containing curing agent.

27. The composition according to claim 1, characterized in that the transmittance of the film-forming polymer, as measured by a twin-beam UV / VIS spectrometer, is at least 75%.

28. The composition according to claim 1, characterized in that the transmittance is at least 70% as measured by a twin-beam UV / VIS spectrometer.

29. The phosphorus is characterized by having an average particle size d50 of 0.1 to 50 μm, as measured in accordance with ISO 13320:2020 and USP 429. The composition according to claim 1.

30. The composition according to claim 1, characterized in that the additive is selected from the group consisting of dispersants, rheological aids, leveling agents, wetting agents, defoaming agents, and UV stabilizers.

31. The composition according to claim 1, characterized in that the curing agent is selected from the group consisting of aliphatic and alicyclic isocyanates.

32. The composition according to claim 1, characterized in that the coating produced therefrom has antibacterial activity against bacteria, yeast, mold, algae, parasites, spores, or viruses.

33. The coating produced from there is - Pathogens of nosocomia infections, -pathogenic environmental organisms, - Pathogens in food and beverages, The composition according to claim 1, characterized in that it has an antibacterial effect against [the target of the substance].

34. Use of the composition according to claim 1 for the manufacture of dispersions, mill bases, adhesives, trowel compounds, renderings, paints, coatings or printing inks, inkjet printers, pulverized resins or pigment concentrates.

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

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

37. An article characterized by being at least partially coated with the curable composition described in claim 1.

38. A phosphor selected from the group consisting of a compound of general formula (I), a compound of general formula (Ia), a compound of general formula (II), and a compound of general formula (IIa), having an essentially crystalline core with a glassy coating, wherein the glassy coating comprises a material selected from the group consisting of inorganic oxides, silicates, borates, phosphates, or mixtures thereof, and the material has 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) (In the formula, 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) (In the formula, 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) (In the formula, b = 0.0001 to 0.5000.)

39. The phosphor according to claim 38, characterized in that the glass-like coating is made of a material having a band gap exceeding 6.0 electron volts (eV).

40. The phosphor according to claim 39, characterized in that the glass-like coating 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 The phosphor according to claim 38, selected from the group consisting of (x = 0.0 to 1.0) or mixtures thereof.

42. The phosphor according to claim 38, characterized in that the crystalline core is produced with the flux of claim 8.

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