阅读说明：本技术 用于产生具有抗微生物性能的涂层的组合物 (Composition for producing coatings with antimicrobial properties ) 是由 S·舒尔特 M·哈尔莱克 S·克鲁森鲍姆 C·扬克 于 2021-06-25 设计创作，主要内容包括：本发明涉及用于产生具有抗微生物性能的涂层的可固化组合物,包含至少一种成膜聚合物,至少一种上转换磷光体,任选存在的至少一种添加剂,任选存在的至少一种固化剂,其中磷光体选自理想化的通式(I),其中a＝0-1,1≥b>0,d＝0-1,e＝0-1,n＝0-1,z＝0-1,u＝0-1,v＝0-1,其中u+v≤1且d+e≤1；Ln＝镨(Pr)、钆(Gd)、铒(Er)、钕(Nd)、钇(Y)、Lu＝镥,Li＝锂：Lu-(3-a-b-)-(n)Ln-(b)(Mg-(1-z)Ca-(z))-(a)Li-(n)(Al-(1-u-v)Ga-(u)Sc-(v))-(5-a-2n)(Si-(1-d-)-(e)Zr-(d)Hf-(e))-(a+2n)O-(12)I。(The present invention relates to a curable composition for producing coatings with antimicrobial properties, comprising at least one film-forming polymer, at least one upconversion phosphor, optionally at least one additive, optionally at least one curing agent, wherein the phosphor is selected from the idealized general formula (I) wherein a ═ 0 to 1, 1 ≧ b>0, d-0-1, e-0-1, n-0-1, z-0-1, u-0-1, v-0-1, wherein u + v ≦ 1 and d + e ≦ 1; ln ═ praseodymium (Pr), gadolinium (Gd), erbium (Er), neodymium (Nd), yttrium (Y), Lu ═ lutetium, Li ═ lithium: lu (Lu) 3‑a‑b‑ n Ln b (Mg 1‑z Ca z ) a Li n (Al 1‑u‑v Ga u Sc v ) 5‑a‑2n (Si 1‑d‑ e Zr d Hf e ) a+2n O 12 I。)

1. A curable composition for producing coatings having antimicrobial properties comprising:

-at least one film-forming polymer,

-at least one up-converting phosphor,

-optionally at least one additive,

-optionally at least one curing agent,

wherein the phosphor is selected from the idealized general formula (I):

Lu_3-a-b-nLn_b(Mg_1-zCa_z)_aLi_n(Al_1-u-vGa_uSc_v)_5-a-2n(Si_1-d-eZr_dHf_e)_a+2nO₁₂ I

wherein a is 0-1, 1 is more than or equal to b >0, d is 0-1,

0-1, v, wherein u + v ≦ 1 and d + e ≦ 1;

ln ═ praseodymium (Pr), gadolinium (Gd), erbium (Er), neodymium (Nd), yttrium (Y),

Lu is equal to lutetium,

li ═ lithium.

2. The composition of claim 1 wherein the phosphor has been doped with praseodymium.

3. Composition according to any one of the preceding claims, characterized in that the phosphor is a solidified melt consisting of a crystalline garnet or a crystalline garnet doped with lanthanide ions, comprising at least one alkali metal ion and/or at least one alkaline earth metal ion, preferably characterized in that the crystalline garnet has been doped with praseodymium and optionally codoped with gadolinium.

4. A composition according to any of the preceding claims, characterized in that the phosphor is selected from the idealized general formula (Ia):

(Lu_1-x-yY_xGd_y)_3-a-b-nLn_b(Mg_1-zCa_z)_aLi_n(Al_1-u-vGa_uSc_v)_5-a-2n(Si_1-d-eZr_dHf_e)_a+2nO₁₂ Ia

wherein a is 0-1, 1 ≧ b >0, d is 0-1, e is 0-1, n is 0-1, x is 0-1, y is 0-1, z is 0-1, u is 0-1, v is 0-1, wherein x + y is ≤ 1, u + v is ≤ 1, and d + e is ≤ 1;

wherein in formula Ia, Ln ═ praseodymium (Pr), erbium (Er), neodymium (Nd), or,

Lu ═ lutetium, Gd ═ gadolinium, Y ═ yttrium, Li ═ lithium.

5. Composition according to any one of the preceding claims, characterized in that the phosphor is selected from the following general formulae:

i) formula Ib

(Lu_1-x-yY_xGd_y)_3-bLn_b(Al_1-u-vGa_uSc_v)₅O₁₂ Ib

Wherein Ln_bIs Ln ═ Pr and b ═ 0.001 to 0.05, x ═ 0 to 1, y ═ 0 to 1, u ═ 0 to 1, v ═ 0 to 1,

ii) formula Ic

(Lu_1-x-yY_xGd_y)_3-b-aLn_b(Mg_1-zCa_z)_a+bAl_5-a-bSi_a+bO₁₂ Ic

Wherein Ln_bIs Ln ═ Pr, where 1 ≥ b >0, a >0, x ═ 0-1, y ═ 0-1, z ═ 0-1,

iii) formula Id

(Lu_1-x-yY_xGd_y)_2-bLn_b(Ca_1-zMg_z)Al₄(Zr_1-fHf_f)O₁₂ Id

Wherein Ln_bIs Ln ═ Pr, b >0, x ═ 0-1, y ═ 0-1, z ═ 0-1, f ═ 0-1

And iv) formula Id

(Lu_1-x-yY_xGd_y)_1-bLn_b(Ca_1-zMg_z)₂Al₃(Zr_1-fHf_f)₂O₁₂ Id*

Wherein Ln_bIs Ln ═ Pr, 0.5 ≧ b >0, x ═ 0-1, y ═ 0-1, z ═ 0-1, and f ═ 0-1.

6. Composition according to any one of the preceding claims, characterized in that the phosphor is selected from the following general formulae:

(Lu_1-x-yY_xGd_y)_3-bPr_b(Al_1-uGa_u)_5-bO₁₂

(Lu_1-x-yY_xGd_y)_3-bPr_b(Al_1-uSc_v)_5-bO₁₂

(Lu_1-x-yY_xGd_y)_3-bPr_b(Ga_1-uSc_v)₅O₁₂

(Lu_1-x-yY_xGd_y)₂Pr_bCaAl₄SiO₁₂

(Lu_1-x-yY_xGd_y)Pr_bCa₂Al₃Si₂O₁₂

(Lu_1-x-yY_xGd_y)₂Pr_bMgAl₄SiO₁₂

(Lu_1-x-yY_xGd_y)Pr_bMg₂Al₃Si₂O₁₂

(Lu_1-x-yY_xGd_y)₂Pr_bCaAl₄(Zr_dHf_e)O₁₂

(Lu_1-x-yY_xGd_y)Pr_bCa₂Al₃(Zr_dHf_e)₂O₁₂

(Lu_1-x-yY_xGd_y)₂Pr_bMgAl₄(Zr_dHf_e)O₁₂

(Lu_1-x-yY_xGd_y)Pr_bMg₂Al₃(Zr_dHf_e)₂O₁₂

wherein b is 0.001-0.05, u is 0-1, v is 0-1, x is 0-1, and y is 0-1.

7. The composition of any of the preceding claims, in a utensilHaving a lower energy and a longer wavelength in the range of 2000nm to 400nm, in particular in the range of 800nm to 400nm, the phosphor emits electromagnetic radiation having a higher energy and a shorter wavelength in the range of 400nm to 100nm, preferably in the range of 300nm to 200nm, wherein the maximum emission intensity of the electromagnetic radiation having a higher energy and a shorter wavelength is at least 1 · 10³Count/(mm)²S), preferably higher than 1 · 10⁴Count/(mm)²S), more preferably higher than 1 · 10⁵Count/(mm)²S) intensity.

