Molded body with biocidal coating for the prevention or reduction of microbial infestation and plant growth, in particular algal growth on surfaces and consumer goods, use of a substance for the manufacture of the molded body and use of the molded body

Abstract

A shaped body designed as a textile nonwoven, knitted textile, textile fiber, filtration membrane, film, floor covering, furniture component, part of a ship, container for fluids, piping element for fluids or granules and whose surface is partially or completely coated with a biocidal coating consisting of a carrier material of one or more polymers, one or more additives and 0.01 to 10 wt.% of a substance with the chemical composition Ce1-xMxO2-y, based on the total weight of the biocidal coating, or consisting of one or more polymers, one or more additives and 10-9 to 50 wt.-% of a substance with the chemical composition Ce1-xMxO2-y, based on the total weight of the molded body; wherein - M is selected from Ca, Ti, V, Fe, Sr, Zr and Nb; - x is a real number with 0 ≤ x ≤ 0.5; - y is a real number with 0 < y ≤ 0.4; characterized in that - the substance with the chemical composition Ce1-xMxO2-y consists of rod-shaped particles with a length of 50 to 800 nm, a cross-sectional area of ​​20 to 40 nm² and an equivalent diameter of 12 to 40 nm; and - a surface of the molded body contains particles with the chemical composition Ce1-xMxO2-y, wherein the particles are force-fitted to the molded body.

Description

The invention relates to a shaped body having a biocidal coating according to claim 1, and to an embodiment thereof according to claim 2, to a use of a substance for producing the shaped body according to claim 3 and to a use of the shaped body according to claim 4.In medicine and numerous technical fields, it is necessary or expedient to prevent or inhibit bacterial infestation and vegetation, in particular algae fouling on the surface of utility goods, such as, for example, furniture, soil sheets, ship hulls, filtration membranes and the like. For this purpose, it is customary to equip the particular item of utility or its surface with a bactericidally acting substance, in particular with antibiotics or metallic particles of silver, copper oxide or zinc oxide.Furthermore, it is known from WO 1995 / 027709 A1 to use haloperoxidases, such as vanadium haloperoxidase, as additive in paint paints. Haloperoxidases are enzymes which catalyze the oxidation of halides to hypohalogenitic acid according to the reaction equation H 2 O 2+ X -+ H + → HOX + H 2 O wherein hydrogen peroxide (H 2 O 2) acts as oxidizing agent and X - is a halogen anion such as I -, Br - or Cl-.U.S. Pat. No. 7,063,970 B1 discloses the use of oxidoreductases as an additive for the preservation of water-based paints as an alternative to conventional, environmentally harmful biocides.EP 0 500 387 B1 describes the use of haloperoxidases in antiseptic pharmaceutical products.WO 2013 / 82641 A1 relates to the use of vanadium pentoxide as biocide and discloses a biocidal composition comprising particles of vanadium pentoxide and methods for avoiding biofouling and for biocidal finishing of substrates. Further prior art is U.S. Pat. No. 7,534,453 B1, WO 2015 / 193 134 A1, JP 2003-171602 A, WO 2011 / 005 770 A1, US 2013 / 0032529 A1, US 2009 / 0107925 A1 and RAGG, E.; TAHIR, M. N.; TREMEL, W.: Solids Go Bio: Inorganic Nanoparticles as Enzyme Mimic. Eur. J. Inorg. Chem., 2026. S.1906-1915 HERGET, K.; FRERICHS, H.; PFITZNER, F.TAHIR, M.N.; TREMEL, W., Functional Enzyme Mimic for Oxidative Halogenation Reactions that Combat Biofilm Formation, Adv. Mater. 2018, 30, 1707073. https: / / doi.org / 10.1002 / adma.2017073, MAYER-GALL, T.; ENGELS, T.; GUTMANN, J.; PFITZNER, F.; PÜTZ, E.; TREMEL, W.; GAZANIS, A.; HEERMANN, R., Cerium oxide nanozymes as biocidal-free antifouling finish for outdoor fabrics, Melliand International, 2022, 28, 121-123.The biocidal coatings and shaped bodies known in the prior art have one or more of the following disadvantages:low resistance to erosion and elution;low effectiveness over longer periods of time;toxicity, biological intolerance and environmental damage;complex production;high costs.The object of the invention is to overcome the above disadvantages and to prevent or reduce microbial infestation and vegetation, in particular algae fouling on surfaces of shaped bodies and articles of use. This object is achieved by biocidal compositions, shaped bodies and articles of use produced from the biocidal compositions or coated with the biocidal compositions.In a first embodiment, which is not claimed, the invention relates to a shaped body according to claim 1.Advantageous embodiments of the coating composition are characterized in thatx is a real number with 0.01 ≤ x ≤ 0.5;x is a real number with 0.05 ≤ x ≤ 0.5;x is a real number with 0.1 ≤ x ≤ 0.3;y is a real number with 0.005 ≤ y ≤ 0.4;y is a real number with 0.01 ≤ y ≤ 0.4;y is a real number with 0.02 ≤ y ≤ 0.4;the substance having the chemical composition comprises