Composition for production of coating comprising improved phosphor

Abstract

To provide a curable composition for production of a coating having an antimicrobial property, its use, and a method for forming an antibacterial coating on a base material.SOLUTION: A curable composition contains at least one film-forming polymer, at least one additive when necessary, at least one curing agent when necessary, and at least one up-conversion phosphor of General formula (I): A1-x-y-zB*yB2SiO4:Ln1x, Ln2z (I) (where, A is selected from Mg, Ca, Sr and Ba; B is selected from Li, Na, K, Rb and Cs; B* is selected from Li, Na and K; B is the same as or different from B*; Ln1 is selected from the group consisting of praseodymium (Pr), erbium (Er), and neodymium (Nd); and Ln2 is selected from gadolinium (Gd)). The phosphor has been prepared using at least one halogen-containing flux.SELECTED DRAWING: Figure 1.1

Description

Technical Field

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

Background Art

[0002] [[ID=S12]]Humans are exposed to millions of microorganisms such as bacteria, fungi, and viruses every day. Many of these microorganisms are useful or essential. However, there are also bacteria, fungi, and viruses that cause diseases or are life-threatening, just like these representative microorganisms with few harms.

[0003] Microorganisms can be transmitted through daily communication with others or by touching items used by others. Especially in places where hygiene is taken seriously, the surface is given an antibacterial finish. The fields of use are especially the surfaces of medical devices and consumer goods in hospitals and outpatient health and welfare facilities. In addition to these, there are surfaces in public places, the food and beverage sector, and animal breeding. The spread of pathogenic microorganisms is a major issue today in the care sector and medicine, and places where people communicate in closed spaces. The current risk worthy of attention is the increasing occurrence of so-called multi-drug resistant bacteria that are resistant to standard antibiotics.

[0004] In order to reduce the risk of pathogen spread through contact surfaces, in addition to standard hygiene measures, antibacterial technologies and materials are used. By using chemical substances or physical methods, it is possible to significantly affect the growth process of microorganisms. Physical methods include, for example, heat, cold air, radiation, or ultrasonic waves. Among chemical methods, halogens, metal ions, organic compounds and dyes, and toxic gases are known.

[0005] Chemical and physical methods are, in most cases, very effective in destroying microorganisms, but their effects are only temporary. Chemical methods are unsuitable for some applications under certain circumstances because they promote the development of resistance and lead to the destruction of the surface that should be protected. However, the biggest drawback, especially in the case of chemical organic substances, is the 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 extremely harmful to the environment.

[0006] Antimicrobial surfaces can make a significant contribution to solving these challenges. Current standard processes for achieving 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 a layer containing both antimonstin oxide and manganese oxide. Those skilled in the art know that a microscale galvanic cell develops in the presence of moisture, and that an antimicrobial surface is generated by the electrochemical properties of metals that produce a bactericidal effect due to a microscale electric field.

[0008] Similarly, UV radiation is known to be usable in medicine or hygiene, for example, to disinfect water, gases, 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 of 200 nm to 280 nm. When using electromagnetic radiation of different wavelengths, it is necessary to consider the different absorption effects of various proteins, amino acids / nucleic acids (e.g., DNA or RNA) present in microorganisms, tissues, or cells, and the peptide bonds of individual acids. For example, DNA / RNA absorbs electromagnetic radiation well in the wavelength range of 200 nm to 300 nm, especially 250 nm to 280 nm, so this radiation is particularly suitable for DNA / RNA inactivation. Thus, pathogenic microorganisms (viruses, bacteria, yeasts, and fungi, among others) can be inactivated by such irradiation. Depending on the duration and intensity of irradiation, the structure of DNA or RNA can be destroyed. Thus, metabolically active cells can be inactivated and / or their ability to proliferate can be severed. The advantage of UV radiation irradiation 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, particularly visible or infrared radiation, into shorter wavelength electromagnetic radiation, thereby enabling the emission of radiation with a desired effect by individual phosphor particles.

[0010] Patent Document 2 relates to an object that emits electromagnetic radiation in the UV wavelength range. Phosphor particles are embedded in the object or in a coating of the object in a region near the surface of the material from which the object is based. It is generally stated in the document that the phosphor particles are added directly to the coating to be formed on the material during the processing process, and that the material must have an appropriate viscosity or consistency. Patent Document 2 does not describe suitable polymers and additives.

[0011] Patent documents 3 and 4 describe phosphorus that can be introduced into polyvinyl chloride, acryloyl butadiene, polyolefin, polycarbonate, polystyrene, or nylon, and that can kill pathogenic microorganisms due to their upconversion properties. These phosphorus are prepared at temperatures of 1,800 to 2,900°C. While patent documents 3 and 4 disclose compositions containing the phosphorus with claimed antimicrobial activity, they do not provide evidence of either upconversion properties or microbiological experiments. The methods disclosed in these documents do not result in phosphorus with upconversion properties, but rather in amorphous, glass-like products.

[0012] Furthermore, Patent Documents 3 and 4 do not describe 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, or plastic. Therefore, on the one hand, a bright, glossy coat layer is required, while on the other hand, a continuous coat layer is needed to ensure chemical and mechanical stability, a certain smoothness of the coating, or a specific feel.

[0014] In contrast to Patent Document 4, Patent Documents 5 and 6, which have not yet been published, disclose phosphors exhibiting upconversion and their preparation. Such phosphors can convert low-energy, long-wavelength electromagnetic radiation in the 2000nm to 400nm range, particularly in the 800nm ​​to 400nm range, to high-energy, short-wavelength electromagnetic radiation in the 400nm to 100nm range, preferably in the 300nm to 200nm range, and as a result they are suitable for use as antimicrobial phosphors in coating layers.

[0015] For example, Patent Document 7, which has not yet been published, describes a composition comprising at least one film-forming polymer, at least one upconversion phosphor as taught in Patent Documents 5 and 6, optionally at least one additive, and optionally at least one curing agent. It has been shown that a coating layer comprising these phosphors has antimicrobial properties without significantly impairing other properties, particularly storage stability.