8. Composition according to any one of the preceding claims, characterized in that the phosphors according to formulae I, Ia, Ib, Ic, Id and Id have XRPD signals in the range 17 ° 2 θ to 19 ° 2 θ and in the range 31 ° 2 θ to 35 ° 2 θ, where (Ln) represents a lanthanide ion selected from praseodymium, gadolinium, erbium, neodymium or co-doped with at least two of these, preferably praseodymium and optionally gadolinium.

9. Composition according to any one of the preceding claims, characterized in that the film-forming polymer contains functional groups, preferably acidic hydrogens reactive with isocyanate-containing curing agents or catalysts.

10. Composition according to any one of the preceding claims, characterized in that the film-forming polymer is chosen from hydroxyl-functional acrylate polymers, hydroxyl-functional polyester polymers and/or hydroxyl-functional polyether polymers, hydroxyl-functional cellulose derivatives, amino-functional aspartic acid polymers or polyester polymers, which are reacted with isocyanate-containing curing agents.

11. Composition according to any one of the preceding claims, characterized in that the film-forming polymer has a low resonance.

12. Composition according to any one of the preceding claims, characterized in that the film-forming polymer has a transmittance of at least 75%, preferably at least 80%, more preferably at least 85%, by means of a two-beam UV/VIS spectrometer.

13. Composition according to any one of the preceding claims, characterized in that the transmittance is at least 70%, preferably at least 75%, more preferably at least 80%, by means of a two-beam UV/VIS spectrometer.

14. The composition according to any of the preceding claims, characterized in that the phosphor has an average particle size measured according to ISO 13320:2020 and USP 429 with d50 ═ 0.1-100 μ ι η, preferably d50 ═ 1-50 μ ι η.

15. Composition according to any one of the preceding claims, characterized in that the additive is chosen from dispersants, rheology auxiliaries, levelling agents, wetting agents, defoamers and UV stabilizers.

16. Composition according to any one of the preceding claims, characterized in that the curing agent is chosen from aliphatic isocyanates and cycloaliphatic isocyanates.

17. Composition according to any one of the preceding claims, characterized in that the coating produced by it has an antimicrobial effect on bacteria, yeasts, moulds, algae, parasites and viruses.

18. Composition according to any one of the preceding claims, characterized in that the coating resulting therefrom has an antimicrobial effect on:

nosocomial infectious pathogens, preferably against Enterococcus faecium (Enterococcus faecalis), Staphylococcus aureus (Staphylococcus aureus), Klebsiella pneumoniae (Klebsiella pneumoniae), Acinetobacter baumannii (Acinetobacter baumannii), Pseudomonas aeruginosa (Pseudomonas aeruginosa), Escherichia coli (Escherichia coli), Enterobacter (Enterobacter), Corynebacterium diphtheriae (Corynebacterium diphteria), Candida albicans (Candida albicans), rotavirus, phage;

-pathogenic environmental organisms, preferably against Cryptosporidium (Cryptosporidium parvum), Giardia lamblia (Giardia lamblia), amebiasis (acanthamoeba spp.), grisea (nageleria spp.), escherichia coli, coliform bacteria (coliform bacteria), faecal streptococci (faecal streptococci), Salmonella (Salmonella spp.), Shigella (Shigella spp.), legionella (legrinonella spec), pseudomonas aeruginosa, Mykobakteria spp., enteroviruses (e.g. polio and hepatitis a virus);

pathogens in food and beverages, preferably against Bacillus cereus, Campylobacter spp, Clostridium botulinum (Clostridium botulinum), Clostridium perfringens (Clostridium perfringens), enterobacter sakazakii (Cronobacter spp), escherichia coli, Listeria monocytogenes (Listeria monocytogenes), salmonella, staphylococcus aureus, Vibrio spp, Yersinia enterocolitica (Yersinia enterocolitica), bacteriophages.

19. Use of a composition according to any of the preceding claims for producing a dispersion, a millbase, an adhesive, a troweling compound, a primer, a paint, a coating or a printing ink, an inkjet, a grinding resin or a pigment concentrate.

20. Use of a composition according to any one of claims 1 to 18 for producing a coating having antimicrobial properties.

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

22. A method of forming an antimicrobial coating on a substrate comprising applying to the substrate a curable film-forming composition comprising:

(a) at least one film-forming polymer containing functional groups reactive with an isocyanate-containing curing agent, optionally catalyzed by a catalyst,

(b) at least one phosphor of formula (I), and

(c) a curing agent containing isocyanate functional groups.

23. The method of claim 22, wherein the substrate comprises metal, mineral substrates, cellulosic substrates, wood and mixtures thereof, dimensionally stable plastics and/or thermoset materials.

24. The method of any one of claims 22-23, wherein a primer composition is applied to the substrate prior to applying a curable film-forming composition.

25. Article characterized in that it is at least partially, preferably completely, coated with a curable composition according to any one of claims 1 to 18.

Technical Field

The present invention relates to curable compositions for producing coatings with antimicrobial properties, their use, as well as coatings produced therefrom and articles coated therewith.

Background

Humans are exposed to thousands of microorganisms, such as bacteria, fungi, and viruses, each day. Many of these microorganisms are useful or even necessary. However, in addition to these less harmful representatives, there are pathogenic and even fatal bacteria, fungi and viruses.

Microorganisms can be transmitted by daily contact with others and with articles used by others. The surface is treated to be antimicrobial, especially in hygienically sensitive areas. The field of use is in particular the surface of medical equipment and consumables in hospitals and in outpatient health and welfare facilities. In addition to this, surfaces also exist in the public domain, in the food and beverage domain and in the animal husbandry domain. The spread of pathogenic microorganisms is a big problem in today's care and medical sectors and where a large number of people move in enclosed spaces. One particular risk at present is the increased incidence of so-called multi-drug resistant bacteria that are not sensitive to standard antibiotics.

In order to reduce the risk of pathogen transmission through the contact surface, antimicrobial techniques and materials are used in addition to standard hygiene measures. The use of chemical substances or physical methods can have a critical influence on the propagation process of the microorganisms. Physical methods include, for example, heat, cold, radiation, or ultrasound, among others. Among chemical methods, halogens, metal ions, organic compounds and dyes, toxic gases, and the like are known.

Although chemical and physical methods are very effective in most cases in the destruction of microorganisms, their effectiveness is short-lived, promotes the development of resistance, and in some cases is not suitable for certain applications because they lead to the destruction of the surface to be protected. However, especially in the case of chemical organic substances, the greatest disadvantage is the danger or toxicity to humans. Certain substances, such as formaldehyde, which have been used as disinfectants for many years, are now suspected to cause cancer or be extremely harmful to the environment.

Surfaces with antimicrobial action can make a significant contribution to solving these problems. The standard methods for producing such antimicrobial properties are now mainly using active ingredients incorporated into the material, such as silver particles, copper particles, metal oxides thereof or quaternary ammonium compounds. This typically involves processing the antimicrobial metal, metal oxide or metal oxide mixture to obtain nanoparticles, which are then mixed into the paint, coating or polymeric material. The widespread use of metal particles is problematic because it is almost impossible to assess the long-term effects of such heavy metals on humans and the environment.

For example, WO2019/197076 discloses particles made with a layer comprising antimony tin oxide and manganese oxide. Those skilled in the art know that antimicrobial surfaces are created by the electrochemical properties of metals that form miniature galvanic cells in the absence of moisture and produce bactericidal action by virtue of miniature electric fields.