Ce 1-x M x O 2-y particles which are partially or completely crystalline;the substance having the chemical composition comprises Ce 1-x M x O 2-y particles which are polycrystalline;the substance having the chemical composition comprises Ce 1-x M x O 2-y particles which have a dimension of ≤500 nm in one or more spatial directions;In a further embodiment, the invention relates to a shaped body, the surface of which is partially or completely coated with a biocidal coating consisting of a carrier material and a substance having the chemical composition Ce 1-x M x O 2-y, according to claim 1 and according to claim 2.the shaped body according to claim 4, for example a table top or a cabinet door, which is the wall of a hull or a propeller, a water tank, a water pipe, or a granulate, anda portion of the particles protrudes from the biocidal coating.Advantageous embodiments of the biocidal shaped body are characterized in thatx is a real number with 0.01 ≤ x ≤ 0.5;x is a real number with 0.05 ≤ x ≤ 0.5;x is a real number with 0.1 ≤ x ≤ 0.3;y is a real number with 0.005 ≤ y ≤ 0.4;y is a real number with 0.01 ≤ y ≤ 0.4;y is a real number with 0.02 ≤ y ≤ 0.4;the substance having the chemical composition comprises Ce 1-x M x O 2-y particles which are partially or completely crystalline;the substance having the chemical composition comprises Ce 1-x M x O 2-y particles which are polycrystalline;the support material of the biocidal coating consists of one or more polymers based on polydimethylsiloxane and one or more additives;the support material of the biocidal coating contains one or more hydrolyzable polymers having a polymeric backbone and functional groups, the polymeric backbone consisting of monomers selected from acrylic, methacrylic, acrylonitrile, acrylamide, methacrylamide, vinyl esters, vinyl ethers, vinyl amide, vinyl ketone, styrene, olefins, monomers having reactive silicon-containing groups, halogen-containing monomers, and mixtures thereof;the support material of the biocidal coating contains one or more hydrolyzable polymers having a polymeric backbone and functional groups, the functional groups being selected from amines, amides, cyclic amides, acid groups and blocked acid groups;the support material of the biocidal coating contains one or more hydrolyzable polymers having a polymeric backbone and functional groups, the functional groups being selected from amines, amides, cyclic amides, acid groups and blocked acid groups, the acid groups being blocked by means of quaternary ammonium groups;the support material of the biocidal coating contains one or more resins of natural origin, such as wood rosin;the support material contains one or more polymers selected from polyarylene ethers, polysulfones, polyethersulfones (PES), polyphenylene sulfones, polyamides (PA), aromatic polyamides, aliphatic polyamides, polyvinyl alcohol (PVA), cellulose acetate (CA), cellulose triacetate (CTA), cellulose esters, cellulose nitrate, regenerated cellulose, polyimides, aromatic polyimides, aliphatic polyimides, polybenzimidazole (PBI), polybenzimidazolone (PBL), polyacrylonitrile (PAN), polyacrylonitrile-polyvinyl chloride copolymer (PAN-PVC), polyacrylonitrile-methallyl sulfonate copolymer, poly(dimethyl-phenylene oxide) (PPO), polycarbonate, polyester, polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF), polypropylene (PP), polyelectrolyte complexes, poly(methyl methacrylate) PMMA, polydimethylsiloxane (PDMS), polyamideimides, aromatic polyamideimides, aliphatic polyamideimides, polymers having phosphatic acid and / or carboxylic acid groups;In a further embodiment, the invention relates to a shaped body which consists of a base material and a substance having the chemical composition Ce 1-x M x O 2-y, according to claim 1, claim 2 and claim 3, whereina portion of the particles protrudes from the surface of the shaped body;Advantageous configurations of the shaped body are characterized in thatx is a real number with 0.01 ≤ x ≤ 0.5;x is a real number with 0.05 ≤ x ≤ 0.5;x is a real number with 0.1 ≤ x ≤ 0.3;y is a real number with 0.005 ≤ y ≤ 0.4;y is a real number with 0.01 ≤ y ≤ 0.4;y is a real number with 0.02 ≤ y ≤ 0.4;the proportion of the substance having the chemical composition Ce 1-x M x O 2-y10-9 is from 10 wt %, based on the total weight of the shaped body;the proportion of the substance having the chemical composition Ce 1-x M x O 2-y0,01 is from 10 wt %, based on the total weight of the shaped body;the shaped body comprises particles having the chemical composition Ce 1-x M x O 2-y which are partially or completely crystalline;the substance having the chemical composition comprises Ce 1-x M x O 2-y particles which are polycrystalline;a surface of the shaped body contains particles having the chemical composition Ce 1-x M x O 2-y wherein the particles are bonded to the solid body in a force-fit manner;a surface of the shaped body contains particles having the chemical composition Ce 1-x M x O 2-y wherein the particles are connected to the shaped