Composition for production of coatings comprising improved phosphors
20220325177 · 2022-10-13
Assignee
Inventors
- Simone Schulte (Essen, DE)
- Markus Hallack (Schermbeck, DE)
- Christina Janke (Essen, DE)
- Sabine Krusenbaum (Essen, DE)
- Bärbel Wolff (Moers, DE)
- Thomas Jüstel (Witten, DE)
- Stefan Fischer (Soest, DE)
- Franziska Schröder (Steinfurt, DE)
- Sven Reetz (Gronau, DE)
- Michael Huth (Maintal, DE)
Cpc classification
C09D5/14
CHEMISTRY; METALLURGY
International classification
C09D5/14
CHEMISTRY; METALLURGY
Abstract
A curable composition for production of coatings having an antimicrobial property, contains at least one film-forming polymer, optionally at least one additive and/or at least one curing agent, and at least one up-conversion phosphor of the general formula (I): A.sub.1-x-y-zB*.sub.yB.sub.2SiO.sub.4:Ln.sup.1.sub.x,Ln.sup.2.sub.z. In the general formula (I), x=0.0001-0.0500; z=0.0000 or z=0.0001 to 0.3000 with the proviso that: y=x+z; A is selected from Mg, Ca, Sr and Ba; B is selected from Li, Na, K, Rb and Cs; B* is selected from Li, Na and K; and preferably B and B* are not the same. Additionally, Ln.sup.1 is selected from praseodymium (Pr), erbium (Er), and neodymium (Nd); and Ln.sup.2 is gadolinium (Gd). The phosphor has been prepared using at least one halogen-containing flux.
Claims
1. A curable composition for the production of coatings having an antimicrobial property, the composition comprising: at least one film-forming polymer, optionally, at least one additive, optionally, at least one curing agent, and at least one up-conversion phosphor of the general formula (I)
A.sub.1-x-y-zB*.sub.yB.sub.2SiO.sub.4:Ln.sup.1.sub.x,Ln.sup.2.sub.z. (I) wherein x=0.0001-0.0500; z=0.0000 or z=0.0001 to 0.3000 with the proviso that: 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; Ln.sup.1 is selected from the group consisting of praseodymium (Pr), erbium (Er), and neodymium (Nd); Ln.sup.2 is gadolinium (Gd); and wherein the at least one up-conversion phosphor has been prepared using at least one halogen-containing flux.
2. The composition according to claim 1, wherein the at least one halogen-containing flux is at least one substance selected from the group consisting of an ammonium halide, an alkali metal halide, an alkaline earth metal halide, and a lanthanoid halide.
3. The composition according to claim 2, wherein a halide of the at least one halogen-containing flux is selected from the group consisting of fluoride, bromide, and chloride.
4. The composition according to claim 2, wherein an alkali metal of the alkali metal halide is sodium or lithium.
5. The composition according to claim 2, wherein a lanthanoid of the lanthanoid halide is praseodymium.
6. The composition according to claim 2, wherein an alkaline earth metal of the alkaline earth metal halide is calcium.
7. The composition according to claim 1, wherein the at least one up-conversion phosphor has been doped with praseodymium.
8. The composition according to claim 1, wherein the at least one up-conversion phosphor has been doped with praseodymium and co-doped with gadolinium.
9. The composition according to claim 1, wherein the at least one up-conversion phosphor is a crystalline silicate or consists of crystalline silicates doped with lanthanoid ions, wherein the at least one up-conversion phosphor comprises at least one alkali metal ion and at least one alkaline earth metal ion.
10. The composition according to claim 1, wherein the at least one up-conversion phosphor is at least partially crystalline.
11. The composition according to claim 1, wherein the at least one up-conversion phosphor is a compound of the general formula (Ia)
A.sub.1-x-y-zB*.sub.yB.sub.2SiO.sub.4:Pr.sub.x,Gd.sub.z, (Ia) wherein A is selected from the group consisting of Mg, Ca, Sr, and Ba; B is selected from the group consisting of Li, Na, K, Rb, and Cs; B* is selected from the group consisting of Li, Na, and K; x=0.0001-0.0500; and z=0.0000 or z=0.0001 to 0.3000 with the proviso that: y=x+z.
12. The composition according to claim 1, wherein the at least one up-conversion phosphor is a compound of the general formula (II)
(Ca.sub.1-aSr.sub.a).sub.1-2bLn.sub.bNa.sub.bLi.sub.2SiO.sub.4 (II) wherein Ln is selected from the group consisting of praseodymium, gadolinium, erbium, and neodymium; a=0.0000 to 1.0000; and b=0.0001 to 0.5000.
13. The composition according to claim 1, wherein the at least one up-conversion phosphor is a compound of the general formula (IIa)
Ca.sub.1-2bPr.sub.bNa.sub.bLi.sub.2SiO.sub.4 (IIa) wherein b=0.0001 to 0.5000.
14. The composition according to claim 1, wherein the at least one up-conversion phosphor is Ca.sub.0.98Pr.sub.0.01Na.sub.0.01Li.sub.2SiO.sub.4 or Ca.sub.0.94Pr.sub.0.03Na.sub.0.03Li.sub.2SiO.sub.4.
15. The composition according to claim 3, wherein the at least one up-conversion phosphor includes a halogen corresponding to the halide of the at least one halogen-containing flux.
16. The composition according to claim 1, wherein the at least one up-conversion phosphor which, on irradiation with electromagnetic radiation having lower energy and longer wavelength in the range from 2000 nm to 400 nm, emits electromagnetic radiation having higher energy and shorter wavelength in the range from 400 nm to 100 nm, where an intensity of an emission maximum of the electromagnetic radiation having higher energy and shorter wavelength is an intensity of at least 1.Math.10.sup.3 counts/(mm.sup.2*s).