[0016] However, it has been found that the phosphors prepared by the methods described in Patent Documents 5 and 6 exhibit a non-uniform particle size distribution. This presents certain challenges when incorporating these phosphors into a coating matrix. Even if an antimicrobial coating layer can be obtained by teaching in Patent Document 7, it would be even more desirable to increase the phosphor release intensity. [Prior art documents] [Patent Documents]

[0017] [Patent Document 1] International Publication Number 2019 / 197076 [Patent Document 2] German Publication Number 10 2015 102 427 [Patent Document 3] U.S. Patent Publication No. 2009 / 0130169A1 [Patent Document 4] International Publication Number 2009 / 064845A2 [Patent Document 5] European Patent Application No. 19202910.6 [Patent Document 6] International Application Number PCT / EP2020 / 077798 [Patent Document 7] European Patent Application No. 21157055.1 [Overview of the project] [Problems that the invention aims to solve]

[0018] Therefore, an object of the present invention is to provide a curable composition of the type described above, which can be used to produce a coating that provides protection against microorganisms, and which uses phosphorus having a uniform particle size distribution and exhibiting higher release intensity. [Means for solving the problem]

[0019] Based on the teachings of Patent Documents 5, 6, and 7, the present invention is a curable composition for producing an antibacterial coating. - At least one film-forming polymer, - At least one additive as needed, - At least one hardener as needed, -General formula (I): A 1-x-y-z B*y B2SiO4:Ln 1 x, Ln 2 z, (I) (In the formula, x=0.0001~0.0500, z=0.0000 or z=0.0001~0.3000, However, 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. B is either the same as or different from B*, preferably B and B* are different. Ln 1 It is selected from the group consisting of praseodymium (Pr), erbium (Er), and neodymium (Nd). Ln 2 It is selected from gadolinium (Gd). At least one upconversion phosphor, It consists of, We propose a curable composition in which the phosphor is prepared using at least one halogen-containing flux.

[0020] Those skilled in the art are familiar with numerous fluxes of all kinds in the prior art (e.g., halides, carbonates, sulfates, oxides, and borates of ammonium, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lead, lanthanum, lutetium, aluminum, bismuth, and borate, respectively, where applicable). Their applications in the field of metallurgy, for example, to accelerate crystal growth or to suppress the formation of foreign phases, are also known.

[0021] Therefore, selecting an appropriate flux to achieve the desired properties was also an objective of the present invention. Thus, the discovery of a suitable flux is particularly important and already constitutes a contribution to the inventiveness.

[0022] In a truly surprising turn of events, it was found that preparing upconversion phosphors in the presence of at least one halogen-containing flux resulted in upconversion phosphors with a more uniform particle size distribution and improved emission intensity or quantum yield compared to phosphors without flux or with different fluxes.

[0023] Treatment with flux is also called fluxing, meaning that flux is applied to the product. In the examples, the particle size distribution of the flux phosphor according to the present invention is similar to a Gaussian distribution that shows particle size uniformity, and therefore its incorporation into a coating matrix can be advantageously and significantly easier to carry out. This is thought to improve coating properties such as the appearance of the coated surface (e.g., gloss, feel and touch).

[0024] Upconversion phosphor emission intensity can be achieved even with simple technical implementation.

[0025] Therefore, a further subject of the present invention is a method for preparing these upconversion phosphors and the upconversion phosphors obtained thereby.

[0026] 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 those prepared with other fluxes.

[0027] The halogen is preferably a fluoride or a chloride.

[0028] The alkali metal is preferably potassium, sodium, or lithium.

[0029] The lanthanoid is preferably praseodymium.

[0030] The alkaline earth metal is preferably calcium or strontium.

[0031] The phosphor is preferably doped with praseodymium and is used in the composition according to the present invention.

[0032] In the case of the composition according to the present invention, the phosphor is preferably doped with praseodymium and co-doped with gadolinium.

[0033] Preferably, the phosphor is at least partially crystalline. Therefore, it is preferred that the phosphor is partially or completely crystalline. Therefore, the phosphor is preferably not completely amorphous at least. Therefore, it is preferred that the phosphor is not a melt (glass) solidified into an amorphous state.

[0034] The phosphor is preferably a single crystalline silicate or consists of a plurality of crystalline silicates, and the crystalline silicate is doped with lanthanoid ions and contains at least one alkali metal ion and at least one alkaline earth metal ion.

[0035] In the case of the composition according to the present invention, the phosphor preferably has the 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, 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, B is either the same as or different from B*, preferably B and B* are different. x = 0.0001 to 0.0500, z=0.0000 or z=0.0001~0.3000, (However, y = x + z.) It is selected from the following compounds.

[0036] B* functions to balance the charge of praseodymium or gadolinium substitutions.

[0037] A is a single element from the group consisting of Mg, Ca, Sr, and Ba, or a combination of two or more elements from this group, i.e., A = (Mg a1 Ca a2 Sr a3 Ba a4 )(wherein the formula 0≦a1≦1, 0≦a2≦1, 0≦a3≦1, 0≦a4≦1, where a1+a2+a3+a4=1).Therefore, A can be, for example, (Ca 0.9 Sr 0.1 ) may be represented as follows.

[0038] In the case of the composition according to the present invention, the phosphor is preferably 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 particularly 0.0050 to 0.0500. It is selected from the following compounds.

[0039] Ln may represent a single element from the group consisting of praseodymium, gadolinium, erbium, and neodymium, or a combination of two elements from this group, i.e., Ln = (Ln 1 x Ln 2 y )(In the formula, 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 in equations (I) and (Ia).

[0040] Ln 1 It is used in doping. For doping, praseodymium is preferred. Ln 2 This is used for any co-doping. Gadolinium is preferably used for any 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.

[0041] Phosphor is given by the 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 0.1000, and particularly 0.0050 to 0.0500.) It is even more preferable to select from the compounds.