body in a force-fit manner and a part of the particles protrudes from the surface of the shaped body; andthe base material contains one or more polymers selected from polyarylene ethers, polysulfones, polyethersulfones (PES), polyphenylene sulfones, polyamides (PA), aromatic polyamides, aliphatic polyamides, polyvinyl alcohol (PVA), cellulose acetate (CA), cellulose triacetate (CTA), cellulose esters, cellulose nitrate, regenerated cellulose, polyimides, aromatic polyimides, aliphatic polyimides, polybenzimidazole (PBI), polybenzimidazolone (PBL), polyacrylonitrile (PAN), polyacrylonitrile-polyvinyl chloride copolymer (PAN-PVC), polyacrylonitrile-methallyl sulfonate copolymer, poly(dimethyl-phenylene oxide) (PPO), polycarbonate, polyester, polytetrafluoroethylene (PTFE), Poly(vinylidene fluoride) (PVDF), polypropylene (PP), polyelectrolyte complexes, poly(methyl methacrylate) PMMA, polydimethylsiloxane (PDMS), polyamideimides, aromatic polyamideimides, aliphatic polyamideimides, polymers having phosphatic acid and / or carboxylic acid groups.A further object of the present invention is to prevent or reduce microbial attack on surfaces of shaped bodies and articles of use.This object is achieved by the use of a substance having the chemical composition Ce 1-x M x O 2-y for the production of shaped bodies or shaped body coatings, whereM is selected from Ca, Ti, V, Fe, Sr, Zr and Nb;x is a real number with 0 ≤ x ≤ 0.5;y is a real number with 0<y≤0.4,the substance having the chemical composition Ce 1-x M x O 2-y comprises rod-shaped particles having a length of 50 to 800 nm, a cross-sectional area of 20 to 40 nm 2 and an equivalent diameter of 12 to 40 nm;a portion of the particles protrudes from the surface of the shaped body or the surface of the shaped body coating; andthe shaped body is formed as a textile nonwoven, textile knitted fabric, textile fiber, filtration membrane, film, floor covering, furniture component, component of a ship, container for fluids, line element for fluids or granules.Advantageous uses of the substance having the chemical composition Ce 1-x M x O 2-y for the production of shaped bodies or shaped body coatings are characterized in thatx is a real number with 0.01 ≤ x ≤ 0.5;x is a real number with 0.05 ≤ x ≤ 0.5;x is a real number with 0.1 ≤ x ≤ 0.3;y is a real number with 0.005 ≤ y ≤ 0.4;y is a real number with 0.01 ≤ y ≤ 0.4;y is a real number with 0.02 ≤ y ≤ 0.4;the substance having the chemical composition comprises Ce 1-x M x O 2-y particles which are partially or completely crystalline; and / orthe substance having the chemical composition comprises Ce 1-x M x O 2-y particles which are polycrystalline.A process for the production of biocidal shaped bodies which is not claimed comprises the steps:providing a shaped body;providing a coating composition comprising a substance having the chemical composition Ce 1-x M x O 2-y whereinM is selected from Ca, Ti, V, Fe, Sr, Zr and Nb;x is a real number with 0 ≤ x ≤ 0.5;y is a real number with 0<y≤0.4;coating the shaped body with the coating composition; andfixing the coating composition on the shaped body.Preferably, the coating composition is fixed to the shaped body by- drying;melting;thermal crosslinking; orcrosslinking by means of UV radiation.A further expedient, non-claimed method for producing a biocidal shaped body comprises the steps of (a) providing a shaped body; (b) providing a substance having the chemical composition Ce 1-x M x O 2-y in the form of a particulate powder, whereinM is selected from Ca, Ti, V, Fe, Sr, Zr and Nbx is a real number with 0 ≤ x ≤ 0.5;y is a real number with 0<y≤0.4;(c) coating the shaped body with the powder by powder coating or spraying; and (d) fixing the powder on the shaped body.Preferably, a surface of the shaped body is coated with an adhesive layer before the shaped body is coated with powder in step (c).In step (d), the powder is advantageously fixed to the shaped body by- drying;melting;thermal crosslinking; orcrosslinking by means of UV radiation.A further process, not claimed, for producing a biocidal shaped body comprises the steps(e) providing a base material;(f) providing a substance having the chemical composition Ce 1-x M x O 2-y, whereinM is selected from Ca, Ti, V, Fe, Sr, Zr and Nb;x is a real number with 0 ≤ x ≤ 0.5;y is a real number with 0<y≤0.4;(g) mixing the base material with the substance having the chemical composition Ce 1-x M x O 2-y; and(h) forming a molded article from the mixture obtained in step (g).In a suitable embodiment of the method, the base material provided in step (e) consists of one or more polymers and one or more additives.In a further expedient embodiment of the method, the base material provided in step (e) consists of one or more ceramic substances and one or more additives.Preferably, the mixture obtained in step (g) is plasticized by means of a gelling unit or an extruder before the molding in step (h).Preferably, the forming in step (h) is carried out by means ofextrusion through a slot