It is also known that ultraviolet radiation can be used in the medical or hygiene field, for example to disinfect water, gases or surfaces. For example, ultraviolet radiation has long been used in drinking water treatment to reduce the number of possible pathogenic microorganisms in the water. This is preferably done using UV-C radiation in the wavelength range between 100nm and 280 nm. The use of electromagnetic radiation of different wavelengths should take into account the different absorption of the different proteins, amino acids/nucleic acids (e.g. DNA) and peptide bonds between the individual acids present in the micro-organism, tissue or cell. For example, DNA has a very good absorption of electromagnetic radiation in the wavelength range between 200nm and 300nm, and a particularly good absorption of electromagnetic radiation in the wavelength range between 250nm and 280nm, so that this radiation is particularly suitable for DNA. Such irradiation can thus be used to inactivate pathogenic microorganisms (in particular viruses, bacteria, yeasts, moulds). Depending on the duration and intensity of the irradiation, the structure of the DNA may be destroyed. Thus, metabolically active cells are inactivated and/or their replicative capacity can be eliminated. The advantage of irradiation with ultraviolet light is that the microorganisms cannot develop tolerance to it.

Furthermore, in addition to direct irradiation with electromagnetic radiation from the ultraviolet light wavelength range, the utilization of the so-called up-conversion (up-conversion) effect is also known. This uses phosphor particles with which electromagnetic radiation of a wavelength higher than ultraviolet light, in particular visible or infrared light, can be converted into electromagnetic radiation having a shorter wavelength, so that radiation emission with the desired effect can be achieved by the respective phosphor particles.

DE 102015102427 relates to a body emitting electromagnetic radiation in the ultraviolet wavelength range. The phosphor particles are embedded in a near-surface region in the body, within the material from which the body is formed, or in a coating on the body. All that is stated herein in general terms is that the phosphor particles are added directly to the coating to be formed on the material during processing, wherein the particular active ingredient should have a suitable consistency or viscosity. DE 102015102427 does not mention suitable polymers and additives.

US 2009/0130169 a1 describes phosphors that may be incorporated into polyvinyl chloride, acryl butadiene, olefins, polycarbonate, styrene or nylon, which kill pathogenic microorganisms by virtue of the upconversion properties of the phosphor. These are phosphors prepared at temperatures of 1800 c to 2900 c. Furthermore, US 2009/0130169 a1 discloses a liquid composition comprising polyurethane, acrylate polymer and filler, and optionally a cross-linking agent. US 2009/0130169 a1 addresses the antimicrobial effect of phosphors but does not discuss the compatibility of the components in the coating composition or the characteristics of the coating surface, e.g., a painted surface. However, the appearance of the coated surface is of paramount importance to the consumer.

The requirements for paints and coatings are varied. In principle, a paint or coating has two tasks or functions: protective functions and decorative functions. Both types of coatings are suitable if only the term "paint coat" is to be explained below. They decorate, protect and preserve materials such as wood, metal or plastic. Thus, there is a need for a bright and glossy paint layer on the one hand and a continuous coating on the other hand to ensure chemical and mechanical stability, a certain slip or a specific feel on the coating.

The problem underlying the present invention was therefore to provide curable compositions of the type specified at the outset with which protective coatings providing long-term antimicrobial properties can be produced without significantly impairing other properties, in particular the storage stability.

Disclosure of Invention

The problem is therefore solved by proposing a curable composition for producing coatings with antimicrobial properties, comprising:

-at least one film-forming polymer,

-at least one up-converting phosphor,

-optionally at least one additive,

-optionally at least one curing agent,

wherein the phosphor is selected from the idealized formula (I):

Lu_3-a-b-nLn_b(Mg_1-zCa_z)_aLi_n(Al_1-u-vGa_uSc_v)_5-a-2n(Si_1-d-eZr_dHf_e)_a+2nO₁₂ I

wherein a is 0-1, 1 is more than or equal to b >0, d is 0-1,

0-1, v, wherein u + v ≦ 1 and d + e ≦ 1;

ln ═ praseodymium (Pr), gadolinium (Gd), erbium (Er), neodymium (Nd), yttrium (Y),

Lu is equal to lutetium,

li ═ lithium.

It has now surprisingly been found that with the composition according to the invention it is possible to produce coatings which have an antimicrobial effect without impairing the surface properties (profile).

The phosphor is preferably doped with praseodymium, which is used in the composition according to the invention.

The phosphor is preferably a solidified melt consisting of a crystalline garnet or of a crystalline garnet doped with lanthanide ions, comprising at least one alkali metal ion and/or at least one alkaline earth metal ion.

The terms "phosphor" and "garnet" may be considered as synonyms hereinafter.

For the composition according to the invention, the phosphor is preferably selected from the idealized general formula (Ia):

(Lu_1-x-yY_xGd_y)_3-a-b-nLn_b(Mg_1-zCa_z)_aLi_n(Al_1-u-vGa_uSc_v)_5-a-2n(Si_1-d-eZr_dHf_e)_a+2nO₁₂ Ia

wherein a is 0-1, 1 ≧ b >0, d is 0-1, e is 0-1, n is 0-1, x is 0-1, y is 0-1, z is 0-1, u is 0-1, v is 0-1, wherein x + y is ≤ 1, u + v is ≤ 1, and d + e is ≤ 1;

wherein in formula Ia, Ln ═ praseodymium (Pr), erbium (Er), neodymium (Nd), or,

Lu ═ lutetium, Gd ═ gadolinium, Y ═ yttrium, Li ═ lithium.

For the composition according to the invention, the phosphor is preferably selected from the following general formulae:

i) formula Ib

(Lu_1-x-yY_xGd_y)_3-bLn_b(Al_1-u-vGa_uSc_v)₅O₁₂ Ib

Wherein Ln_bIs Ln ═ Pr and b ═ 0.001 to 0.05, x ═ 0 to 1, y ═ 0 to 1, u ═ 0 to 1, v ═ 0 to 1,

ii) formula Ic

(Lu_1-x-yY_xGd_y)_3-b-aLn_b(Mg_1-zCa_z)_a+bAl_5-a-bSi_a+bO₁₂ Ic

Wherein Ln_bIs Ln ═ Pr, where 1 ≥ b >0, a >0, x ═ 0-1, y ═ 0-1, z ═ 0-1,

iii) formula Id

(Lu_1-x-yY_xGd_y)_2-bLn_b(Ca_1-zMg_z)Al₄(Zr_1-fHf_f)O₁₂ Id

Wherein Ln_bWhere Ln is Pr, b is >0, x is 0-1, y is 0-1, z is 0-1, f is 0-1,

and iv) formula Id

(Lu_1-x-yY_xGd_y)_1-bLn_b(Ca_1-zMg_z)₂Al₃(Zr_1-fHf_f)₂O₁₂ Id*

Wherein Ln_bIs Ln ═ Pr, 0.5 ≧ b >0, x ═ 0-1, y ═ 0-1, z ═ 0-1, and f ═ 0-1.

For the composition according to the invention, the phosphor is particularly preferably selected from the following formulae

(Lu_1-x-yY_xGd_y)_3-bPr_b(Al_1-uGa_u)_5-bO₁₂

(Lu_1-x-yY_xGd_y)_3-bPr_b(Al_1-uSc_v)_5-bO₁₂

(Lu_1-x-yY_xGd_y)_3-bPr_b(Ga_1-uSc_v)₅O₁₂

(Lu_1-x-yY_xGd_y)₂Pr_bCaAl₄SiO₁₂

(Lu_1-x-yY_xGd_y)Pr_bCa₂Al₃Si₂O₁₂

(Lu_1-x-yY_xGd_y)₂Pr_bMgAl₄SiO₁₂

(Lu_1-x-yY_xGd_y)Pr_bMg₂Al₃Si₂O₁₂

(Lu_1-x-yY_xGd_y)₂Pr_bCaAl₄(Zr_dHf_e)O₁₂

(Lu_1-x-yY_xGd_y)Pr_bCa₂Al₃(Zr_dHf_e)₂O₁₂

(Lu_1-x-yY_xGd_y)₂Pr_bMgAl₄(Zr_dHf_e)O₁₂

(Lu_1-x-yY_xGd_y)Pr_bMg₂Al₃(Zr_dHf_e)₂O₁₂

Wherein b is 0.001-0.05, u is 0-1, v is 0-1, x is 0-1, and y is 0-1.