[0042] Phosphor is Ca 0.98 Pr 0.01 Na 0.01 It is particularly preferable that the material be Li2SiO4.

[0043] Preferably, the upconversion phosphor according to the present invention contains a halogen corresponding to the halide of the flux.

[0044] The phosphor preferably emits high-energy, short-wavelength electromagnetic radiation in the range of 400 nm to 100 nm, preferably in the range of 300 nm to 200 nm, when irradiated with low-energy, long-wavelength electromagnetic radiation in the range of 2000 nm to 400 nm, particularly in the range of 800 nm to 400 nm. The maximum emission intensity of the high-energy, short-wavelength electromagnetic radiation is at least 1.10 3 Count / (mm) 2 *s), preferably 1 × 10 4 Count / (mm) 2 *s) exceeding, and particularly preferably 1.10 5 Count / (mm) 2 It is even more preferable that the values ​​exceed *s). To measure these indices, it is preferable to induce the emission by a laser, particularly a laser having an output of 75 mW at 445 nm and / or 150 mW at 488 nm.

[0045] The phosphors relating to equation (II) preferably have XRPD signals in the ranges of 23°2Θ to 27°2Θ and 34°2Θ to 39.5°2Θ, and these signals have Bragg-Brentano type geometry and Cu-K α The measurement is performed using a line. Details of the measurement method are described in Patent Documents 5 and 6, which have not yet been published.

[0046] Patent documents 5 and 6, which have not yet been published, relate to the preparation of phosphors (particularly phosphors of formula (I), formula (Ia), and formula (II)) without the addition of flux.

[0047] Moving beyond the methods described in these documents, the method according to the present invention comprises the following steps. -i)~iv): i) Lanthanide nitrates, lanthanide carbonates, lanthanide carboxylic acids, preferably lanthanide acetates, lanthanide sulfates, lanthanide oxides, particularly preferably Pr6O 11and / or at least one lanthanide salt selected from Gd2O3 (the lanthanide ions in the lanthanide oxide or lanthanide salt are selected from praseodymium, gadolinium, erbium, and neodymium, and at least two of these are selected in the case of co-doping), ii) Silicates, preferably silicate salts, particularly preferably alkali metal salts of silicates, or silicon dioxide, iii) at least one alkaline earth metal salt and at least one alkali metal salt, preferably selected from lithium salts or lithium compounds, and optionally sodium salts and potassium salts, preferably salts of lithium salts, preferably alkali metal silicates or alkali metal carbonates selected from lithium carbonate, calcium carbonate, and sodium carbonate. iv) 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, or lithium chloride), alkaline earth metal halides (preferably calcium chloride or calcium fluoride), and lanthanoid halides (preferably praseodymium fluoride or praseodymium chloride). The process of preparing - a) a step of mixing i), ii), iii), and iv) by grinding to obtain a mixture, or b) a step of mixing i), ii), and iii) in an organic polar or nonpolar solvent that is not an aprotic solvent to obtain a mixture. The mixture from (step b) is calcined at 600-1000°C (step 1a) to remove organic components. It is preferable to obtain the calcined mixture by calcining at 600-1000°C for at least 1 hour, preferably 2 hours or more, under a standard (air) atmosphere. - A step in which the mixture from step a) or the calcined mixture from step b) is calcined at a temperature lower than the melting temperature of the silicate material, preferably in air. (Preferably at 800-900°C, particularly preferably at about 850°C, for at least 3 hours, preferably at least 12 hours, preferably in air, to crystallize the silicate material, at least partial crystallization is preferably carried out in another firing step (step 1b) at a temperature 50-200°C lower than the melting temperature of the silicate material, for at least 3 hours, preferably in air.) - In another firing step, the temperature is raised, preferably above 800°C and 50 to 200°C lower than 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, the lanthanides are converted to Ln 3+ The process of reducing to ions, - Preferably, after cooling, a silicate-based lanthanide ion-doped material is obtained.

[0048] Further detailed embodiments of the method can be found in Patent Documents 5 and 6, and describe the flux used in the method according to the present invention.

[0049] In a truly astonishing turn of events, it was possible to modify known methods using sophisticated techniques, which further resulted in optimized upconversion phosphors with exceptional and unexpected properties in terms of improved particle size distribution and emission intensity.

[0050] Preferably, a flux of 0.01% to 3.5% by weight, more preferably 0.5% to 3.5% by weight, and especially preferably 1.0% to 3.5% by weight, relative to the total amount of reactants, can be used.

[0051] Surprisingly, the phosphorus according to the present invention, prepared according to the teachings of Patent Documents 5 and 6, was found to possess the necessary upconversion properties that contribute to antibacterial activity. In other words, these phosphors can convert electromagnetic radiation with wavelengths exceeding UV radiation, particularly visible or infrared light, into shorter wavelength electromagnetic radiation, especially in regions where they can disrupt or mutate, for example, the DNA or RNA of microorganisms. Therefore, these phosphors are very well compatible with the compositions according to the present invention.

[0052] 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 Pr6O 11 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 an 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 ground in an agate mortar.

[0053] It should be noted that phosphorus can be ground according to the teachings of Patent Documents 5 and 6 to first obtain a uniform particle size, and then the desired particle size. However, in this case, the energy input will be greater, and the grinding process will last longer due to the non-uniformity of the prepared material and its particle size distribution.

[0054] Another problem that the present invention aims to solve is the selection of film-forming polymers that can be used in curable compositions having antibacterial properties. In principle, all film-forming polymers known from the prior art are useful.

[0055] The film-forming polymer preferably has a functional group that is reactive with an isocyanate-containing curing agent and is optionally catalyzed by a catalyst, preferably acidic hydrogen.

[0056] 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 aspartate polymers, or amino-functional polyester polymers, and reacts with an isocyanate-containing curing agent.

[0057] The film-forming polymer preferably has low resonance properties.