die;extrusion through a profile die;injection molding;melt spinning;solution spinning; and / orphase inversion in a precipitation bath.In a suitable embodiment of the method, a shaped body produced in step (h) is sintered.In the context of the present invention, the term "substance having the chemical composition Ce 1-x M x O 2-y" denotes a preferably crystalline or polycrystalline compound in which M is calcium (Ca), titanium (Ti), vanadium (V), iron (Fe), strontium (Sr), zirconium (Zr) or niobium (Nb), and the atoms cerium (Ce), M and oxygen (O) are present in the ratio (1-x):x:(2-y) where 0≤x≤0.5 and 0<y≤0.4.The invention is based on the finding that a substance having the chemical composition Ce 1-x M x O 2-y catalyzes the oxidation of halogen anions X -, such as I -, Br - and Cl - to give hypohalogenitic acid HOX, according to the reaction equation: H 2 O 2+ X -+ H+→HOX+H2OAccordingly, the molded articles and articles for use made of a material having the chemical composition Ce 1-x M x O 2-y produced according to the invention are preferably used in a medium containing hydrogen peroxide (H 2 O 2) and halogen anions such as I -, Br - and Cl -.The inventors have also found that a certain oxygen deficit, i.e. y>0, is required for the catalytic activity of the substance Ce 1-x M x O 2-y.The invention is based further on the finding that halogen anions, such as I -, Br - and Cl -, and hydrogen peroxide are present in seawater, inner waters and the feed water or raw water and also the permeate of desalting and clarifying plants or are formed continuously. In particular, hydrogen peroxide is continuously formed in water exposed to the interior light or the light of UV lamps. UV lamps are used, inter alia, in desalting and clarifying plants for disinfection.The invention is explained in more detail below with reference to figures and examples. It shows FIG. 1 shows a shaped body with a biocidal coating of a carrier material and particles of Ce 1-x M x O 2-y; FIG. 2 shows a shaped body containing particles of Ce 1-x M x O 2-y; FIG. 3 shows a shaped body whose surface is coated with particles of Ce 1-x M x O 2-y; FIG. 4 shows the bacterial infestation on polymeric coatings with a CeO 2- content of 0% by weight, 5% by weight and 10.0% by weight; FIG. 5 shows the algae infestation on marine lacquers containing CeO 2- and weathered in seawater.FIG. 1 shows a schematic sectional view of a surface of a molded body 1 made of a base material 5 having a region 4 close to the surface and a coating 6. the coating 6 comprises a carrier material 7 and particles 8 having the chemical composition Ce 1-x M x O 2-y. The particles 8 are embedded in the carrier material 7, wherein a portion of the particles 8 protrudes from the surface of the molded body 2 or from the coating 6 and is in direct contact with a medium surrounding the molded body 2.FIG. 2 shows a schematic sectional view of a surface of a molded body 2 made of a base material 5 having a region 4 close to the surface. the molded body 2 comprises particles 8 having the chemical composition Ce 1-x M x O 2-y. The particles 8 are embedded in the base material 5, wherein a part of the particles 8 protrudes from the surface of the molded body 2 and is in direct contact with a medium surrounding the molded body 2.FIG. 3 shows a schematic sectional view of a surface of a molded body 3 made of a base material 5 with a region 4 close to the surface. particles 8 with the chemical composition Ce 1-x M x O 2-y are arranged on the surface of the molded body 3. The particles 8 are connected to the surface of the molded body 3 in a force-fitting manner and are in direct contact with a medium surrounding the molded body 3. The force-locking adhesion of the particles 8 to the surface of the shaped body 3 is mediated by three alternative measures or mechanisms (i) to (iii): (i) the surface of the shaped body 3 is coated with an adhesive layer not shown in FIG. 3 ; (ii) the particles 8 are coated with an adhesive layer not shown in FIG. 3 ; (iii) the particles 8 are partially embedded in the region 4 of the shaped body 3 close to the surface (not shown in FIG. 3 );The adhesive layer listed under item (i) and (ii) consists of a solvent-based adhesive, a thermoplastic adhesive or an adhesive that can be chemically, thermally or by means of light, in particular UV light. After the deposition of the particles 8 on the surface of the shaped body 3 by means of powder coating or spraying, the adhesive layer is dried, melted or crosslinked and the particles 8 are permanently mechanically fixed on the surface of the shaped body 3.In the embodiment described under item (iii), the base material 5 of the molded body 3 is thermoplastic. After the particles 8 have been deposited on the surface of the shaped body 3 by means of powder coating or spraying, the region 4 close to the surface is softened or melted by means of a suitable heat source, such as an infrared lamp or a hot air fan, with the result that the particles 8 are partially surrounded by the