It should be noted here that the phosphors required for the present invention are disclosed from a previously unpublished european patent application with application reference number EP 19292897.5.

The phosphor is preferably a phosphor which emits electromagnetic radiation having a higher energy and a shorter wavelength in the range of 400nm to 100nm, preferably in the range of 300nm to 200nm, upon irradiation with electromagnetic radiation having a lower energy and a longer wavelength in the range of 2000nm to 400nm, especially in the range of 800nm to 400nm, wherein the maximum emission intensity of the electromagnetic radiation having a higher energy and a shorter wavelength is at least 1 · 10³Count/(mm)²S), preferably higher than 1 · 10⁴Count/(mm)²S), more preferably higher than 1 · 10⁵Count/(mm)²S) intensity. The emission spectrum is excited by a laser, in particular a laser with 75mW power at 445nm and/or 150mW power at 488 nm.

The phosphors of formulae I, Ia, Ib, Ic, Id and Id preferably have XRPD signals in the range of 17 ° 2 θ to 19 ° 2 θ and in the range of 31 ° 2 θ to 35 ° 2 θ, where (Ln) represents a lanthanide ion selected from praseodymium, gadolinium, erbium, neodymium or co-doped with at least two of these, preferably praseodymium and optionally gadolinium, wherein the signals are determined by Bragg-Brentano geometry and Cu-ka radiation. Details of the test method can be found in the not yet published european patent application EP 19292897.5.

The unpublished European patent application EP 19292897.5 is directed to the preparation of phosphors, in particular phosphors of the formulae I, Ia, Ib, Ic, Id and Id. It describes a process comprising the following steps:

i) providing at least one lanthanide salt selected from lanthanide nitrates, lanthanide carbonates, lanthanide carboxylates, preferably lanthanide acetates, lanthanide sulfates and/or lanthanide oxides or mixtures of at least two of these, wherein the lanthanide oxide or lanthanide ion salt in the lanthanide is selected from praseodymium, gadolinium, erbium, neodymium, and for co-doping at least two of these are used,

ii) providing at least one element selected from a lutetium source, a silicon source, an aluminum source, or an yttrium source for forming a garnet lattice, wherein the source is selected from:

a) at least one lanthanide salt or lanthanide oxide, preferably a lanthanide nitrate, a lanthanide carbonate, a lanthanide carboxylate, a lanthanide acetate, a lanthanide sulphate and/or a lanthanide oxide or a mixture of at least two of these, more preferably the lanthanide salt is a lanthanide oxide and/or the lanthanide salt is a lutetium salt, and/or

b) Silicon source and/or

c) An aluminium source, and/or

d) Yttrium salts or yttrium oxides or mixtures thereof,

iii) optionally providing at least one alkaline earth metal salt and/or alkaline earth metal oxide and/or

iv) optionally providing at least one alkali metal salt, and

v) providing a complexing agent, wherein the complexing agent is,

-dissolving i), ii), iii), iv) and v) in an acid,

evaporating the acid and the optional complexing agent at elevated temperature, optionally with stirring,

-obtaining a concentrated reaction product, wherein the reaction product is dried at a temperature of more than 100 ℃,

-obtaining an intermediate, wherein the reaction product is heated at a temperature of up to at least 600 ℃ for 1 to 10 hours to remove organic compounds,

-heating the intermediate up to 1200 ℃ for 0.5 to 10 hours,

-cooling, and

-obtaining a lanthanide ion doped garnet.

Further detailed embodiments of the process can be found in EP 19292897.5.

It was surprisingly found that the phosphors according to EP 19292897.5 have the required upconversion properties leading to an antimicrobial effect. In other words, these phosphors can convert electromagnetic radiation of a wavelength higher than ultraviolet light, in particular visible or infrared light, into electromagnetic radiation having a shorter wavelength, in particular in areas where, for example, microbial DNA can be destroyed. These phosphors are therefore very suitable for the composition according to the invention.

Another problem addressed by the present invention is the selection of film-forming polymers useful in curable compositions having antimicrobial properties. In principle, all film-forming polymers known from the prior art are usable.

The film-forming polymer preferably has functional groups, preferably acidic hydrogens, reactive with the isocyanate-containing curing agent, and is optionally catalyzed by a catalyst.

Advantageously, the film-forming polymer is selected from hydroxyl-functional acrylate polymers, hydroxyl-functional polyester polymers and/or hydroxyl-functional polyether polymers, hydroxyl-functional cellulose derivatives, amino-functional aspartic acid polymers or polyester polymers, which are reacted with isocyanate-containing curing agents.

The film-forming polymer preferably has low resonance.

The physical interaction at the surface is known to those skilled in the art. Depending on the material and its material surface, light incident on the surface produces a variety of effects. The incident light is partly absorbed, partly reflected and, depending on the material surface, also scattered. The light may be absorbed before being emitted. In case of an opaque, translucent or transparent material, light may also penetrate (transmit) through the body. In some cases, the light is polarized or diffracted even at the surface. Some objects may even emit light (illuminated displays, LED sections, displays) or emit fluorescence or phosphorescence of different colors (afterglow).

By "low resonance" in the context of the present invention is meant that the film-forming polymer has low absorption, reflection, reflectivity and scattering. In contrast, the transmission should preferably be significant.

This is because it may have been surprisingly found that the film-forming polymers of the invention having low resonance have an improved antimicrobial effect, because more electromagnetic radiation having lower energy and higher wavelengths in the range of 2000nm to 400nm, in particular in the range of 800nm to 400nm, is transmitted, and therefore they can emit more electromagnetic radiation having higher energy and shorter wavelengths in the range of 400nm to 100nm, in particular in the range of 300nm to 200 nm.

It has been found that the higher the transmission, the higher the emission, which is crucial for the antimicrobial effect.

The transmission of the film-forming polymer measured at a wavelength of 260nm is preferably at least 75%, more preferably at least 80%, particularly preferably at least 85%.

The transmission of the film-forming polymer measured at a wavelength of 500nm is preferably at least 75%, more preferably at least 80%, particularly preferably at least 85%.

By way of illustration, it should be noted herein that transmittance may be defined as at different wavelengths; see fig. 1. For the present invention, a wavelength of 260nm is selected, for example, for the emission wavelength and a wavelength of 500nm is selected, for example, for the excitation wavelength, which are firstly responsible for the upconversion and secondly largely for the antimicrobial action.

At 100% transmission, for example measured at a wavelength of 260nm, the same amount of radiation is converted and emitted; in other words, there is no loss by absorption, scattering, or the like. At 80% transmission, for example measured at a wavelength of 260nm, 20% is not transmitted, which may be due to absorption, reflection, reflectivity and/or scattering. Thus, only 80% of the radiation with a wavelength of 260nm can be emitted.

This important finding is important for the selection of film-forming polymers. For example, polymers having 0% transmission are not suitable for use in the curable composition according to the present invention. They do not transmit any electromagnetic radiation of lower energy and higher wavelength and therefore the phosphors present in the composition are not capable of converting such electromagnetic radiation into electromagnetic radiation of higher energy and shorter wavelength and emitting it, which is necessary for the antimicrobial action.