[0058] Those skilled in the art are familiar with the physical interactions at a surface. Depending on the material and its surface, multiple effects occur at the surface in response to incident light. Incident light is partially absorbed, partially reflected, and scattered depending on the material surface. Light can also be absorbed first and then re-emitted. In the case of opaque, translucent, or transparent materials, light can also penetrate the object (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), or emit fluorescence or phosphorescence with light of different colors (afterglow).

[0059] In the context of this specification, "low resonance" means that the film-forming polymer exhibits low absorption, reflectivity, reactivity, and scattering in the 240–500 nm UV region or the blue region. In contrast, transmittance should preferably be significant.

[0060] Surprisingly, the more low-energy, long-wavelength electromagnetic radiation in the 2000nm to 400nm range, particularly in the 800nm ​​to 400nm range, is transmitted, the more high-energy, short-wavelength electromagnetic radiation in the 400nm to 100nm range, preferably in the 300nm to 200nm range, can be emitted. This is because it has been found that the film-forming polymer according to the present invention, which has low resonance, improves antibacterial activity.

[0061] It has been found that the higher the transmittance, the higher the release, which is essential for antibacterial action.

[0062] 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%.

[0063] 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%.

[0064] For example, it should be noted that transmittance may be defined at different wavelengths (see Figure 1). In the present invention, a wavelength of 260 nm was selected as an example of the emitted wavelength, and a wavelength of 500 nm was selected as an example of the excitation wavelength. These are involved in upconversion on the one hand, and to a considerable extent in antibacterial activity on the other hand.

[0065] For example, if the transmittance is 100%, measuring at a wavelength of 260 nm will show that the same amount of radiation is converted and emitted. In other words, there is no loss due to absorption or scattering. If the transmittance is 80%, measuring at a wavelength of 260 nm will show that 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.

[0066] This significant discovery 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 low-energy, high-wavelength electromagnetic radiation, and therefore, phosphors present in the composition cannot convert and emit this electromagnetic radiation into high-energy, short-wavelength electromagnetic radiation. This conversion and emission is necessary for antibacterial activity.

[0067] 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.

[0068] 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%, when measured at 500 nm.

[0069] The transient curve is preferably measured using Analytik Jena's "Specord 200Plus" 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 comparison channel, allowing for direct measurement against a comparison sample. The radiation transmitted through the sample is detected and processed by a photodiode to generate an electrical signal.

[0070] It is conceivable to use compositions with a transmittance of less than 70%. They will probably still have antibacterial properties, but their efficiency will be very moderate.

[0071] The phosphor preferably has an average particle size d50 of 0.1 to 50 μm, preferably 0.1 to 25 μm, and particularly preferably 0.1 μm to 5 μm, measured using a Horiba LA-950 laser particle size analyzer in accordance with ISO 13320:2020 and USP 429.

[0072] Various additives can be added to efficiently incorporate and / or stabilize phosphorus in the composition according to the present invention.

[0073] The additive is preferably selected from the group consisting of dispersants, rheological aids, leveling agents, wetting agents, defoaming agents, and UV stabilizers.

[0074] Surprisingly, it was found that adding an additive to the composition according to the present invention reduces its transmittance.

[0075] Therefore, in another embodiment in which additives are used, the composition according to the present invention preferably has a transmittance of at least 70%, preferably at least 75%, and particularly preferably at least 80%, as measured at 260 nm.

[0076] Therefore, in another embodiment in which additives are used, the composition according to the present invention preferably has a transmittance of at least 70%, preferably at least 75%, and particularly preferably at least 80%, as measured at 500 nm.

[0077] Preferably, the composition according to the present invention comprises a curing agent selected from the group of aliphatic or alicyclic isocyanates.

[0078] 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 based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI), as well as uretdione and biuret. Examples of commercially available products include Covestro's trade name 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® HAT2500LV, VESTANAT® HB2640LV, or VESTANAT® T1890E. Examples of isocyanate prepolymers include Covestro's DESMODUR® EXP2863, DESMODUR® XP2599, or DESMODUR® XP2406. Other isocyanate prepolymers known to those skilled in the art may also be used.

[0079] A catalyst may be used for curing. A catalyst selected from organic Sn(IV), Sn(II), Zn, Bi compounds, or tertiary amines may be used.

[0080] It is preferable to use a catalyst selected from the group consisting of organotin catalysts, titanates or zirconates, organometallic compounds of aluminum, iron, calcium, magnesium, zinc, or bismuth, Lewis acids or organic acids / bases, linear or cyclic amidines, guanidines or amines, or mixtures thereof.

[0081] The curing catalyst used is preferably an organotin compound, such as dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin dilaurate, dioctyltin diacetylacetonate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, or dioctyltin oxide, preferably dioctyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, or dioctyltin oxide, and particularly preferably dioctyltin diacetylacetonate and dioctyltin dilaurate. Furthermore, zinc salts (e.g., zinc octanoate, zinc acetylacetonate, and zinc 2-ethylcaproate) or tetraalkylammonium compounds (e.g., N,N,N-trimethyl-N-2-hydroxypropylammonium hydroxide, N,N,N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate, or choline 2-ethylhexanoate) can also be used. The use of zinc octoate (zinc 2-ethylhexanoate) and tetraalkylammonium compounds is preferred, and the use of zinc octate is particularly preferred.More preferably are bismuth catalysts, e.g., TIB Kat (TIB GmbH, Mannheim), or Borchi® catalysts, titanates, e.g., titanium(IV) isopropoxide, iron(III) compounds, e.g., iron(III) acetylacetonate, aluminum compounds, e.g., aluminum triisopropoxide, aluminum trisecbutoxide, other alkoxides and aluminum acetylacetonate, calcium compounds, e.g., calcium disodium ethylenediamine tetraacetate or calcium diacetylacetonate, or amines, e.g., triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]unde-7-ene, 1,5-diazabicyclo[4.3.0]no-5-nene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, N-ethylmorpholine, etc. Furthermore, preferred catalysts include organic or inorganic Brønsted acids, such as acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, or benzoyl chloride, hydrochloric acid, phosphoric acid, and their monoesters and / or diesters, such as butyl phosphate, (iso)propyl phosphate, and dibutyl phosphate. Guanidine-containing organic and organosilicon compounds are also preferred. Of course, it is also possible to use two or more catalysts in combination. In addition, as described in International Publication No. 2005 / 100482, it is also possible to use photolatent bases as catalysts.