base material 5 and, after cooling, are mechanically anchored therein.Powder coating of shaped bodies with particulate Ce 1-x M x O 2-y is preferably carried out with the aid of methods established in the prior art, such as electrostatic or triboelectric powder coating.Comparative Example 1: Synthesis of CeO2-ynanorodsTo produce nanoscale CeO 2-y an aqueous solution of NaOH (100 ml, 9 M, 37.8 g) was added directly to an intensively stirred solution of cerium(III) nitrate hexahydrate in high-purity water (MilliQ water according to ISO 3696) (5.2 g of Ce(NO 3)3 · 6 H 2 O in 20 ml, corresponding to 0.6 M). After stirring vigorously for 30 minutes, the lilac mixture was transferred to a steel autoclave having a capacity of 270 ml and maintained at a temperature of 100°C for 24 hours. Thereafter, the lilac color product contained in the turbid solution was separated by centrifugation (3000 U / min, 10 min) and washed five times with MilliQ water (15 ml each). After drying at 60° C. for 12 hours, the product obtained was carefully ground in order to break up the agglomerates formed during the precipitation. The gravimetrically determined yield was greater than 70%. The powdery product was finally suspended by ultrasonic wave at a concentration of 1 mg / mL in MilliQ water, placed on sample grids for a high resolution transmission electron microscope (HRTEM), and dried under normal conditions. The structure of the obtained CeO 2-y- powder was observed by a high-resolution transmission electron microscope (HRTEM). The CeO 2-y- powder consists of polycrystalline rods having a length of 100 to 800 nm, the average length being about 200 nm and only a few rods having a length of more than 500 nm. The diameter of the rods is 5 to 20 nm. The electron diffraction-caused stripes in the HRTEM images can be assigned to lattice planes of the cubic phase of CeO 2. The surface of the rods comprises regions or crystal facets with crystal lattice orientations of the type

[110] ,

[110] and

[111] .Comparative Example 2: Antibacterial Membrane CoatingsA solution consisting of 32 g of polyethersulfone (Ultrason® E6020P, BASF SE), 12 g of polyvinylpyrrolidone (Luvitec® K30, BASF, SE) and 1.6 g of nanoscale CeO 2-y- rods (having an average length of about 100 nm) in 156 g of dimethylacetamide (purity 99%, Sigma-Aldrich) is heated to 60° C. and degassed. The degassed solution is applied to a Teflon disk at a temperature of 25° C. and a relative humidity of 50% and spread out by means of a rubber doctor to form an approximately 200 μm thick film. The Teflon disk coated with the solution is immersed in a precipitation bath or a precipitation mixture of 7 parts by weight of water and 3 parts by weight of isopropanol. The membrane produced by precipitation is kept for two hours in an aqueous NaOCl solution (0.2% by weight) tempered to 60° C. Thereafter, the membrane is washed with deionized water and stored in deionized water.To demonstrate the antibacterial activity of CeO 2-y three stainless steel sample supports each having an area of 2×2 cm 2 were coated beforehand with a polymer matrix mixture, the mixture containing no CeO 2-y for the first sample. In contrast, nanoscale CeO 2-y- particles with a weight fraction of 5% by weight and, respectively, 10.0% by weight were added to the mixtures for the second and third samples. The samples thus prepared were stored for 96 hours in a bacterial suspension of 200 μL of chemically competent Shot® TOP10 Escherichia colicells (ThermoFisch Scientific) in 15 mL of LB medium at a temperature of 37° C. Initially and at regular intervals of 3 hours, 150 μL of aqueous KBr solution (100 mM) and H 2 O 2- solution (10 mM) were added to the bacterial suspension, respectively. After the end of the 96 hours, the samples were taken from the bacterial suspension, washed in LB medium, stained with 4',6-diamidino-2-phenylindole (1 μg / mL DAPI in a sterile mixture of water and glycerol in a volume ratio of 1:1) and imaged by means of a fluorescence microscope (Olympus AHBT3 with AH3-RFC addition for incident light fluorescence). The images of the three samples with a CeO 2-y- content of 0% by weight, 5% by weight and 10.0% by weight recorded with the fluorescence microscope are shown in FIGS. 4 a, 4 band 4 c, respectively, wherein white spots correspond to areas with severe E. coli attack. It is immediately evident from FIGS. 4 aand 4 bthat the polymer coating with a CeO 2-y- content of 5 wt % already has a high antibacterial activity.Comparative Example 3: Antifouling marine paintIn order to examine the antifouling effect of CeO 2-y in marine operation, coatings were produced on the basis of two conventional antifouling marine paint formulations and were exposed to weathering in seawater over a period of 51 days (Ophoven-Kinrooi, Marina De Spaanjerd, Maas, Belgium). The sample substrates or coating supports used were plates made of stainless steel having an area of 2×2 cm 2. in each case. Several steel plaques were uncoated prior to weathering and served as