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

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

The transmittance is preferably measured with a "Specord 200 Plus" dual beam UV/VIS spectrometer from Analytik Jena. Holmium oxide filters are used for internal wavelength calibration. Monochromatic light from a deuterium lamp (ultraviolet range) or tungsten halogen lamp (visible range) passes through the sample. The spectral bandwidth was 1.4 nm. The monochromatic light is divided into a measurement channel and a reference channel, and a reference sample can be directly measured. Radiation transmitted through the sample is detected by the photodiode and processed.

It is conceivable to use compositions with a transmission of less than 70%; they may also have antimicrobial effects, but the efficiency is very mild.

The phosphor preferably has an average particle diameter according to ISO 13320:2020 and USP 429 of from 0.1 to 100 μm d50, preferably from 1 to 50 μm d50, for example as measured using an instrumental LA-950 laser particle size analyzer from Horiba.

In order to effectively incorporate and/or stabilize the phosphor in the composition according to the present invention, various additives may preferably be added.

The additives are preferably selected from the group consisting of dispersants, rheology auxiliaries, levelling agents, wetting agents, defoamers and UV stabilizers.

It has surprisingly been found that the addition of any additive to the composition according to the invention reduces the transmission.

Thus, in a further embodiment wherein an additive is used, the composition according to the invention preferably has a transmittance of at least 70%, preferably at least 75%, more preferably at least 80%, measured at 260 nm.

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

Preferably, the composition according to the invention comprises a curing agent selected from aliphatic or cycloaliphatic isocyanates.

Examples of isocyanate-containing curing agents are monomeric isocyanates, polymeric isocyanates and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates because of their lower toxicity. Examples of polyisocyanates are isocyanurates, uretdiones and biurets based on diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI). Examples of commercially available products are under the trade nameFrom Covestro or from Evonik Industries under the tradename vestnat. The product known is from CovestroN3400、N3300、N3600N75、XP2580、Z4470、XP2565 andand VL. Other examples are from Evonik IndustriesHAT 2500 LV、HB 2640 LV orT1890E. An example of an isocyanate prepolymer is from CovestroE XP 2863、XP 2599 orXP 2406. Other isocyanate prepolymers known to those skilled in the art may also be used.

Curing using a catalyst is contemplated. Subsequent catalysts selected from organic sn (iv), sn (ii), Zn, Bi compounds or tertiary amines may be used.

Preference is given to using organometallic compounds selected from organotin catalysts, titanates or zirconates, aluminum, iron, calcium, magnesium, zinc or bismuth, Lewis acids or organic acids/bases, linear or cyclic amidines, guanidines or amines, or mixtures thereof.

The curing catalysts used are preferably organotin compounds, for example dibutyltin dilaurateDibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate or dioctyltin dilaurate, dioctyltin diacetylacetonate, dioctyltin diketonate, dioctyltin dicarboxylate, dioctyltin oxide, preferably dioctyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin diketonate, dioctyltin dicarboxylate, dioctyltin oxide, more preferably dioctyltin diacetylacetonate and dioctyltin dilaurate. In addition, zinc salts such as zinc octoate, zinc acetylacetonate and zinc 2-ethylhexanoate, or tetraalkylammonium compounds such as N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide, ammonium N, N, N-trimethyl-N-2-hydroxypropyl 2-ethylhexanoate or 2-ethylhexanoate chloride (choline 2-ethylhexoate) can also be used. Preference is given to using zinc octoate (zinc 2-ethylhexanoate) and tetraalkylammonium compounds, particular preference being given to zinc octoate. Further preferred are bismuth catalysts, for example TIB Kat (TIB Mannheim) orCatalysts, titanates, e.g. titanium (IV) isopropoxide, iron (III) compounds, e.g. iron (III) acetylacetonate, aluminium compounds, e.g. aluminium triisopropoxide, aluminium tri-sec-butoxide and also other alkoxides and aluminium acetylacetonate, calcium compounds, e.g. calcium disodium ethylenediaminetetraacetate or calcium diacetylacetonate, or amines, examples being triethylamine, tributylamine, 1, 4-diazabicyclo [2.2.2 ] 2]Octane, 1, 8-diazabicyclo [5.4.0]Undec-7-ene, 1, 5-diazabicyclo [4.3.0]Non-5-ene, N-bis (N, N-dimethyl-2-aminoethyl) methylamine, N-dimethylcyclohexylamine, N-dimethylphenylamine, N-ethylmorpholine, and the like. Also preferred as catalysts are organic or inorganic bronsted acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid or benzoyl chloride, hydrochloric acid, phosphoric acid and mono-and/or diesters thereof, e.g. butyl phosphate, (iso) propyl phosphate, dibutyl phosphate and the like. Also preferred are organic and organosilicon compounds with guanidine. Of course, combinations of two or more catalysts may also be used. Furthermore, photolatent bases can also be used as catalysts, as described in WO 2005/100482.

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

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

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

Preferably, the coating produced by the composition according to the invention has an antimicrobial effect on bacteria, yeasts, moulds, algae, parasites and viruses.

The coatings produced according to the invention preferably have an antimicrobial effect on:

nosocomial infectious pathogens, preferably against Enterococcus faecium (Enterococcus faecalis), Staphylococcus aureus (Staphylococcus aureus), Klebsiella pneumoniae (Klebsiella pneumoniae), Acinetobacter baumannii (Acinetobacter baumannii), Pseudomonas aeruginosa (Pseudomonas aeruginosa), Escherichia coli (Escherichia coli), Enterobacter (Enterobacter), Corynebacterium diphtheriae (Corynebacterium diphteria), Candida albicans (Candida albicans), rotavirus, phage;

-environmental organisms that may be pathogenic, preferably against Cryptosporidium (Cryptosporidium parvum), Giardia lamblia (Giardia lamblia), amebiasis (acanthamoeba spp.), grisea (Naegleria spp.), escherichia coli, coliform bacteria (coliform bacteria), faecal streptococci (faecal streptococci), Salmonella (Salmonella spp.), Shigella (Shigella spp.), legionella (legginonella spec.), pseudomonas aeruginosa, Mykobakteria spp.), enteroviruses (e.g. polio and hepatitis a virus);

pathogens in food and beverages, preferably against Bacillus cereus, Campylobacter spp, Clostridium botulinum (Clostridium botulinum), Clostridium perfringens (Clostridium perfringens), enterobacter sakazakii (Cronobacter spp.), escherichia coli, Listeria monocytogenes (Listeria monocytogenes), salmonella, staphylococcus aureus, vibrio spp, Yersinia enterocolitica (Yersinia enterocolitica), bacteriophages.

The invention further provides for the use of a composition according to the invention for producing dispersions, millbases, adhesives, troweling compounds, render substrates (renderers), paints, coatings or printing inks, inkjet, grinding resins or pigment concentrates.

Preferred is the use of the composition according to the invention for producing coatings with antimicrobial properties.

A coating having an antimicrobial effect or antimicrobial properties means herein that the coating has an antimicrobial surface that limits or prevents the growth and replication of microorganisms.

It has also surprisingly been found that the coating according to the invention is chemically and mechanically stable. Chemical and mechanical stability is particularly important because antimicrobial coatings are often used in areas where regular disinfection and other hygiene measures are required.

The present invention also includes a method of forming an antimicrobial coating on a substrate comprising applying to the substrate a curable film-forming composition comprising:

a. at least one film-forming polymer containing functional groups reactive with an isocyanate-containing curing agent, optionally catalyzed by a catalyst,

b. at least one phosphor of formula (I), and

c. a curing agent containing isocyanate functional groups.