[0082] 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, and particularly preferably 0.1% to 3% by weight, relative to the total weight of the curable composition.

[0083] In the case of film-forming polymers that harden through physical drying, there is no need to add a reactive curing agent.

[0084] 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 at room temperature or high temperature.

[0085] Preferably, a coating produced from the composition according to the present invention has antimicrobial activity against bacteria, yeast, mold, algae, parasites, and viruses.

[0086] The coating produced according to the present invention preferably has antibacterial activity against the following: - Pathogens of hospital-acquired infections, preferably Enterococcus faecalis, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, Escherichia coli, Enterobacter species, Corynebacterium diphtheriae, Candida albicans, Rotavirus, Bacteriophages, - Facultative anaerobic pathogenic environmental organisms, preferably Cryptosporidium, Giardia, amoeba (Acanthamoeba, Naegleria), Escherichia coli, coliform bacteria, Streptococcus fecal, Salmonella, Shigella, Legionella, Pseudomonas aeruginosa, Mycobacteria, Enterovirus (e.g., polio, hepatitis A virus), - Pathogens in food and beverages, preferably Bacillus cereus, Campylobacter, Clostridium botulinum, Clostridium perfringens, Chronobacter species, Escherichia coli, Listeria monocytogenes, Salmonella species, Staphylococcus aureus, Vibrio species, Yersinia enterocolitica, bacteriophages

[0087] It has been found that the integration of the upconversion phosphor according to the present invention has been significantly improved.

[0088] Upconversion phosphor and phosphor are used as synonyms.

[0089] The present invention further provides the use of compositions according to the present invention for producing dispersions, mill bases, adhesives, trowel compounds, refined oils, paints, coatings or printing inks, inkjet printers, pulverized resins, or pigment concentrates.

[0090] It is preferable to use the composition according to the present invention for producing an antibacterial coating.

[0091] An antimicrobial coating means that the coating has an antimicrobial surface that restricts or prevents the growth and proliferation of microorganisms.

[0092] Surprisingly, the coating according to the present invention was also found to possess 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.

[0093] The present invention relates to a method for forming an antibacterial coating on a substrate, and is described below: 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, The method also includes a step of applying a curable film-forming composition consisting of the above to a substrate.

[0094] Preferably, the substrate is a metal, a mineral substrate (e.g., concrete, natural rock, or glass), a cellulose substrate, wood and its mixtures, a dimensionally stable plastic, and / or a thermosetting material.

[0095] The term "dimensionally stable plastics" is understood to mean, though not exhaustively, 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).

[0096] Preferably, the primer composition may be applied to the substrate before applying the curable film-forming composition.

[0097] 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.

[0098] This includes all public facilities such as schools, nursing homes, industrial kitchens, or daycare centers.

[0099] A further invention is an article at least partially, preferably completely, coated with the curable composition according to the present invention.

[0100] Please note that the terms "antibacterial effect," "antibacterial efficacy," "antibacterial action," and "antibacterial properties" are used as synonyms.

[0101] It should be noted 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 means of killing microorganisms are physical. Therefore, such materials are not subject to biocide regulations (as of 2019, Regulation (EU) No. 528 / 2012 of the European Parliament and the Council of Europe, dated 22 May 2012).

[0102] The following are examples provided solely to illustrate the present invention to those skilled in the art and do not constitute any limitation with respect to all of the claimed subject matter. [Brief explanation of the drawing]

[0103] [Figure 1.1] Figure 1.1 shows the X-ray powder diffraction pattern of the phosphor from Experimental Example 1 (top figure) compared with the non-flux comparative phosphor (lower normalized X-ray powder diffraction pattern). [Figure 1.2]Figure 1.2 shows the emission spectrum (dashed line) of Experimental Example 1 compared to a comparative phosphor that was not flux-treated with PrF3. [Figure 1.3] Figure 1.3 shows the particle size distribution for Experimental Example 1. [Figure 2.1] Figure 2.1 shows the X-ray powder diffraction pattern (X-ray diffraction diagram) of the phosphor from Experimental Example 2 (upper figure) compared with the non-flux comparative phosphor (lower normalized X-ray diagram). [Figure 2.2] Figure 2.2 shows the emission spectrum (dashed line) of Experimental Example 2 compared to a comparative phosphor that was not fluxed with CaF2. [Figure 2.3] Figure 2.3 shows the particle size distribution of Experimental Example 2 after the subsequent grinding process. [Figure 2.4] Figure 2.4 shows the particle size distribution of comparative phosphor. [Figure 3.1] Figure 3.1 shows the X-ray powder diffraction pattern (X-ray diffraction diagram) of the phosphor from Experimental Example 3 (upper figure) compared with a non-flux comparative phosphor (lower normalized X-ray diagram). [Figure 3.2] Figure 3.2 shows the emission spectrum (dashed line) of Experimental Example 2 compared to a comparative phosphor that was not flux-treated with H3BO3. [Figure 4.1] Figure 4.1 shows a recorded image of CaLi2SiO4:Pr3+,Na+(1%) phosphor without flux. [Figure 4.2] Figure 4.2 shows a recorded image of CaLi2SiO4:Pr3+,Na+(1%) phosphor containing NaF as the flux. [Examples]

[0104] method - Particle size distribution in accordance with ISO 13320:2020 and USP 429, using Horiba's LA-950 laser particle size analyzer. - Qualitative elemental analysis by EDX using Hitachi's Tabeltop 4000Plus and a 15kV BSE detector (magnification: 1000x). - Powder XRD: X-ray powder diffraction patterns of the sample were obtained using a Panalytical X'Pert PRO MPD diffractometer operating with Bragg-Brentano geometry, for Cu-K α The data was recorded using radiation and line-scan CCD detectors. The integration time was 20 seconds, and the step size was 0.017°²Θ. - The emission spectrum was recorded using an Edinburgh Instruments FLS920 spectrometer equipped with a Coherent 488 nm continuous-wave OBIS laser and a Hamamatsu Peltier-cooled (-20°C) single-photon counting photomultiplier tube (R2658P). A bandpass filter was used to suppress nth-order reflections caused by the monochromator.