a reference. One of the antifouling marine paint formulations used in the experiments (Toplac International® AkzoNobel) is based on silicone alkyd. Ship lacquers based on silicone or polydimethylsiloxane are hydrophobic, which reduces the adhesion of bacteria and algae. The second antifouling marine paint formulation used in the experiments is referred to in specialist circles as "abrasive" and comprises resins with soluble and / or swelling constituents, in particular wood rosin of natural origin, and zinc oxide and / or copper oxide as essential components. Abrasive marine paints are continuously eroded in seawater and in inner waters due to hydrolysis and the shear force exerted by the water flow, the zinc or copper oxide contained therein being exposed and finally rinsed out. Zinc and copper oxide are highly toxic to many marine organisms and thus counteract infestation with algae and mussels. On the other hand, the zinc and copper oxide released from abrasive ship lacquers causes massive environmental damage in the environment of heavily frequented ship routes. In the tests carried out within the scope of the present invention, in order to eliminate the antibacterial activity of the zinc oxide and / or copper oxide present in commercial marine paints, a specially produced, purely polymeric abrasive formulation based on polyether resins was used.Figures 5 show photographs of the surfaces of six samples after 51 days of weathering in seawater, dark areas indicating severe infestation with algae and / or other marine organisms. In contrast, light areas correspond to areas with little infestation. Figures 5a and 5b show uncoated stainless steel sample supports. FIGS. 5 cand 5 d show samples with a coating of the above-described ship coatings (5 cToplac International® 5 dabrasive ship coating). The coatings of the samples shown in Figures 5c and 5d are purely polymeric and do not contain a metal oxide. The coatings shown in FIGS. 5 eand 5 f, on the other hand, contain 2% by weight of nanoscale CeO 2-y- particles, based on the total weight of the coatings. The coating of the samples shown in FIGS. 5 cand 5 econsists of toplac International® based on silicone alkyd, or of toplac International® with 2% by weight nanoscale CeO 2-y- particles, based on the total weight of the coating. From the samples shown in FIGS. 5 cand 5 e, the antifouling effect of the CeO 2-y- particles is readily apparent. The same applies to the samples shown in FIGS. 5 dand 5 f, the coating of which consists of abrasive ship paint without metal oxide and abrasive ship paint with 2% by weight nanoscale CeO 2-y- particles.The relative proportion of the surface of the samples covered with algae and other organisms was determined by means of the image analysis software image) (Fiji) on the basis of the number of image pixels whose gray value is below a predetermined gray value threshold, based on the total number of all image pixels. On the basis of the gray value histogram of each of the images 5 ato 5 f, the gray value threshold has been established in such a way that, in the case of a variation of the gray value threshold by ±10% gray values, the ratio of the image pixels is practically constant. The following values were found for the algae infestation or area fraction determined by means of image analysis: 5a:99.5%; 5b:98.9%; 5c:94.9%; 5d:85.5%; 5e:50.5%; 5f:45.9%.Comparative Example 4: Catalytic activity of Ce1-xLaxO2-yAnalogously to the synthesis process described in Example 1, nanoscale rods were produced from Ce 1-x La x O 2-y by addition of cerium(III) nitrate hexahydrate (Ce(NO 3)3 · 6 H 2 O) and lanthanum(III) nitrate hexahydrate (La(NO 3)3 · 6 H 2 O) in various mixing ratios to an aqueous solution of NaOH.The catalytic activity of the nanoparticles obtained was determined spectrophotometrically by means of a phenol red assay. The conversion of phenol red (phenolsulfonephthalein) to bromophenol blue (3,3',5,5'-tetrabromophenolsulfonephthalein) was measured by the emission of bromophenol at 590 nm (ε(590 nm)∼72.2 mM -1 cm -1). For the measurements, a Cary 5G UV-Vis-NIR spectrophotometer (Varian Inc., Palo Alto, CA, USA) and a Cary 300 spectrophotometer (Agilent) with magnetic stirrer and an integration sphere arranged in the beam path after the sample cuvette were used. The catalytic conversion of phenol red to bromophenol blue is shown below. A weighed amount of Ce 1-x La x O 2-y- nanoparticles was added to an assay solution of MilliQ water, phenol red, potassium bromide (KBr, Cat. No. P0838 BioTra, >99.0%, Sigma-Aldrich) or ammonium bromide (NH 4 Br, Cat. No. AB203189, Puratronic® ; 99.999%) and hydrogen peroxide (H 2 O 2, Cat. No. 8070.1, ROTIPURAN® Carl Roth GmbH & Co. KG Karlsruhe, Germany). The concentration of the components of the assay solution was:Phenol red10 or 50 μMKBr or NH 4 Br25 mMH 2 O 2300 μMThe concentration of H 2 O 2 was verified from the absorbance of the assay solution at a wavelength of 240 nm, and a molar absorption coefficient of 43.6 M -1 · cm -1 was