17. The composition according to claim 12, wherein the at least one up-conversion phosphor according to formula (II) has XRPD signals in the range from 23° 2θ to 27° 2θ and from 34° 2θ to 39.5° 2θ.
18. The composition according to claim 1, wherein the at least one film-forming polymer contains functional groups that are reactive with an isocyanate-containing curing agent or with a catalyst.
19. The composition according to claim 1, wherein the at least one film-forming polymer is selected from the group consisting of a hydroxy-functional acrylate polymer, a hydroxy-functional polyester polymer, a hydroxy-functional polyether polymer, a hydroxy-functional cellulose derivative, an amino-functional aspartic polymer, and a polyester polymer, wherein the at least one film-forming polymer reacts with an isocyanate-containing curing agent.
20. The composition according to claim 1, wherein the at least one film-forming polymer has low resonance.
21. The composition according to claim 1, wherein a transmittance of the at least one film-forming polymer is at least 75%, measured by a twin-beam UV/VIS spectrometer.
22. The composition according to claim 1, wherein a transmittance of the composition is at least 70%, measured by a twin-beam UV/VIS spectrometer.
23. The composition according to claim 1, wherein the at least one up-conversion phosphor has an average particle size of d50=0.1−50 μm, measured to ISO 13320:2020 and USP 429.
24. The composition according to claim 1, wherein the at least one additive is selected from the group consisting of a dispersant, a rheology aid, a levelling agent, a wetting agent, a defoamer, and a UV stabilizer.
25. The composition according to claim 1, wherein the at least one curing agent is selected from the group consisting of an aliphatic isocyanate and a cycloaliphatic isocyanate.
26. The composition according to claim 1, wherein a coating produced therefrom has antimicrobial action against bacteria, yeasts, moulds, algae, parasites, and viruses.
27. The composition according to claim 1, wherein a coating produced therefrom has antimicrobial action against pathogens of nosocomial infections, pathogenic environmental organisms, or pathogens in food and drink.
28. A method, comprising: producing a dispersion, a millbase, an adhesive, a trowelling compound, a render, a paint, a coating, a printing ink, an inkjet, a grinding resin, or a pigment concentrate; with the composition according to claim 1.
29. A method, comprising: producing a coating with the composition according to claim 1, wherein the coating has an antimicrobial property.
30. A method, comprising: coating a substrate with the composition according to claim 1, wherein the substrate is for a hygiene facility, a hospital, or for the food and drink industry.
31. A process for forming an antimicrobial coating on a substrate, the process comprising: applying a curable film-forming composition to a substrate, wherein the substrate comprises: (a) at least one film-forming polymer containing functional groups which are reactive with an isocyanate-containing curing agent, optionally catalysed by a catalyst, (b) at least one phosphor of the formula (II)
(Ca.sub.1-aSr.sub.a).sub.1-2bLn.sub.bNa.sub.bLi.sub.2SiO.sub.4 (II) wherein Ln is selected from the group consisting of praseodymium, gadolinium, erbium, and neodymium, a=0.0000 to 1.0000, and b=0.0001 to 0.5000; and (c) a curing agent containing isocyanate-functional groups.
32. The process according to claim 31, wherein the substrate comprises metal, a mineral substrate, a cellulosic substrate, wood or a hybrid thereof, a dimensionally stable plastic, and/or a thermoset.
33. The process according to claim 31, wherein a primer composition is applied to the substrate prior to the application of the curable film-forming composition.
34. An article, coated at least partly with the composition according to claim 1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
[0099] The person skilled in the art is aware of a great number of fluxes of all kinds from the prior art, such as halides, carbonates, sulfates, oxides and borates of, where respectively applicable, ammonium, lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, lead, lanthanum, lutetium, aluminium, bismuth and boric acid. Also known are their applications in the field of metallurgy, for example for accelerating crystal growth or suppressing the formation of extraneous phases.
[0100] Therefore, it was also an object of the invention to select a suitable flux so that the desired properties could be achieved. The discovery of suitable fluxes was therefore particularly important, such that here too a contribution to inventiveness already exists.
[0101] It was found, completely surprisingly, that the preparation of the up-conversion phosphors in the presence of at least one halogen-containing flux resulted in up-conversion phosphors having a homogeneous particle size distribution and also increased intensity of the emission or greater quantum yield, compared to phosphors without the addition of a flux or comprising a different flux.
[0102] Treatment with fluxes is also called fluxing, that is to say the product has been fluxed.
[0103] It has been shown in the examples that the particle size distribution of the fluxed phosphor according to the invention resembles a Gaussian distribution, which points to the homogeneity of the particle size, and so the incorporation thereof in a coating matrix can advantageously be conducted significantly more easily. It is assumed that the coating properties, such as the appearance of the coating surface, for example the gloss, feel and touch, were improved as a result of this.
[0104] The intensity of the emission of the up-conversion phosphors could also be achieved through a simple technical implementation.
[0105] A further subject of the invention is thus also a process for the preparation of these up-conversion phosphors and also the up-conversion phosphors obtainable thereby.
[0106] Preferably, the halogen-containing flux used is at least one substance from the group of the ammonium halides, alkali metal halides, alkaline earth metal halides and lanthanoid halides. It has surprisingly been found with halides from these groups that up-conversion phosphors prepared using them have a higher emission intensity than with other fluxes.
[0107] The halides are preferably fluorides or chlorides.
[0108] The alkali metals are preferably potassium, sodium or lithium.
[0109] The lanthanoid is preferably praseodymium.
[0110] The alkaline earth metals are preferably calcium or strontium.
[0111] The phosphor has preferably been doped with praseodymium, which is used in the composition according to the invention.
[0112] For the composition according to the invention, the phosphor has preferably been doped with praseodymium and co-doped with gadolinium.