[0105] I. Phosphor Experimental Example 1: The present invention contains 33 mol% PrF as flux and phosphor(Ca 0.94 Pr 0.03 Na 0.03 )Li2SiO4 CaCO3 2.8225 g (28.2 mmol), Li2CO3 2.2167 g (30.0 mmol), SiO2 1.8025 g (30.0 mmol), Na2CO3 0.0477 g (0.45 mmol), and PrF3 0.1781 g (0.9 mmol) were mixed with 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) to obtain the desired product. Phosphor was recovered for further measurement.

[0106] Figure 1.1 shows the X-ray powder diffraction pattern (top) of the phosphor from Experimental Example 1 compared to the non-flux comparative phosphor (lower normalized X-ray powder diffraction pattern). This demonstrates that the desired phosphor was prepared. Figure 1.2 shows the emission spectrum (dashed line) of Experimental Example 1 compared to a comparative phosphor that was not fluxed with PrF3. The comparative phosphor (black line) was prepared in the same manner as in Experimental Example 1, but without PrF3. The spectrum clearly shows that the intensity can be improved in the desired wavelength range by adding flux. Figure 1.3 shows the particle size distribution of Experimental Example 1. 10 , D 50 and D 90 The following value was measured: D 10 :14.0μm, D 50 :26.7μm, D 90 : 44.7 μm.

[0107] Experimental Example 2: Phosphor(Ca)(Ca)(Ca)(Ca)(Ca)(Ca)(Ca)(Ca)(Ca)(Ca))))) 0.98 Pr 0.01 Na 0.01 )Li2SiO4 CaCO3 2.9426g (29.4 mmol), Li2CO3 2.2167g (30.0 mmol), SiO2 1.8025g (30.0 mmol), Pr6O 11 0.0511 g (0.05 mmol), 0.0159 g (0.15 mmol) of Na2CO3, and 0.1102 g (2.2029 mmol) of CaF2 were mixed with 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) to obtain the desired product.

[0108] Figure 2.1 shows the X-ray powder diffraction pattern (X-ray diffraction diagram) (upper figure) of the phosphor of Experimental Example 2 compared with the comparison non-flux phosphor (lower normalized X-ray diagram). This demonstrates that the desired phosphor was prepared. Figure 2.2 shows the emission spectrum (dashed line) of Experimental Example 2 compared to a comparative phosphor that was not fluxed with CaF2. The comparative phosphor (black line) was prepared in the same manner as in Experimental Example 1, but without CaF2. The spectrum clearly shows that the intensity can be improved in the desired wavelength range by adding flux. Figure 2.3 shows the particle size distribution of Experimental Example 2 after the subsequent grinding process. Therefore, the particle size was powdery. D 10 , D 50 and D 90 The following value was measured: D 10 :7.7μm, D 50 :12.9μm, D 90 : 20.7 μm. Figure 2.4 shows the particle size distribution of comparative phosphor. 10 , D 50 and D 90 The following value was measured: D 10 :11.1μm, D 50 :28.9μm, D 90 : 85.4 μm.

[0109] The particle size of the phosphor according to the present invention as a result of fluxing (Figure 1.3) was found to be more uniform than the particle size of the comparative phosphor (Figure 2.4). Therefore, the phosphor according to the present invention can be easily incorporated into the coating matrix, which can lead to improvements in coating properties such as the appearance of the coating surface (e.g., gloss, feel, and texture).

[0110] Experimental Example 3: Comparative example using different fluxes, containing 1 wt% H3BO3 (Ca 0.98 Pr 0.01 Na 0.01 )Li2SiO4 CaCO3 2.9426g (29.4 mmol), Li2CO3 2.2167g (30.0 mmol), SiO2 1.8025g (30.0 mmol), Pr6O 110.0511 g (0.05 mmol), 0.0159 g (0.1500 mmol) of Na2CO3, and 0.0441 g (0.7132 mmol) of H3BO3 were mixed with 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) to obtain the desired product. The phosphorus was recovered for further measurement.

[0111] Figure 3.1 shows the X-ray powder diffraction pattern (X-ray diffraction diagram) of the phosphor of Experimental Example 3 (upper figure) compared with the non-flux comparative phosphor (lower normalized X-ray diagram). This demonstrates that the desired phosphor was prepared. Figure 3.2 shows the emission spectrum (dashed line) of Experimental Example 2 compared to a comparative phosphor that was not fluxed with H3BO3. The comparative phosphor (black line) was prepared in the same manner as in Experimental Example 1, but without H3BO3. The spectrum clearly shows that the intensity of the phosphor in Experimental Example 3 decreased in the desired wavelength range upon the addition of H3BO3. This flux appears to be inappropriate. Therefore, no further measurements were taken.

[0112] Experimental Example 4: Visual comparison using recorded images of flux-treated and unflux-treated phosphors. Two CaLi2SiO4:Pr 3+ Na + (1%) phosphor was prepared in the same manner, and NaF was added as a flux to one of the phosphors. CaCO3 2.9426g (29.4 mmol), Li2CO3 2.2167g (30.0 mmol), SiO2 1.8025g (30.0 mmol), Pr6O 110.0511 g (0.05 mmol), 0.0159 g (0.15 mmol) of Na2CO3, and 0.1855 g (3.0 mmol) of NaF were mixed with 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) to obtain the desired product.