Preferably, the substrate comprises a metal, a mineral substrate (e.g. concrete, natural rock or glass), a cellulosic substrate, wood and mixtures thereof, or a dimensionally stable polymer and/or thermoset material.

The term "dimensionally stable polymer" is to be understood as the following (although not decisive): acrylonitrile Butadiene Styrene (ABS), Polyamide (PA), polylactic acid (PLA), polymethyl methacrylate (PMMA), Polycarbonate (PC), polyethylene terephthalate (PET), Polyethylene (PE), polypropylene (PP), Polystyrene (PS), Polyetheretherketone (PEEK), polyvinyl chloride (PVC).

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

Preferably, the curable composition according to the invention is used for coating of substrates in sanitary facilities and hospitals as well as in the food and beverage industry.

This may include all settings in the public domain, such as schools, geriatric homes, industrial kitchens or nurseries.

Another invention is an article at least partially, preferably completely, coated with a curable composition according to the invention.

It should be noted that the terms "antimicrobial effect", "antimicrobial efficacy", "antimicrobial effect" and "antimicrobial performance" are used herein as synonyms.

The examples shown below are only intended to clarify the invention to a person skilled in the art and do not constitute any limitation to all subject matter claimed.

Method

Measurement of the transmittance

The transmittance measurements were determined using a "Specord 200 Plus" dual beam UV/VIS spectrometer from Analytik Jena. Holmium oxide filters are used for internal wavelength calibration. Monochromatic light from a deuterium lamp (ultraviolet range) or tungsten halogen lamp (visible range) passes through the sample. The spectral bandwidth was 1.4 nm. The monochromatic light is divided into a measurement channel and a reference channel, and enables direct measurement of a reference sample. Radiation transmitted through the sample is detected by the photodiode and processed. The measurements were performed in transmission mode. The measurement range was 190 to 1100nm with a step size of 1 nm. The measurement speed was 10nm/s, corresponding to an integration time of 0.1 s.

Instrument for measuring the position of a moving object

Speedmixer from Hauschild Engineering, model FAC 150.1 FVZ

Dispermat, from Getzmann, Instrument type CV2-SIP

Reflectometer from Zehnner Testing Instruments, Instrument type ZGM 1130

Grid tester (Cross-cut tester), DIN EN ISO 2409, MTV Messtechnik oHG, type: CCP grid template set (cross-cut steel set)

Erichsen cupping test (Erichsen cup test) from Erichsen, type 202

MEK two-pass (twist-stroke) test from Bruno Pellizzato, type: veslic type tester

Rotational viscometer from Anton Paar, instrument: viskotherm VT2

Spectrophotometer (measurement for color point determination), from X-Rite, Instrument type SP 62

Laboratory balance, Sartorius MSE 6202S 100 DO

Hemocytometer (Thoma cell): from Brandt

Stirring and water bath: GFL 1083 from Byk Gardner

Specord200 Plus double-beam UV/VIS spectrometer from Analytik Jena

Nutrient medium

Caso broth: from Merck KGaA Millipore

CASO nutrient agar plate: from Oxoid

Disinfectant

AF: from Hartmann

Material

Table 1: overview of the raw materials of the Polymer matrix used

Table 2: overview of the additives used

Drawings

FIG. 1: transmission spectra of polymer matrices P1-P6 and uncoated quartz glass as reference.

FIG. 2: and (5) constructing an agar plate test.

Phosphor samplesApplication to a plated inoculated nutrient agar plateAnd incubated at room temperature under constant light for 24. + -. 1 h. To verify the antimicrobial efficacy by the effect of the up-conversion, the samples were additionally incubated in the dark.

FIG. 3: and (5) constructing a transfer method.

The polymer matrix containing the phosphors present is pressed onto a well-seeded nutrient agar plate of defined weight (1). The bacteria thus transferred are incubated at room temperature in the light or in the dark (2). Antimicrobial effect was tested by contact with nutrient agar at the indicated weight (3).

FIG. 4: in the light and dark state, in the presence of Lu₂LiAl₃Si₂O₁₂Culturability of Bacillus subtilis after incubation on a polymeric substrate of Pr. Bacillus subtilis was incubated with and without light at room temperature for 0 hours, 1 hour, 2 hours, 3 hours, and 6 hours. The subsequent incubation of the cells on CASO agar was performed at 30 ℃ for 24. + -.1 hours. The figure shows a representative photograph.

Detailed Description

1. Selection of film-forming polymers

Using the measured transmittance, a suitable film-forming polymer for use in the composition according to the invention is selected.

1.1 preparation of compositions without phosphors and additives

The polymer matrices P1-P6 were produced as follows, wherein P1 and P2 are physically dry 1-component systems. P3-P6 are chemically curing 2-component systems.

The polymers in table 1 were diluted or dissolved in butyl acetate in the amounts listed in table 3. (Exception: polyimide)It is used in pure form). Subsequently, 20g of this polymer solution were weighed into a 50ml plastic cup. The curing agent and/or catalyst is added only shortly before application. The polymer matrix was then homogenized in a Speedmixer at 2000rpm for 1 minute.

Table 3: composition of the Polymer matrices P1-P6, 100g each

1.2 coating of the Polymer substrate onto a Quartz plate

P1-P6 were coated onto a quartz plate using a suitable spin coater in order to achieve a dry layer thickness of 30 μm in the dry state. These coating films were dried/cured at room temperature (23 ℃) for 10 days.

1.3 measurement of Transmission

Subsequently, the UV/VIS transmission spectrum was measured.

The polymer matrices P1, P4 and P6 showed high transmittance in the wavelength range of 450 to 500nm (blue light) and 250 to 300nm (UV-C/B light) (fig. 1), and table 4 shows the transmittance at wavelengths of 260nm and 500 nm.

P1, P4, and P6 all have greater than 80% transmission at both wavelengths. Thus, the film-forming polymer can be64/12 (in P1),AC 3820 (in P4) and CAB^TM381-2P6 (in P6) for combination according to the inventionFor producing coatings with antimicrobial properties. Polyimide in P2Can be used as a comparative polymer because the polymer has zero transmission at a wavelength of 260 nm.

TABLE 4 Transmission overview at 260nm and 500nm

Polymer matrix	Transmittance at 260nm [% ]]	Transmittance at 500nm [% ]]
			P1	89.45	93.3
P2	0	89.2
			P3	57.72	92.4
P4	84.85	92.2
			P5	54.45	92.4
P6	86.31	92.8

2. Selection of additives

In order to optimize the coating properties and the stability of the phosphor, for example to prevent sedimentation in the liquid composition according to the invention, various additives were tested in the polymer matrix P4. In addition to the functional suitability of the additives, their suitability for the effect on transmittance was also tested. For this purpose, the UV/VIS transmission spectra of the formulations of the various additives in the polymer matrix P4 were measured.

2.1 measurement of the transmittance

For this purpose, 20g of the polymer matrix P4 and a quantity of the additive to be tested (see Table 5) were weighed out and homogenized in a Speedmixer at 2000rpm for 1 minute. Shortly before application, the curing agent and catalyst were added and the mixture was again homogenized in a Speedmixer at 2000rpm for 1 minute. These mixtures P4-1 to P4-17 were applied to quartz glass plates and aluminum plates with a screw coater and dried/cured at room temperature for 10 days. Their transmittance and coating properties were tested.

Reference to UV/VIS Transmission Spectroscopy, additiveDispers 628、Dispers 670、Dispers 688、DP0111、DP0112、DP0115、R 972、200、BENTONEBENTONEAnd38 are suitable for use in the compositions according to the invention, since they do not significantly reduce the desired transmission, even in the case of film-forming polymers (see table 2). The transmittance is greater than 70%.