[0113] It is preferable that the phosphor is at least partially crystalline. It is thus preferable that the phosphor is partially or fully crystalline. The phosphor is thus preferably at least not entirely amorphous. It is therefore preferable that the phosphor is not an amorphously solidified melt (glass).
[0114] The phosphor is preferably a crystalline silicate or consists of crystalline silicates doped with lanthanoid ions, comprising at least one alkali metal ion and at least one alkaline earth metal ion.
[0115] For the composition according to the invention, the phosphor is preferably selected from compounds of the general formula (Ia)
A.sub.1-x-y-zB*.sub.yB.sub.2SiO.sub.4:Pr.sub.x,Gd.sub.z, (Ia)
with A being selected from the group consisting of Mg, Ca, Sr, Ba;
B being selected from the group consisting of Li, Na, K, Rb and Cs;
B* being 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*, and preferably B and B* are not the same;
x=0.0001-0.0500;
z=0.0000 or z=0.0001 to 0.3000 with the proviso that: y=x+z.
B* serves here to balance the charge of the praseodymium or gadolinium substitution.
A here may represent a single element from the group consisting of Mg, Ca, Sr and Ba, or else a combination of two or more elements from this group, i.e., for example A=(Mg.sub.a1 Ca.sub.a2 Sr.sub.a3Ba.sub.a4) with 0≤a1≤1, 0≤a2≤1, 0≤a3≤1, 0≤a4≤1, and with the proviso that: a1+a2+a3+a4=1. A may thus represent (Ca.sub.0.9Sr.sub.0.1), for example.
[0116] For the composition according to the invention, the phosphor is preferably selected from compounds of the general formula (II)
(Ca.sub.1-aSr.sub.a).sub.1-2bLn.sub.bNa.sub.bLi.sub.2SiO.sub.4 II
where:
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, especially 0.0050 to 0.0500.
[0117] Ln here may represent a single element from the group consisting of praseodymium, gadolinium, erbium and neodymium, or else represent a combination of two elements from this group, i.e., for example, Ln=(Ln.sup.1.sub.x Ln.sup.2.sub.y) where Ln.sup.1 and Ln.sup.2 are selected from the group consisting of praseodymium, gadolinium, erbium and neodymium, and where x and y are as defined for formulae (I) and (Ia).
[0118] Ln.sup.1 serves for doping. Preference is given to using praseodymium for the doping. Ln.sup.2 serves for optional co-doping. Preference is given to using gadolinium for the optional co-doping. The phosphor has preferably not been co-doped; in other words, Ln preferably represents a single element from the group consisting of praseodymium, gadolinium, erbium and neodymium.
[0119] It is even more preferable for the phosphor to be selected from compounds of the general formula (IIa)
Ca.sub.1-2bPr.sub.bNa.sub.bLi.sub.2SiO.sub.4 (IIa)
with b=0.0001 to 0.5000, preferably 0.0001 to 0.1, especially 0.005 to 0.0500.
[0120] It is very particularly preferable for the phosphor to be Ca.sub.0.98Pr.sub.0.01Na.sub.0.01Li.sub.2SiO.sub.4.
[0121] Preferably, the up-conversion phosphor according to the invention includes a halogen, corresponding to the halide of the flux.
[0122] The phosphor is preferably one which, on irradiation with electromagnetic radiation having lower energy and longer wavelength in the range from 2000 nm to 400 nm, especially in the range from 800 nm to 400 nm, emits electromagnetic radiation having higher energy and shorter wavelength in the range from 400 nm to 100 nm, preferably in the range from 300 nm to 200 nm. It is further preferable for the intensity of the emission maximum of the electromagnetic radiation having higher energy and shorter wavelength to be an intensity of at least 1.Math.10.sup.3 counts/(mm.sup.2*s), preferably higher than 1.Math.10.sup.4 counts/(mm.sup.2*s), particularly preferably higher than 1.Math.10.sup.5 counts/(mm.sup.2*s). For determination of these indices, emission is preferably induced by means of a laser, especially a laser having a power of 75 mW at 445 nm and/or a power of 150 mW at 488 nm.
[0123] The phosphor according to formula (II) preferably has XRPD signals in the range from 23° 2θ to 27° 2θ and from 34° 2θ to 39.5° 2θ, the signals being determined by means of the Bragg-Brentano geometry and Cu-K.sub.α radiation. Details of the method of measurement can be found in the as-yet unpublished European patent applications EP 19202910.6 and PCT/EP2020/077798.
[0124] The as-yet unpublished European patent applications EP 19202910.6 and PCT/EP2020/077798 are dedicated to the preparation of phosphors, especially of phosphors of formula (I), formula (Ia) and formula (II), without the addition of fluxes.