[0113] Figure 4.1 shows CaLi2SiO4:Pr without flux. 3+ Na + The image shows a (1%) phosphor recording. The recording was performed using a 15kV BSE detector at 1000x magnification. Figure 4.2 shows CaLi2SiO4:Pr containing NaF as flux. 3+ Na + The image shows a (1%) phosphor recording. The recording was performed using a 15kV BSE detector at 1000x magnification. It is clear that samples with added flux produce more uniform particle images.

[0114] II. Application Examples The procedure is similar to the example in European Patent Application No. 21157055.1. The method, apparatus, and materials were identical to those in European Patent Application No. 21157055.1. Only the (flux-treated) phosphor according to the present invention was substituted. To avoid copying the quoted text and tables, the numbering of European Patent Application No. 21157055.1 is formally listed below. 1. Selection of film-forming polymers 1.1 Preparation of a composition free of phosphors and additives 1.2 Coating of a polymer matrix onto a quartz plate 1.3 Measurement of Transmittance 2. Selection of additives 2.1 Measurement of Transmittance 2.2 Testing of coating properties of phosphorus-free polymer matrices 3. Testing of antibacterial effect 3.1 Selection of Phosphor - CaLi2SiO4:Pr flux-treated with 10 mol% NaF according to Experimental Example 4 3+ Na + (1%) - CaLi2SiO4:Pr flux-treated with 22.5 wt% CaF according to Experimental Example 2 3+ Na + (1%) 3.2 Testing of the antibacterial effect of the composition according to the present invention

[0115] Please note that the terms "antibacterial effect," "antibacterial efficacy," "antibacterial action," and "antibacterial properties" are used as synonyms. To test the antimicrobial effect, flux-treated phosphors from II.3.1 were incorporated into each curable composition C. They were prepared according to the data in Table 1. 50 g of glass beads were added to each composition, and the mixture was pulverized in a speed mixer at 2,000 rpm for 5 minutes. After filtering off the glass beads, each composition was coated onto a high-gloss rolled aluminum panel, crosslinked, and a film with a dry thickness of approximately 50 μm was formed. With a coating on the substrate, the coating surface should have antimicrobial activity, and the comparative example is expected to lack antimicrobial activity. Comparative example CE does not contain phosphor.

[0116] [Table 1]

[0117] 3.2.1 Transcription Method The tests were conducted using Bacillus subtilis, which is used in UV-based biodose measurement tests within the DVGW (German Association for Gas and Water Technology) standard W294, "UV-Gerates for Disinfection in Water Supply" (Arbeitsblatt W 294 “UV-Gerate zur Desinfektion in der Wasserversorgung”). Bacillus subtilis is a Gram-positive, endospore-forming bacterium and is particularly insensitive to ultraviolet light, making it suitable as a worst-case scenario when testing the antibacterial effects of ultraviolet light. The test organism used was a subspecies of Bacillus subtilis subsp. spizizenii (DSM347, ATCC6633). To ensure confluent coating of the nutrient agar medium, the final concentration should be 10 7 One mL of Bacillus subtilis suspension, with a cell / mL concentration, was uniformly distributed onto a sterile CASO agar plate. The applied bacterial suspension was equilibrated on nutrient agar at room temperature (22±2°C) for 300±30 seconds. Bacterial suspensions were prepared by diluting the pre-cultures of each bacterial strain. Dilution was performed with sterile deionized water. Pre-cultures of the test organisms were prepared in sterile CASO broth. The Bacillus subtilis pre-cultures were incubated in a stirred water bath at 30°C for 16±1 hours with constant stirring. The cell titer of the pre-cultures was measured by microscopic examination using a hemocytometer (Toma hemocytometer).

[0118] The purpose of the transfer method is to simulate the antimicrobial activity of the coated surface under realistic conditions on a dry, animate surface. For this purpose, the coating obtained as described above was cut to a size of 2.5 cm × 4 cm and pressed onto a nutrient agar plate confluently inoculated with Bacillus subtilis at a specified weight of 90 ± 1 g for 60 ± 5 seconds. This process transferred the bacteria in a semi-dried form to the coated surface. Subsequently, the substrate was placed in an empty Petri dish with the coated and inoculated side facing up and incubated under illumination at room temperature for 0, 1, 2, 3, and 5 hours.

[0119] To test the antibacterial effect due to the upconversion effect, the substrates with the coated and inoculated sides were further cultured at room temperature in the dark for 0, 1, 2, 3, and 5 hours.

[0120] All samples, along with a comparative example that did not contain UV upconverter particles, were tested three times, with or without illumination during the incubation period.

[0121] The antibacterial effect after an appropriate incubation period is detected by measuring the culture properties through a contact test (Figure 1 of European Patent Application No. 21157055.1).

[0122] To test the cultureability of Bacillus subtilis, after incubation times of 0, 1, 2, 3, and 5 hours, the coated and inoculated sides of the substrate were pressed onto a sterile nutrient agar plate with a specified weight of 90 ± 1 g for 60 ± 5 seconds. The nutrient agar was then incubated under static conditions at 30°C for 24 ± 1 hours. The formed bacterial colonies were qualitatively evaluated visually.

[0123] 3.2.2 Results of the transcription method By reducing the culturability of Bacillus subtilis, the inhibitory effect on bacterial growth can be confirmed in the transcription method.

[0124] The phosphorus according to the inventions of Experimental Examples 2 and 4 resulted in a significant decrease in the cultureability of Bacillus subtilis in the curable compositions C2-1, C2-2, C4-1, and C4-2 according to the present invention, compared with CE and dark-cultured samples (Table 1). The cultureability of bacteria attached to the coating surface of the comparative sample of curable composition CE showed significant inhibition of growth with increasing culture period. This decrease was measurable even after 1 hour of culture under constant lighting. The decrease in cultureability progressed up to 5 hours of culture under constant lighting. The compositions cultured in the dark showed no decrease in cultureability throughout the 5-hour culture period.