For additivesDispers 710、Dispers 650、Dispers 652、Dispers 630、Dispers 689 anddispers 1010, capable of measuring transmission below 70%. (Table 5).

Table 5: the UV/VIS transmission [% ] profile at 260nm and 500nm of the composition consisting of film-forming polymer P4 and additives.

2.2 coating Performance testing of phosphor-free Polymer matrices

The liquid polymer matrix was applied to a Bonder 26s 6800 OC sheet with a spiral coater and dried/cured at 23 ℃ for 10 days. A final dry layer thickness of 30 μm was achieved.

The following coating properties were verified according to the standards DIN and ISO:

gloss degree

Keniger pendulum (C)pendulum) hardness

Lattice test

Erichsen cupping test

MEK two-pass test

Chemical stability to tomato paste, coffee, sulfuric acid (50% aqueous solution), sodium hydroxide solution (10% aqueous solution) and sunscreen. After application to the coating surface, the sunscreen was subjected to 60 ℃ in an oven for 1 hour; all other chemicals were kept at room temperature for 16 hours before removal and then evaluated for damage to the coating surface.

Bacillus double stroke test:AF is suitable for rapid disinfection of alcohol resistant surfaces by a spraying/wiping process.

The coating properties were tested in polymer matrices P3-P6 (Table 6). The polymer matrices P4 and P6 were found to meet typical coating properties. These can therefore be used for further testing.

Table 6: coating Properties of P3 to P6

3. Testing for antimicrobial efficacy

3.1 selection of phosphors

The following phosphors were used:

lu prepared according to example 5 of unpublished European patent application EP 19202897.5₂LiAl₃Si₂O₁₂:Pr

Li prepared by the following method₄P₂O₇：

1.8473g (25.0000mmol) of Li were placed in an agate mortar₂O₃And 2.8756g (25.000mmol) of NH₄H₂PO₄Mixed in acetone. The prepared mixture was calcined at 500 ℃ for 6 hours under standard atmospheric pressure (air). Further calcination was carried out at 650 ℃ for 12 hours under standard atmospheric pressure (air) to obtain a product.

BaY prepared by the following Process₂SI₃O₁₀:Pr³⁺

2.1273g (10.7800mmol) of BaCO were placed in an agate mortar₃1.9828g (33.0000mmol) of SiO₂2.4839g (11.0000mmol) and 0.0187g (0.0183mmol) of Pr₆O₁₁Mixed in acetone. The prepared mixture was calcined at 1400 ℃ for 6 hours under a CO atmosphere to obtain a product.

Ca prepared as follows₃Sc₂Si₃O₁₂:Pr³⁺，Na⁺(1％)：

1.8119g (18.1030mmol) of CaCO₃0.0104g (0.0102mmol) of Pr₆O₁₁0.8428g (6.1110mmol) of Sc₂O₃And 0.0032g (0.0306mmol) of Na₂CO₃Dissolved in hot concentrated nitric acid. The solution was concentrated to obtain nitrate. Water was added to the nitrate while stirring continuously. 1.1043g (18.3790mmol) SiO₂Mixed with 20mL of water and placed in an ultrasonic bath to isolate the agglomerates. The dispersion was added to the water/nitrate solution described above and mixed. 11.1314g (121.1300mmol) of C were added thereto₄H₁₁NO₃. The solution was concentrated. The reaction product was dried at 150 ℃. The reaction product was then calcined in a muffle furnace at 1000 ℃ for 2 hours under standard atmospheric pressure (air). In forming gas (N)₂/H₂(ii) a 95%/5%) at 1300 ℃ for 4 hours to obtain the product.

3.2 antimicrobial efficacy testing of phosphors

First, the antimicrobial efficacy of the phosphor itself was tested. The efficacy of the phosphors was tested against gram positive and gram negative test organisms.

The test was carried out on Bacillus subtilis, which was used for DVGW (German society for gas and Water technology science) Arbeitsblatt W294'zur Desingfection in der Wasserversorung "[ Standard W294" UV Instruments for Disinfection in Water Supply apparatus "]Biological dosimetry testing of the UV system of (1). As a gram-positive spore-forming bacterium, it is particularly insensitive to uv radiation and is therefore well suited as a worst case test for antimicrobial action of uv radiation.

In addition, antimicrobial efficacy tests were also performed on E.coli to show antimicrobial action against gram-negative bacteria. Coli is a gram-negative aerobic bacterium that is mainly present in the human intestinal tract and is therefore a typical indicator of fecal contamination. In the case of other tissues contaminated with E.coli, the result is often an infectious disease, such as urogenital infections.

3.2.1 agar plate assay

The antimicrobial effect of the phosphors on the test organisms bacillus subtilis and escherichia coli was verified using agar plate tests.

For testing, solid nutrient agar plates were flooded with a bacterial suspension of the test organism. Phosphor samples were applied to the inoculated nutrition plates (fig. 2). The plates were incubated under appropriate growth conditions. After incubation of the plates, growth inhibition properties were assessed by the formation of zones that did not grow concentric colonies at and around the phosphor accumulated on the nutrient plate.

The test organisms used were Bacillus subtilis subspecies Spizzinii (DSM 347, ATCC6633) and E.coli (DSM 1116; ATCC 9637). Test organisms at a final concentration of 10⁷Individual cells/ml were used in suspension.

Bacterial suspensions were produced by diluting precultures of the respective bacterial strains. Dilution was performed in sterile deionized water. Pre-cultures of test organisms were produced in sterilized casein peptone-soya peptone (CASO) broth. The preculture of Bacillus subtilis was incubated for 16. + -.1 h at 30 ℃ with constant stirring in a stirred water bath. In a magnetic stirring bar with heat insulation of conical flask, at 350rpm continuous stirring at 36 degrees C temperature incubation of Escherichia coli pre culture. The cell titer of the preculture was determined by microscopy using a hemocytometer (Thoma counting chamber).

For agar plate assay, 1.0ml of 10⁷The bacterial suspension of individual cells/ml was evenly distributed on sterile CASO agar plates to ensure confluent coverage of nutrient agar. The applied bacterial suspension was equilibrated on nutrient agar for 300 + -30 seconds at room temperature (22 + -2 deg.C) before the phosphor was centrally applied. In addition, calcium carbonate and copper oxide were also each applied centrally to the nutrition board as negative and positive references. It is well known that copper oxide has a growth inhibitory effect, whereas calcium carbonate must not exhibit any growth inhibitory effect.

The nutrition plates were incubated at room temperature under constant light for 24 ± 1 hour. The same preparation was also incubated in the dark additionally.

Incubation in light and dark, if any growth inhibitory effect, should indicate the up-conversion properties of the phosphor.

All samples and reference homogeneity are triplicated over an incubation period of 24 ± 1 hour and tested with and without light.

Phosphor and phosphor particles are used synonymously.

3.2.2 results of agar plate assay

The growth inhibitory effect of the phosphors on bacteria was visually examined after 24 + -1 hours at room temperature (Table 7).

The growth inhibitory effect is indicated when a concentric region of no bacterial colony growth occurs around and at the accumulated phosphor particles or reference particles on the nutrient agar.

When bacterial colony growth was detected on nutrient agar around and at the accumulated phosphor particles or reference particles, no growth inhibition was indicated.

After 24 + -1 hours incubation at room temperature with light, the phosphor Lu can be detected₂LiAl₃Si₂O₁₂Pr has growth inhibiting effect on Bacillus subtilis and Escherichia coli. No growth inhibitory effect could be detected around the other phosphors (table 7).