[0125] Proceeding from the process described in these documents, the process according to the invention comprises the following steps: [0126] i) providing at least one lanthanoid salt selected from lanthanoid nitrates, lanthanoid carbonates, lanthanoid carboxylates, preferably lanthanoid acetates, lanthanoid sulfates, lanthanoid oxides, particularly preferably Pr.sub.6O.sub.11 and/or Gd.sub.2O.sub.3, where the lanthanoid ion in the lanthanoid oxides or lanthanoid salts is selected from praseodymium, gadolinium, erbium, neodymium and, for co-doping, at least two of these, [0127] ii) providing a silicate, preferably a silicate salt, particularly preferably an alkali metal salt of the silicate, or a silicon dioxide, [0128] iii) providing at least one alkaline earth metal salt and at least one alkali metal salt, preferably an alkali metal silicate or an alkali metal carbonate selected from a lithium salt or a lithium compound and optionally selected from a sodium salt and potassium salt, preferably the salt of the lithium salt, preferably a lithium carbonate, a calcium carbonate and a sodium carbonate, [0129] iv) providing at least one flux from the group of the 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, [0130] a) mixing i), ii), iii) and iv) by means of grinding to obtain a mixture, or [0131] b) mixing i), ii) and iii) in an organic polar or nonpolar solvent that is not a protic solvent to obtain a mixture; the mixture from b) is calcined (step 1a) at 600 to 1000° C. to remove the organic component: preference is given to performing the calcination at 600 to 1000° C. for at least 1 h, preferably not less than 2 h, under standard (air) atmosphere to obtain a calcined mixture, [0132] calcining the mixture from a) or the calcined mixture from b) in a calcination step, preferably under air at a temperature below the melting temperature of the silicate-based material, wherein at least partial crystallization takes place, preferably in a further calcination step (step 1b) at a temperature of 50 to 200° C. below the melting temperature of the silicate-based material for at least 3 h, preferably under air, in order to crystallize the silicate-based material, preferably at a temperature of 800 to 900° C., particularly preferably at about 850° C., for at least 3 h, preferably for at least 12 h, preferably under air. [0133] in a further calcination step with rising temperature, preferably above 800° C. and 50 to 200° C. below the melting point (step 2) of the material, for example at 850° C. for at least 3 h, particularly preferably for at least 6 h, under a reducing atmosphere, reducing the lanthanoids to Ln.sup.3+ ions, [0134] obtaining a silicate-based lanthanoid ion-doped material, preferably after cooling the material.
[0135] Further detailed embodiments of the process can be gathered from EP 19202910.6 and PCT/EP2020/077798, a flux being used for the process according to the invention.
[0136] Completely surprisingly, it was possible to modify the known process in an elegant manner, additionally leading to optimized up-conversion phosphors with exceptional and unexpected properties with respect to the particle size distribution and increase in the emission intensity.
[0137] Preferably, 0.01% by weight-3.5% by weight, preferably 0.5%-3.5% by weight, particularly preferably 1.0%-3.5% by weight, of flux can be used, based on the total amount of the reactants.
[0138] It has been found that, surprisingly, the phosphors according to the invention, prepared in accordance with the teaching of EP 19202910.6 and PCT/EP2020/077798, have the required up-conversion properties responsible for the antimicrobial action. In other words, these phosphors can convert electromagnetic radiation having wavelengths above UV radiation, especially visible light or infrared light, to electromagnetic radiation having shorter wavelength, specifically in the region in which, for example, the DNA or RNA of the microorganisms can be destroyed or mutated. Accordingly, these phosphors are of very good suitability for the composition according to the invention.
[0139] It is also conceivable to prepare the phosphor according to the invention as follows: Starting materials used are CaCO.sub.3 (Alfa Aesar, 99.5%), Li.sub.2CO.sub.3 (Alfa Aesar, 99%), SiO.sub.2 (Aerosil 200, Evonik), Pr.sub.6O.sub.11 (Treibacher, 99.99%), and Na.sub.2CO.sub.3 (Merck, 99.9%) and also a CaF.sub.2 (Sigma-Aldrich, 99.9%) flux. A stoichiometric mixture of these compounds is mixed in acetone for 30 minutes. Once the acetone has evaporated fully at room temperature, the mixture is transferred to a corundum crucible. The mixture is calcined twice. The first calcination is conducted in a melting furnace at 850° C. for 12 h with supply of air, and the second calcination at 850° C. for 6 h under 95/5 N.sub.2/H.sub.2. The end product is then ground in an agate mortar.
[0140] It should be mentioned here that it is possible to use a subsequent milling of the phosphor in accordance with the teaching of EP 19202910.6 and PCT/EP2020/077798 to firstly achieve homogeneity of the particle size and secondly to achieve the desired particle size. However, in this case the energy input would be higher and the milling process would last longer due to the inhomogeneity and particle size distribution thereof after the preparation.
[0141] A further problem addressed by the invention is the selection of film-forming polymers that can be used for the curable composition having an antimicrobial property. In principle, all film-forming polymers known from the prior art are useful.
[0142] The film-forming polymer preferably has functional groups, preferably acidic hydrogens, that are reactive with an isocyanate-containing curing agent, and is optionally catalysed by a catalyst.
[0143] Advantageously, the film-forming polymer is selected from the group of the hydroxy-functional acrylate polymers, hydroxy-functional polyester polymers, and/or hydroxy-functional polyether polymers, hydroxy-functional cellulose derivatives, amino-functional aspartic polymers or polyester polymers, which reacts with an isocyanate-containing curing agent.
[0144] The film-forming polymer preferably has low resonance.
[0145] The person skilled in the art is aware of the physical interactions at the surface. Depending on the material and its material surface, a plurality of effects occur at the surface on incidence of light. The incident light is partly absorbed, partly reflected and, depending on the material surface, also scattered. Light can also first be absorbed and then emitted again. In the case of opaque, semitransparent or transparent materials, the light can also penetrate through the body (transmission). In some cases, the light is even polarized or diffracted at the surface. Some objects can even emit light (illuminated displays, LED segments, display screens), or fluoresce or phosphoresce in light of a different colour (afterglow).
[0146] What is meant by “low resonance” in the context of the present invention is that the film-forming polymer has low absorption, reflection, remission and scatter in the UV region or in the blue region at 450-500 nm. By contrast, transmittance should preferably be pronounced.
[0147] This is because it has been found that, surprisingly, the film-forming polymers according to the invention that have low resonance have improved antimicrobial action, because more electromagnetic radiation having lower energy and higher wavelength in the range from 2000 nm to 400 nm, especially in the range from 800 nm to 400 nm, is transmitted and, as a result, more electromagnetic radiation having higher energy and shorter wavelength in the range from 400 nm to 100 nm, preferably in the range from 300 nm to 200 nm, can be emitted.
[0148] It has been found that the higher the transmittance, the higher the emission as well, which is crucial for antimicrobial action.
[0149] Preferably, the transmittance of the film-forming polymer is at least 75%, preferably at least 80% and particularly preferably at least 85%, measured at a wavelength of 260 nm.