set for the calculation. The amount of Ce 1-x La x O 2-y- nanoparticles added was varied in the range of 0 to 0.05 mg / ml. The Ce 1-x La x O 2-y- nanoparticles were continuously added to the assay solution at a temperature of 24±2° C. over a period of 5 min.As a control, measurements were made on assays that (i) contained no KBr, NH 4 Br or H 2 O 2 and (ii) contained KBr or NH 4 Br and H 2 O 2 in the concentration ranges given above and that were commercially available quasi-stoichiometric ceria (CeO 2, Cat. No. 221899, Sigma Aldrich, Steinheim, Germany) was added in an amount of 0.025 mg / ml. No activity was observed in the control measurement (i). In the control measurement (ii), a low activity was measured, since the quasi-stoichiometric cerium oxide has a comparatively low number of defects.Figure 6 shows the result of the assays, i.e. the catalytic bromination activity of noninventive Ce 1-x La x O 2-y- nanoparticles as a function of the substitution number x. At a substitution number of x=0.2, the catalytic activity assumes a maximum value.Measuring MethodIn the context of the present invention, the term "equivalent diameter" of a nanoscale particle denotes the diameter of a sphere which has the same volume as the nanoscale particle. The dimensions and volumes of nanoscale particles of Ce 1-x M x O 2-y are determined according to the invention by means of a scanning electron microscope or a transmission electron microscope and image analysis software, such as Image) (http: / / imagej.nih.gov / ij). In this case, using digitized scanning electron microscopic images, at least 100, preferably at least 1000, nanoscale particles are digitally measured with the aid of the image analysis software. Due to the high lateral resolution of transmission electron microscopes and scanning electron microscopes of the prior art, which, depending on the setting of the electron optics and the beam parameters, is in the range of a few angstroms up to 10 nm, the equivalent diameter of the nanoparticles can be determined with high reliability.To determine the equivalent diameters of nanoscale particles of Ce 1-x M x O 2-y the powder to be analyzed is suspended in demineralized water at a concentration of about 0.5 mg / ml by means of ultrasound and a drop of this suspension, i.e. about 40 μl, is dropped onto a planar, preferably circular graphitized copper lattice (CF300-Cu, Electron Microscopy Sciences, Hatfield (PA), USA) having an area of about 9.3 mm 2. The grid coated with the suspension is stored in a horizontal position under clean room conditions for about 30 min until the water has evaporated and is transferred into the scanning electron microscope. The sample preparation described above ensures that adjacent nanoparticles on the grid are spaced apart sufficiently far from one another and are imaged as separate objects in the scanning electron microscope.Software-based methods for evaluating digital images of nanoparticles recorded by means of a transmission electron microscope or scanning electron microscope are known in the prior art and comprise the following steps:algorithm creation of a gray value histogram;interactive determination of a suitable threshold value in the gray value histogram in order to classify each image pixel as belonging to the background or to a nanoparticle, depending on whether the gray value of the image pixel is above or below the threshold value;algorithmally binarizing the image, i.e. converting the gray-scale image into a black-and-white image;optionally algorithm binary dilation and erosion (closing) to close gaps or binary erosion and dilation (opening) to eliminate artifacts caused by image noise, such as pseudo particles with a size of less than 5 nm; andAlgorithm identification of contiguous areas from adjacent (black) image pixels, which are assigned to nanoscale particles, and determination of the size or the number of image pixels contained in the respective area.Software algorithms of the type described above are typically part of the scope of modern transmission and scanning electron microscopes or are available as an option. Alternatively, generic image analysis programs such as Image) (http: / / imagej.nih.gov / ij) may be used.The ratio of Ce(III) / Ce(IV) of the substance used according to the invention having the chemical composition Ce 1-x M x O 2-y is determined by means of X-ray photoelectron spectroscopy (XPS: X-ray photoelectron spectroscopy / ESCA: electron spectroscopy for chemical analysis). Using the XPS (for example: ESCA 5600 (XPS) (Physical Electronics GmbH)) with monochromatic X-ray radiation (for example: Al-Kα radiation (1486 eV at 250.0 W)), the Ce(III) / Ce(IV) ratio can be determined from the relative area fractions of the unfolded signals according to the following formula at the surface. For the spin-orbit coupling state 3d (5 / 2) the ratio for Ce 3+ to.As sample carriers, glass carriers (standard object carriers, Carl-Roth) are cut into glass carriers 1.5 cm×1.5 cm in size and coated with a gold