[0125] Since the number of culturable bacteria on the surface of the dark-cultured sample did not change over 5 hours, it can be shown that the antimicrobial effect of phosphor is only obtained under irradiated conditions.

[0126] The curable composition CE without upconverter particles did not show any growth inhibitory effect against Bacillus subtilis under both illuminated and dark conditions (Table 1).

[0127] Furthermore, the polymer matrix showed no pure contamination. This was confirmed by contact testing of sample pieces that had not been pre-transferred with bacteria.

[0128] As a result, it can be concluded that flux-treated phosphor exhibits an antibacterial effect in the coating according to the present invention, which is manufactured from the curable composition according to the present invention.

[0129] [Table 2]

Claims

1. A curable composition for manufacturing antibacterial coatings, - At least one film-forming polymer, - At least one additive as needed, - At least one hardener as needed, -General formula (I): A １－ｘ－ｙ－ｚ B * ｙ B ２ SiO ４ :Ln １ ｘ ,Ln ２ ｚ , (I) (In the formula, x=0.0001 to 0.0500, z = 0.0000 gz = 0.0001 to 0.3000, However, 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 * It is selected from the group consisting of Li, Na, and K. B is, B * The same as, or different from, 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).) At least one upconversion phosphor, It consists of, The phosphor is a curable composition prepared by calcining a starting material mixture in the presence of at least one halogen-containing flux added to the starting material mixture.

2. The composition according to claim 1, wherein 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.

3. The composition according to claim 1, wherein the halogenated compound is a fluoride, bromide, or chloride.

4. The composition according to claim 2, wherein the alkali metal is sodium or lithium.

5. The composition according to claim 2, wherein the lanthanoid is praseodymium.

6. The composition according to claim 2, wherein the alkaline earth metal is calcium.

7. The composition according to claim 1, wherein the phosphor is doped with praseodymium.

8. The composition according to claim 1, wherein the phosphor is doped with praseodymium and simultaneously doped with gadolinium.

9. The phosphor is either a single crystalline silicate or consists of multiple crystalline silicates. The composition according to claim 1, wherein the crystalline silicate is doped with lanthanide ions and comprises at least one alkali metal ion and at least one alkaline earth metal ion.

10. The composition according to claim 1, wherein the phosphor is at least partially crystalline.

11. The aforementioned phosphor is given by the 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 * It is selected from the group consisting of Li, Na, and K. B is, B * The same as, or different from, x=0.0001~0.0500, z = 0.0000 gz = 0.0001 to 0.3000, (However, y = x + z.) The composition according to claim 1, selected from the compounds.

12. The aforementioned phosphor is given by 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=0.0000~1.0000, b = 0.0001 to 0.5000. The composition according to claim 1, selected from the compounds.

13. The aforementioned phosphor is given by general formula (IIa): Ca １－２ｂ Pr ｂ Na ｂ Li ２ SiO ４ (IIa) (In the formula, b = 0.0001 to 0.5000.) The composition according to claim 1, selected from the compounds.

14. 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.

15. The composition according to claim 1, wherein the phosphor comprises a halogen corresponding to the halide of the flux.

16. When the aforementioned phosphor is irradiated with low-energy, long-wavelength electromagnetic radiation in the range of 2000 nm to 400 nm, it emits high-energy, short-wavelength electromagnetic radiation in the range of 400 nm to 100 nm. The maximum emission intensity of the aforementioned high-energy, short-wavelength electromagnetic radiation is at least 1.103 counts / (mm²). ２ *s) The composition according to claim 1.

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

18. The composition according to claim 1, wherein the film-forming polymer comprises a functional group that is reactive with an isocyanate-containing curing agent or catalyst.

19. The composition according to claim 1, wherein the film-forming polymer is selected from the group consisting of a hydroxy-functional acrylate polymer, a hydroxy-functional polyester polymer, and / or a hydroxy-functional polyether polymer, a hydroxy-functional cellulose derivative, an amino-functional aspartic acid polymer, or an amino-functional polyester polymer, which react with an isocyanate-containing curing agent.

20. The composition according to claim 1, wherein the film-forming polymer has low resonance properties.

21. The composition according to claim 1, wherein the transmittance of the film-forming polymer to electromagnetic radiation at a wavelength of 260 nm is at least 75%, as measured by a twin-beam UV / VIS spectrometer.

22. The composition according to claim 1, wherein the transmittance to electromagnetic radiation with a wavelength of 500 nm is at least 70% as measured by a twin-beam UV / VIS spectrometer.

23. The composition according to claim 1, wherein 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.

24. The composition according to claim 1, wherein the curing agent is selected from the group consisting of dispersants, rheological additives, leveling agents, wetting agents, defoaming agents, and UV stabilizers.

25. The composition according to claim 1, wherein the curing agent is selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates.

26. A coating manufactured from the composition described in Claim 1, which has antimicrobial activity against bacteria, yeast, mold, algae, parasites, and viruses.

27. ​​A coating manufactured from the composition described in Claim 1, - Pathogens of hospital-acquired infections, -pathogenic environmental organisms, - Pathogens in food and beverages A coating that has antibacterial properties against [the target of the antimicrobial agent].

28. Use of the composition according to claim 1 for producing an antibacterial coating.

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

30. This is a method for forming an antibacterial coating on a substrate. below: (a) At least one film-forming polymer having a functional group that is reactive with an isocyanate-containing curing agent and optionally catalyzed by a catalyst, (b) at least one phosphor of formula (II) and (c) A curing agent containing an isocyanate functional group, A method comprising the step of applying a curable film-forming composition consisting of the above to the substrate.

31. The method according to claim 30, wherein the substrate comprises a metal, a mineral substrate, a cellulose substrate, wood and its mixtures, a dimensionally stable plastic, and / or a thermosetting product.

32. The method according to claim 30, wherein a primer composition is applied to the substrate before applying the curable film-forming composition.

33. An article at least partially coated with the curable composition according to claim 1.

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