[0150] Preferably, the transmittance of the film-forming polymer is at least 75%, preferably at least 80% and particularly preferably at least 85%, measured at a wavelength of 500 nm.
[0151] By way of illustration, it should be noted here that transmittance may be defined at a different wavelength; see
[0152] In the case of 100% transmittance, for example, measured at a wavelength of 260 nm, the same amount of radiation is converted and emitted; in other words, there are no losses through absorption, scatter or the like. In the case of 80% transmittance, measured at a wavelength of 260 nm, 20% is not transmitted, probably owing to absorption, reflection, remission and/or scatter. Accordingly, only 80% of the radiation of wavelength 260 nm can be emitted.
[0153] This significant finding is important in the selection of the film-forming polymers. Polymers having 0% transmittance, for example, are unsuitable for the curable composition according to the invention. They do not transmit any electromagnetic radiation having lower energy and higher wavelength and, accordingly, phosphors present in the composition cannot convert this electromagnetic radiation to electromagnetic radiation having higher energy and shorter wavelength and emit it, which is required for the antimicrobial action.
[0154] Preferably, the composition according to the invention has a transmittance of at least 75%, preferably at least 80% and particularly preferably at least 85%, measured at 260 nm.
[0155] Preferably, the composition according to the invention has a transmittance of at least 75%, preferably at least 80% and particularly preferably at least 85%, measured at 500 nm.
[0156] The transmittance curves are preferably measured with a “Specord 200 Plus” twin-beam UV/VIS spectrometer from Analytik Jena. 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) is passed through the samples. The spectral range is 1.4 nm. The monochromatic light is divided into a measurement channel and a reference channel and enables direct measuring against a reference sample. The radiation transmitted through the sample is detected by a photodiode and processed to form electrical signals.
[0157] It is conceivable to use a composition having a low transmittance of less than 70%; they possibly also still have antimicrobial action, but the efficiency is very moderate.
[0158] The phosphors preferably have an average particle size of d50 of 0.1-50 μm, preferably d50=0.1-25 μm, particularly preferably d50=0.1 μm-5 μm, measured to ISO 13320:2020 and USP 429, for example with an LA-950 Laser Particle Size Analyzer from Horiba.
[0159] In order to efficiently incorporate and/or stabilize the phosphors in the composition according to the invention, it is preferably possible to add various additives.
[0160] The additives are preferably selected from the group of the dispersants, rheology aids, levelling agents, wetting agents, defoamers and UV stabilizers.
[0161] It has been found that, surprisingly, any addition of additives to the composition according to the invention reduces transmittance.
[0162] Accordingly, the composition according to the invention, in a further embodiment in which additives are used, preferably has a transmittance of at least 70%, preferably at least 75% and particularly preferably at least 80%, measured at 260 nm.
[0163] Accordingly, the composition according to the invention, in a further embodiment in which additives are used, preferably has a transmittance of at least 70%, preferably at least 75% and particularly preferably at least 80%, measured at 500 nm.
[0164] Preferably, the composition according to the invention includes a curing agent selected from the group of the aliphatic or cycloaliphatic isocyanates.
[0165] Examples of isocyanate-containing curing agents are monomeric isocyanates, polymeric isocyanates and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates on account of their lower toxicity. Examples of polyisocyanates are isocyanurates, uretdiones and biurets based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanates (HDI) and isophorone diisocyanate (IPDI). Examples of commercially available products are those under the trade name DESMODUR® from Covestro or VESTANAT from Evonik Industries. Known products are DESMODUR® N3400, DESMODUR® N3300, DESMODUR® N3600 DESMODUR® N75, DESMODUR® XP2580, DESMODUR® Z4470, DESMODUR® XP2565 and DESMODUR® VL from Covestro. Further examples are VESTANAT® HAT 2500 LV, VESTANAT® HB 2640 LV or VESTANAT® T 1890E from Evonik Industries. Examples of isocyanate prepolymers are DESMODUR® E XP 2863, DESMODUR® XP 2599 or DESMODUR® XP 2406 from Covestro. Further isocyanate prepolymers known to the person skilled in the art may be used.
[0166] It is conceivable to use catalysts for the curing. The catalysts that follow, selected from organic Sn(IV), Sn(II), Zn, Bi compounds or tertiary amines, may be used.
[0167] Preference is given to using catalysts selected from the group of organotin catalysts, titanates or zirconates, organometallic compounds of aluminium, iron, calcium, magnesium, zinc or bismuth, Lewis acids or organic acids/bases, linear or cyclic amidines, guanidines or amines or a mixture thereof.
[0168] Curing catalysts used are preferably organic tin compounds, for example, dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin dilaurate, dioctyltin diacetylacetonate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, dioctyltin oxide, preferably dioctyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, dioctyltin oxide, particularly preferably dioctyltin diacetylacetonate and dioctyltin dilaurate. In addition, it is also possible to use zinc salts, such as zinc octoate, zinc acetylacetonate and zinc 2-ethylcaproate, or tetraalkylammonium compounds, such as N,N,N-trimethyl-N-2-hydroxypropylammonium hydroxide, N,N,N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate or choline 2-ethylhexanoate. Preference is given to the use of zinc octoate (zinc 2-ethylhexanoate) and of the tetraalkylammonium compounds, particular preference to that of zinc octoate. Further preferred are bismuth catalysts. e.g. TIB Kat (TIB Mannheim) or Borchi® catalysts, titanates, e.g. titanium(IV) isopropoxide, iron(III) compounds, e.g. iron(III) acetylacetonate, aluminium compounds, such as aluminium triisopropoxide, aluminium tri-sec-butoxide and other alkoxides and also aluminium acetylacetonate, calcium compounds, such as calcium disodium ethylenediaminetetraacetate or calcium diacetylacetonate, or else amines, examples being triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5 diazabicyclo[4.3.0]non-5-ene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, N-ethylmorpholine, etc. Also preferred as catalysts are organic or inorganic Brønsted acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid or benzoyl chloride, hydrochloric acid, phosphoric acid and the monoesters and/or diesters thereof, for example butyl phosphate, (iso)propyl phosphate, dibutyl phosphate, etc. Also preferred are guanidine-bearing organic and organosilicon compounds. It is of course also possible to use combinations of two or more catalysts. In addition, it is also possible to use photolatent bases as catalysts, as described in WO 2005/100482.