layer of about 15 nm by means of a coating system (Med 020, BAL-TEC) using a quartz microbalance (QSG 070, Bal-TEC).Prior to the XPS measurement, the samples are heated to about 900-1000° C. in order to remove any water of crystallization present. The substance used according to the invention having the chemical composition Ce 1-x M x O 2-y is present as a particulate powder which is pressed into a pellet with a smooth surface before the XPS measurement. In order to eliminate any influence of the sample morphology during the XPS measurement, an XPS spectrum is recorded and evaluated at a plurality of sample positions which differ from one another and the derived element ratios are averaged.The relative proportions of the components of the substance used according to the invention, having the chemical composition Ce 1-x M x O 2-y( here based on proportions Ce and M in the substance used), can be determined by energy dispersive X-ray spectroscopy (EDX). Using a scanning electron microscope (SEM) (for example: Nova NanoSEM, FEI) with a corresponding EDX module (for example: EDAX Apollo 10 SDD, AMETEK), the components are assigned to the energies and the relative proportion is accessible by quantification of the component signals.Prior to the EDX measurement, the substance used according to the invention having the chemical composition Ce 1-x M x O 2-y is suspended and / or dispersed in aqueous and / or organic solvents. The suspension and / or dispersion is applied to a silicon wafer (dimension about 7.5 mm×7.5 mm) and this is fixed on a carbon guide tab (for example: PLANO guide tabs 12 mm Ø). The solvent is evaporated (drying at normal conditions and / or at elevated temperatures (20° C.<temperature<100° C.) and / or under vacuum). If necessary, the sample is coated with a gold or silver layer 5 nm to 15 nm thick using a coating system (for example: Med 020 (BAL TEC) with quartz microbalance (QSG 070, BAL TEC)).

Claims

Shaped body which is formed as a textile nonwoven, textile knitted fabric, textile fiber, filtration membrane, film, floor covering, furniture component, component of a ship, container for fluids, line element for fluids or granules and - the surface of which is partially or completely coated with a biocidal coating consisting of a carrier material of one or more polymers, one or more additives and 0.01 to 10% by weight of a substance having the chemical composition Ce 1-x M x O 2-y, based on the total weight of the biocidal coating, or - of one or more polymers, one or more additives and 10 -9 to 50% by weight of a substance having the chemical composition Ce 1-x M x O 2-y based on the total weight of the shaped body; wherein - M is selected from Ca, Ti, V, Fe, Sr, Zr and Nb; - x is a real number with 0≤x≤0.5; - y is a real number where 0<y≤0.4; characterized in that - the substance having the chemical composition Ce 1-x M x O 2-y consists of rod-shaped particles having a length of 50 to 800 nm, a cross-sectional area of 20 to 40 nm 2 and an equivalent diameter of 12 to 40 nm; and - a surface of the shaped body contains particles having the chemical composition Ce 1-x M x O 2-y wherein the particles are connected to the shaped body in a force-fitting manner.Shaped body according to Claim 1, characterized in that some of the particles protrude from the biocidal coating or the surface of the shaped body.Use of a substance having the chemical composition Ce 1-x M x O 2-y for the production of biocidal shaped bodies according to Claim 1, wherein - the shaped body is designed as a textile fleece, textile knitted fabric, textile fiber, filtration membrane, film, floor covering, furniture component, component of a ship, container for fluids, line element for fluids or granulate; - M is selected from Ca, Ti, V, Fe, Sr, Zr and Nb; - x is a real number with 0 ≤ x ≤ 0.5; y is a real number where 0<y≤0.4; characterized in that the substance having the chemical composition Ce 1-x M x O 2-y consists of rod-shaped particles having a length of 50 to 800 nm, a cross-sectional area of 20 to 40 nm 2 and an equivalent diameter of 12 to 40 nm, and some of the particles project from the biocidal coating or from the surface of the shaped body.Use of a shaped body comprising a fabric having the chemical composition Ce 1-x M x O 2-y and formed as a textile fleece, textile knitted fabric, textile fiber, filtration membrane, film, component of a ship, container for fluids, conduit element for fluids or granules according to claim 1 in a medium containing H 2 O 2 and halogen anions such as I -, Br - and Cl - ; wherein - M is selected from Ca, Ti, V, Fe, Sr, Zr and Nb; x is a real number where 0≤x≤0.5; y is a real number where 0<y≤0.4; characterized in that the substance having the chemical composition Ce 1-x M x O 2-y consists of rod-shaped particles having a length of 50 to 800 nm, a cross-sectional area of 20 to 40 nm 2 and an equivalent diameter of 12 to 40 nm, and some of the particles protrude from the biocidal coating or the surface of the shaped body.

Images