Whereas for all phosphors no bacterial colony growth could be detected around and at the accumulated phosphor particles under dark incubation conditions.

These results clearly show that the phosphor Lu₂LiAl₃Si₂O₁₂The antimicrobial effect of Pr is a physical effect of ultraviolet emission in the light excited state. No up-conversion occurs in the dark state, so the antimicrobial effect of the phosphor is not detected in the dark state.

The reference using calcium carbonate did not show any areas with bacterial colony growth under bright or dark conditions. In contrast, the reference with copper oxide shows concentric areas where no bacterial colonies grow under both bright and dark conditions.

Furthermore, the phosphor did not show any real contamination.

The results show that the phosphor Lu₂LiAl₃Si₂O₁₂Pr is suitable for use in the curable composition according to the invention.

Table 7: results of agar plate test

3.3 testing of the antimicrobial efficacy of the compositions according to the invention

At 3.2, the phosphor Lu is shown₂LiAl₃Si₂O₁₂Pr itself has an antimicrobial effect. It is now to be determined whether such antimicrobial effect is still suitable for use in the composition according to the invention.

It is noted herein that the terms "antimicrobial effect", "antimicrobial efficacy", "antimicrobial effect" and "antimicrobial performance" are used as synonyms.

To test the antimicrobial efficacy of the compositions according to the invention, three phosphors and film-forming polymer matrices P4, P2 and P6 were used, with P2 being used as comparative example.

Using a phosphor Lu₂LiAl₃Si₂O₁₂:Pr。

3.3.1 preparation of curable compositions

Curable compositions according to the invention Z4-1 and Z6-1 and comparative example VZ2-1 were prepared according to the details in Table 8. 50g of glass beads are added to the corresponding composition and the mixture is milled in a Speedmixer at 2000rpm for 5 minutes. After filtering off the glass beads, the corresponding composition was applied to a polymer film, crosslinked to form a film. A coating is then present on the substrate, the surface of which coating should have an antimicrobial effect.

The formulation of the composition is clear in table 8.

3.3.2 transfer method

The test organism used was again Bacillus subtilis subspecies Sphaeroides (DSM 347, ATCC 6633). 1ml of 10 final concentration⁷Individual cell/ml suspension of Bacillus subtilisThe solution was evenly distributed on sterile CASO agar plates to ensure confluent coverage of nutrient agar. The applied bacterial suspension was equilibrated on nutrient agar for 300. + -.30 seconds at room temperature (22. + -. 2 ℃). Bacterial suspensions were produced by diluting precultures of the respective bacterial strains. Dilution was performed in sterile deionized water. Pre-cultures of test organisms were produced in sterilized CASO broth. The preculture of Bacillus subtilis was incubated for 16. + -.1 h at 30 ℃ with constant stirring in a stirred water bath. The cell titer of the preculture was determined by microscopy with a hemocytometer (Thoma counting chamber).

The purpose of the transfer method is to simulate the antimicrobial action of the coated surface under near-real conditions on a dry inanimate surface. For this purpose, the coating obtained as described above is cut into 2.5cm x 4cm sizes and pressed for 60. + -.5 seconds on nutrient agar plates with a defined weight of 90. + -.1 g which are replated with Bacillus subtilis. This step transfers the bacteria in semi-dry form to the surface of the coating. Subsequently, the substrate was placed in an empty petri dish with the coated and inoculated side facing up and incubated under light at room temperature for 0 hours, 1 hour, 2 hours, 3 hours, 6 hours.

To test the antimicrobial efficacy by the up-conversion effect, the substrates with the coated and inoculated faces were additionally incubated for 0 h, 1 h, 2 h, 3 h, 6 h at room temperature in the dark.

The control references chosen were again calcium carbonate (no growth inhibitory effect) and copper oxide (with growth inhibitory effect).

All samples and references were in triplicate during the incubation period and tested with and without light.

The culturability was measured by contact test to examine the antimicrobial effect after a suitable incubation time (FIG. 3).

To test the culturability of Bacillus subtilis, the substrate was pressed on the coated and inoculated side for 60. + -.5 seconds after incubation times of 0 h, 1 h, 2 h, 3 h, 6 h on sterile nutrient agar plates with a defined weight of 90. + -.1 g. The nutrient agar was then incubated under static conditions at 30 ℃ for 24. + -.1 h. The formed bacterial colonies were assessed visually and qualitatively.

Table 8: formulation of curable compositions for transfer processes

3.3.3 results of the transfer method

In the transfer method, any growth inhibitory effect can be examined by reduction of culturability of Bacillus subtilis.

The culturability of the adherent bacteria on the coated surfaces of Z4-1 and Z6-2 showed a significantly reduced replication with increasing incubation time (FIG. 4). The phosphor Lu in the curable composition according to the invention compares to the blank sample and the sample incubated in the dark₂LiAl₃Si₂O₁₂Pr results in a significant reduction in the culturability of Bacillus subtilis. This reduction can be measured even after only 1 hour of incubation under constant light. The decrease in culturability increased until 6 hours of incubation under constant light. The composition incubated in the dark did not show any reduction in culturability over the 6 hour incubation period. For Z4-1, a representative image is shown in FIG. 4.

Since the number of culturable bacteria did not change over the 6 hour period, it could be shown that the antimicrobial effect of the phosphor was only present in the illuminated state. There is therefore also an up-conversion effect here.

In the case of comparative composition VZ2-1 (Table 9), the antimicrobial effect of the phosphor tested was not detectable. It can be inferred therefrom thatAC 3820 and Polymer CAB^TM381-2 comparison, polymeric polyimideAre not suitable film-forming polymers for use in the curable composition according to the invention.

In the calcium carbonate reference, a decrease in culturability of bacillus subtilis in light or dark state could not be detected. By adding copper oxide, a significant decrease in culturability can be detected in the dark and light conditions.

Furthermore, the polymer matrix does not show any real contamination.

Table 9: antimicrobial efficacy of curable compositions

Physical Properties of the compositions according to the invention

An important characteristic of curable compositions is storage stability. Conclusions regarding storage stability can be drawn by measuring the viscosity and properties of the deposit, such as homogenization of the curable composition Z6-1 according to the invention according to table 8 and formation of a slurry (serum), without using any curing agent or any catalyst. Hereinafter referred to as Z6-1. Using a phosphor Lu₂LiAl₃Si₂O₁₂:Pr。

Viscosity of

Z6-1 contains no curing agent and no catalyst, but the corresponding additives, the viscosity of which is measured by cone and plate rotational viscometer. After a period of 1 week and 2 weeks at 40 ℃, the viscosity was checked for differences from the initial values directly after mixing (table 10).

It has been found that all compositions containing additives show a moderate increase in viscosity over a period of 2 weeks similar to the composition without additives in terms of storage stability at 40 ℃.

Deposition and homogenization

In addition, the formation of deposits was checked after a period of 1 week and 2 weeks at 40 ℃ (table 11).

Evaluation criteria:

deposit [% ] -height of deposit [ cm ] compared to the total height [ cm ] of the wet coating

Homogenization is mild, moderate or severe, where the mixture is stirred with a spatula.

As can be seen from Table 11, compositions Z6-2 anddispers 628 and Z6-2 anddispers 688 showed very good results in terms of particle deposition. At 40 ℃, only very slight particle deposition occurred within 2 weeks. At Z6-2 anddispers 628 and Z6-2 andin the case of Dispers 688, after a period of 1 week, the granules were easily re-homogenized without additives and withThis is not the case with the composition of Dispers 670.

Table 10: viscosity [ mPa ]

Table 11: deposition and homogenization