[0169] The curing catalyst is preferably used in amounts 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, based on the total weight of the curable composition.
[0170] In the case of film-forming polymers that cure through physical drying, the addition of reactive curing agents is not required.
[0171] The composition according to the invention may preferably be used in 1K (one-component) coating systems or 2K (two-component) coating systems, in melamine baking systems, or room- or high-temperature systems.
[0172] Preferably, coatings produced from the composition according to the invention have antimicrobial action against bacteria, yeasts, moulds, algae, parasites and viruses.
[0173] The coatings produced according to the invention preferably have antimicrobial action against
pathogens of nosocomial infections, preferably against Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, Escherichia coli, Enterobacter, Corynebaterium diphtheriae, Candida albicans, rotavirus, bacteriophages;
facultatively pathogenic environmental organisms, preferably against Cryptosporidium parvum, Giardia lamblia, amoebas (Acanthamoeba spp., Naegleria spp.), E. coli, coliform bacteria, faecal streptococci, Salmonella spp., Shigella spp., Legionella spec., Pseudomonas aeruginosa, Mycobacterium spp., enteral viruses (e.g. polio and hepatitis A virus);
pathogens in food and drink, preferably against Bacillus cereus, Campylobacter spp., Clostridium botulinum, Clostridium perfringens, Cronobacter spp., E. coli, Listeria monocytogenes, Salmonella spp., Staphylococcus aureus, Vibrio spp., Yersinia enterocolitica, bacteriophages.
[0174] It has been found that the incorporation of the up-conversion phosphors according to the invention was markedly improved.
[0175] Up-conversion phosphors and phosphors are used as synonyms.
[0176] The invention further provides for the use of the composition according to the invention for the production of dispersions, millbases, adhesives, trowelling compounds, renders, paints, coatings or printing inks, inkjets, grinding resins or pigment concentrates.
[0177] Preference is given to the use of the composition according to the invention for the production of coatings having an antimicrobial property.
[0178] What is meant here by a coating having antimicrobial action or an antimicrobial property is that the coating has an antimicrobial surface that limits or prevents the growth and propagation of microorganisms.
[0179] It has also been found that, astonishingly, the coatings according to the invention have chemical and mechanical stability. Chemical and mechanical stability is particularly important since antimicrobial coatings are frequently used in areas that require regular disinfection and further hygiene measures.
[0180] The invention also includes a process for forming an antimicrobial coating on a substrate, comprising the application of a curable film-forming composition to the substrate, comprising: [0181] a. at least one film-forming polymer containing functional groups which are reactive with an isocyanate-containing curing agent, optionally catalysed by a catalyst, [0182] b. at least one phosphor of the formula (II) and [0183] c. a curing agent containing isocyanate-functional groups.
[0184] Preferably, the substrate is metal, mineral substrates (for instance concrete, natural rock or glass), cellulosic substrates, wood and hybrids thereof, dimensionally stable plastics and/or thermosets.
[0185] The term “dimensionally stable plastics” is understood to mean, albeit non-exhaustively, the following polymers: acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polylactate (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polystyrene (PS), polyether ether ketone (PEEK), polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE).
[0186] Preferably, a primer composition may be applied to the substrate prior to the application of the curable film-forming composition.
[0187] Preferably, the curable composition according to the invention is used for the coating of substrates in hygiene facilities and hospitals and in the food and drink industry.
[0188] This includes all settings in the public sphere, for example schools, old people's homes, industrial kitchens or nurseries.
[0189] A further invention is an article that has been coated at least partly, preferably fully, with the curable composition according to the invention.
[0190] It should be noted here that the terms “antimicrobial effect”, “antimicrobial efficacy”, “antimicrobial action” and “antimicrobial property” are used as synonyms.
[0191] It should be noted here that the article according to the invention may preferably have antimicrobial action even without release of an antimicrobial active ingredient if the coating comprises specific phosphors as described. In this way, the route via which the microorganisms are then killed is physical. Therefore, such materials are not covered by the biocide regulation (Regulation (EU) No 528/2012 of the European Parliament and of the Council of 22 May 2012 in the current text of 2019).
[0192] Adduced hereinafter are examples that serve solely to elucidate this invention to the person skilled in the art and do not constitute any restriction at all of the subject-matter as described.
Methods
[0193] Particle size distribution to ISO 13320:2020 and USP 429, with a Horiba LA-950 Laser Particle Size Analyzer
[0194] Qualitative elemental analysis by means of EDX with a Tabeltop 4000Plus from Hitachi, kV BSE detector, 1000× magnification
[0195] Powder XRD: The X-ray powder diffractograms of the samples were recorded using a Panalytical X′Pert PRO MPD diffractometer operating in Bragg-Brentano geometry, using Cu-K.sub.α radiation and a line scan CCD detector. The integration time was 20 s and the step width was 0.017° 2θ.
[0196] The emission spectra were recorded with the aid of an Edinburgh Instruments FLS920 spectrometer equipped with a 488 nm continuous-wave OBIS laser from Coherent and a Peltier-cooled (−20° C.) single-photon counting photomultiplier from Hamamatsu (R2658P). Bandpass filters were used to suppress nth-order reflections caused by the monochromators.
I. Phosphors
Example 1 Phosphor According to the Invention (Ca.SUB.0.94.Pr.SUB.0.03.Na.SUB.0.03.)Li.SUB.2.SiO.SUB.4 .with 3 mol % of PrF.SUB.3 .as Flux
[0197] 2.8225 g (28.2 mmol) of CaCO.sub.3, 2.2167 g (30.0 mmol) of Li.sub.2CO.sub.3, 1.8025 g (30.0 mmol) of SiO.sub.2, 0.0477 g (0.45 mmol) of Na.sub.2CO.sub.3 and 0.1781 g (0.9 mmol) of PrF.sub.3 were mixed in acetone in an agate mortar. This mixture was calcined at 850° C. for 12 h in air to remove organic constituents. The calcination is then conducted at 850° C. for a further 6 h in a forming gas atmosphere (5% H.sub.2/95% N.sub.2), which results in the desired product. The phosphor was withdrawn for further measurements.
[0198]
[0199]
[0200]
D.SUB.10.: 14.0 μm
D.SUB.50.: 26.7 μm
D.SUB.90.: 44.7 μm
Example 2 Phosphor According to the Invention (Ca.SUB.0.98.Pr.SUB.0.01.Na.SUB.0.01.)Li.SUB.2.SiO.SUB.4 .with 2.5% by Weight of CaF.SUB.2 .as Flux
[0201] 2.9426 g (29.4 mmol) of CaCO.sub.3, 2.2167 g (30.0 mmol) of Li.sub.2CO.sub.3, 1.8025 g (30.0 mmol) of SiO.sub.2, 0.0511 g (0.05 mmol) of Pr.sub.6O.sub.11, 0.0159 g (0.15 mmol) of Na.sub.2CO.sub.3 and 0.1102 g (2.2029 mmol) of CaF.sub.2 were mixed in acetone in an agate mortar. This mixture was calcined at 850° C. for 12 h in air to remove organic constituents. The calcination is then conducted at 850° C. for a further 6 h in a forming gas atmosphere (5% H.sub.2/95% N.sub.2), which results in the desired product.
[0202]
[0203]
[0204]
D.SUB.10.: 7.7 μm
D.SUB.50.: 12.9 μm
D.SUB.90.: 20.7 μm
[0205]
D.SUB.10.: 11.1 μm
D.SUB.50.: 28.9 μm
D.SUB.90.: 85.4 μm
[0206] It was found that the particle size of the phosphor according to the invention (
Example 3 Comparative Example Using a Different Flux, (Ca.SUB.0.98.Pr.SUB.0.01.Na.SUB.0.01.)Li.SUB.2.SiO.SUB.4 .with 1% by Weight of H.SUB.3.BO.SUB.3
[0207] 2.9426 g (29.4 mmol) of CaCO.sub.3, 2.2167 g (30.0 mmol) of Li.sub.2CO.sub.3, 1.8025 g (30.0 mmol) of SiO.sub.2, 0.0511 g (0.05 mmol) of Pr.sub.6O.sub.11, 0.0159 g (0.1500 mmol) of Na.sub.2CO.sub.3 and 0.0441 g (0.7132 mmol) of H.sub.3BO.sub.3 were mixed in acetone in an agate bowl. This mixture was calcined at 850° C. for 12 h in air to remove organic constituents. The calcination is then conducted at 850° C. for a further 6 h in a forming gas atmosphere (5% H.sub.2/95% N.sub.2), which results in the desired product. The phosphor was withdrawn for further measurements.
[0208]
[0209]
[0210] Further measurements were therefore not performed.
Example 4 Visual Comparison Using Recorded Images of Fluxed and Unfluxed Phosphors
[0211] Two CaLi.sub.2SiO.sub.4:Pr.sup.3+,Na.sup.+(1%) phosphors were prepared in analogous fashion, NaF being added as flux to one of the phosphors.
[0212] 2.9426 g (29.4 mmol) of CaCO.sub.3, 2.2167 g (30.0 mmol) of Li.sub.2CO.sub.3, 1.8025 g (30.0 mmol) of SiO.sub.2, 0.0511 g (0.05 mmol) of Pr.sub.6O.sub.11, 0.0159 g (0.15 mmol) of Na.sub.2CO.sub.3 and 0.1855 g (3.0 mmol) of NaF were mixed in acetone in an agate mortar. This mixture was calcined at 850° C. for 12 h in air to remove organic constituents. The calcination is then conducted at 850° C. for a further 6 h in a forming gas atmosphere (5% H.sub.2/95% N.sub.2), which results in the desired product.
[0213]
[0214]
II. Application Examples
[0215] The procedure was analogous to the examples from EP 21157055.1. Methods, devices and materials were identical to those from EP 21157055.1. Only the phosphor according to the invention (fluxed) was substituted.
[0216] The numbering of EP 21157055.1 is listed formally here in order to avoid a copy of the cited passages and tables.
1. Selection of the film-forming polymers
1.1 Preparation of the composition without phosphors and additives
1.2 Coating of the polymer matrices onto quartz plates
1.3 Measurement of transmittance
2. Selection of additives
2.1 Measurement of transmittance
2.2 Testing of the coating properties of the polymer matrices without phosphors
3. Testing of antimicrobial efficacy
3.1 Selection of phosphors [0217] CaLi.sub.2SiO.sub.4:Pr.sup.3+,Na.sup.+(1%) fluxed with 10 mol % NaF, according to Example 4 [0218] CaLi.sub.2SiO.sub.4:Pr.sup.3+,Na.sup.+(1%) fluxed with 2.5% by weight CaF.sub.2, according to Example 2
3.2 Testing of the antimicrobial efficacy of a composition according to the Invention
[0219] It should be noted here that the terms “antimicrobial effect”, “antimicrobial efficacy”, “antimicrobial action” and “antimicrobial property” are used as synonyms.
[0220] To test the antimicrobial efficacy, the fluxed phosphors from II. 3.1 were each formulated into a curable composition C. They were prepared according to the data from Table 1. 50 g of glass beads were added to the respective composition and the mixture was ground in a Speedmixer at 2000 rpm for 5 min. After filtering off the glass beads, the respective composition was coated onto a high-gloss rolled aluminium panel and crosslinked to form a film having a dry film thickness of approximately 50 μm. On the substrate there is now a coating, the coating surface of which should have an antimicrobial action, and the reference thereof without expected antimicrobial action. Comparative example CE does not contain any phosphors.
TABLE-US-00001 TABLE 1 Formulations of the curable compositions for the transfer method CE C2-1 C2-2 C4-1 C4-2 [g] [g] [g] [g] [g] CAB ™ 381-2 6.82 6.82 6.82 6.82 6.82 Butyl acetate 38.64 38.64 38.64 38.64 38.64 CaLi.sub.2SiO.sub.4:Pr.sup.3+, Na.sup.+(1%) CaF.sub.2 0.90 1.33 CaLi.sub.2SiO.sub.4:Pr.sup.3+, Na.sup.+(1%) NaF 0.90 1.33 TIB Kat ® 218 0.05 0.05 0.05 0.05 0.05 Desmodur ® N 3390 4.55 4.55 4.55 4.55 4.55
3.2.1 Transfer method
[0221] Testing was effected on Bacillus subtilis, which is used for biodosimetric testing of UV systems in DVGW (German Technical and Scientific Association for Gas and Water) Arbeitsblatt W 294 “UV-Geräte zur Desinfektion in der Wasserversorgung” [Standard W 294 “UV Instruments for Disinfection in Water Supply”]. Being a Gram-positive spore-forming bacterium, it is particularly insensitive to UV radiation and hence of good suitability as a worst case for testing of the antimicrobial action of UV radiation.
[0222] The test organism used was Bacillus subtilis subsp. spizizenii (DSM 347, ATCC 6633). 1 ml of a B. subtilis suspension with a final concentration of 10.sup.7 cells/ml was distributed homogeneously over a sterile CASO agar plate in order to assure confluent coverage of the nutrient agar. The bacteria suspension applied was equilibrated on the nutrient agar at room temperature (22±2° C.) for 300±30 s. The bacteria suspensions were produced by dilutions of pre-cultures of the respective bacterial strain. Dilution was effected in sterile deionized water. The pre-cultures of the test organisms were produced in sterilized CASO broth. The pre-culture of B. subtilis was incubated at 30° C. with constant agitation in an agitated water bath for 16±1 h. The cell titre of the pre-cultures was determined by microscopy with a haemocytometer (Thoma counting chamber).
[0223] The aim of the transfer method is to simulate the antimicrobial action of the coating surface under close-to-real conditions on a dry inanimate surface. For this purpose, the coatings obtained as described above were cut to a size of 2.5 cm×4 cm and pressed onto a nutrient agar plate confluently inoculated with B. subtilis with a defined weight of 90±1 g for 60±5 s. This step transferred the bacteria in semi-dry form to the surface of the coating. Subsequently, the substrates were placed into an empty petri dish with the coated and inoculated side upwards and incubated under illumination at room temperature for 0 h, 1 h, 2 h, 3 h, 5 h.
[0224] For testing of the antimicrobial action through the up-conversion effect, the substrates with the coated and inoculated side were additionally also incubated in the dark at room temperature for 0 h, 1 h, 2 h, 3 h, 5 h.
[0225] All samples and the reference without UV up-converter particles were tested in triplicate and with and without illumination over the incubation time.
[0226] The antimicrobial effect after the appropriate incubation time is detected via the determination of culturability by a contact test (FIG. 1 of EP 21157055.1).
[0227] For the testing of the culturability of B. subtilis, the substrates, after the incubation time of 0 h, 1 h, 2 h, 3 h, 5 h. were pressed with the coated and inoculated side against a sterile nutrient agar plate with a defined weight of 90±1 g for 60±5 s. The nutrient agar was then incubated under static conditions at 30° C. for 24±1 h. The bacterial colonies formed were qualitatively assessed visually.
3.2.2 Results of the transfer method
[0228] Any growth-inhibiting effect on the bacteria can be checked in the transfer method by a decrease in the culturability of B. subtilis.
[0229] The phosphors according to the invention of Examples 2 and 4 bring about a significant reduction in the culturability of B. subtilis in the curable compositions C2-1, C2-2, C4-1 and C4-2 according to the invention compared to CE and the samples incubated in the dark (Table 1). The culturability of the adherent bacteria on the coating surface of the comparative samples of the curable composition CE showed significant growth inhibition with increasing incubation period. This reduction was measurable under constant illumination even after incubation for 1 h. The drop in culturability increases until the incubation time of 5 h under constant illumination. The compositions incubated in the dark did not show any reduction in culturability over the incubation period of 5 h.
[0230] By virtue of the unchanged number of culturable bacteria over the period of 5 h on the sample surfaces incubated in the dark, it is possible to show that the antimicrobial effect of the phosphor exists only in the illuminated state.
[0231] The curable composition CE without the addition of up-converter particles did not show a growth-inhibiting action on B. subtilis either in the illuminated or in the darkened state (Table 1).
[0232] The polymeric matrices additionally did not show any genuine contamination. This was checked by a contact test of sample pieces without prior transfer of bacteria thereto.
[0233] It can consequently be determined that the fluxed phosphors exhibit an antimicrobial efficacy in the coating according to the invention produced from the curable composition according to the invention.
TABLE-US-00002 TABLE 2 Antimicrobial efficacy of the curable compositions Antimicrobial effect Composition Illuminated Darkened CE No No C2-1 Yes No C2-2 Yes No C4-1 Yes No C4-2 Yes No