WO2018078171A1

WO2018078171A1 - Biocidal composition containing cerium oxides and products produced therewith

Info

Publication number: WO2018078171A1
Application number: PCT/EP2017/077827
Authority: WO
Inventors: Karoline HERGET; Wolfgang Tremel
Original assignee: Johannes Gutenberg-Universität Mainz
Priority date: 2016-10-31
Filing date: 2017-10-30
Publication date: 2018-05-03
Also published as: DE102016120736A1

Abstract

The invention relates to a moulded body comprising a material having the chemical composition Ce_1-xM_xO_2-y as biocide.

Description

MANUFACTURED PRODUCTS

The invention relates to biocidal compositions, biocidal moldings and moldings with a biocidal coating.

In medicine and numerous technical fields, it is necessary or expedient to prevent or inhibit the bacterial infestation and plant growth, in particular algae growth on the surface of consumer goods, such as furniture, floor panels, ship hulls, filtration membranes and the like. For this purpose, it is customary to equip the respective commodity or its surface with a bactericidal substance, in particular with antibiotics or metallic particles of silver, copper or zinc oxide. Furthermore, it is known from WO 1995/027009 to use haloperoxidases, such as vanadium haloperoxidase as an additive in enamel paints. Haloperoxidases are enzymes that catalyze the oxidation of halides to hypohalogenic acid according to the reaction equation

H ₂ O ₂ + X ^" + H ⁺ - ^> HOX + H ₂ O where hydrogen peroxide (H ₂ O ₂ ) acts as an oxidant and X ^{~ is} a halide anion such as Γ, Br ^" or Cl ^" .

US 7,063,970 Bl 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 a biocide and discloses a biocidal composition comprising particles of vanadium pentoxide and methods for preventing biofouling and for biocidal finishing of substrates.

The biocidal coatings and moldings known in the prior art have one or more of the following disadvantages: low resistance to erosion and efflux;

- low efficacy over longer periods of time;

- toxicity, biological incompatibility and environmental damage;

- elaborate production; - high costs.

The invention has the object to overcome the above disadvantages and to prevent or reduce microbial infestation and plant growth, in particular algae growth on surfaces of moldings and consumer goods. This object is achieved by biocidal compositions, molded articles and consumer goods produced from the biocidal compositions or coated with the biocidal compositions.

In a first embodiment, the invention relates to a molded body whose surface is partly or completely with particles having the chemical composition Cei_ _x M _x 0 ₂ - is equipped _y, wherein - M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

Advantageous embodiments of the biocidal shaped body are characterized in that

- x 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 particles with the chemical composition Cei_ _x M _x 0 ₂ - _{y are} positively connected to the molding;

- A part of the particles with the chemical composition Cei_ _x M _x 0 ₂ - _y protrudes from the surface of the molding;

- The particles with the chemical composition Cei_ _x M _x 0 ₂ - _y protrude from the surface of the molding; - Part of the particles with the chemical composition Cei_ _x M _x 0 ₂ - _y protrudes partially from the surface of the molding;

- the particles with the chemical composition Cei_ _x M _x 0 ₂ - _y partly from the

Protrude surface of the molding; - The particles with the chemical composition Cei_ _x M _x 0 ₂ - _{y are} polycrystalline;

- The particles with the chemical composition Cei_ _x M _x 0 ₂ - _y in one or more

Spatial directions have a dimension of <500 nm;

- The particles with the chemical composition Cei_ _x M _x 0 ₂ - _y an equivalent

Have diameters of 2 to 5000 nm; the particles having the chemical composition Cei_ _x M _x 0 ₂ - _y an equivalent

Diameter of 2 to 15 nm, 10 to 20 nm, 15 to 25 nm, 20 to 30 nm, 25 to 35 nm, 30 to 40 nm, 35 to 45 nm, 40 to 50 nm, 45 to 55 nm, 50 to 60 nm, 55 to 65 nm, 60 to 70 nm, 65 to 75 nm, 70 to 80 nm, 75 to 85 nm, 80 to 90 nm, 85 to 95 nm, 90 to 100 nm, 100 to 200 nm, 150 to 250 nm, 200 to 300 nm, 250 to 350 nm, 300 to 400 nm, 350 to 450 nm, 400 to 500 nm, 450 to 550 nm or 500 to 600 nm;

- The particles with the chemical composition Cei_ _x M _x 0 ₂ - _{y are} rod-shaped and have a length of 50 to 800 nm and a cross-sectional area of 20 to 40 nm ² ;

- The particles with the chemical composition Cei_ _x M _x 0 ₂ - _{y are} rod-shaped and have 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;

- The particles having the chemical composition Cei_ _x M _x 0 ₂ - _y are dispersed on the surface of the molding such that their average area coverage 0.001 to 35%, 0.001 to 30%, 0.001 to 25%, 0.001 to 20%, 0.001 to 15%, 0.001 to 10%, 0.001 to 5% or 0.001 to 1%; - The molded body is a textile structure;

- The molded body is a textile nonwoven fabric;

- The molded body is a textile knitted fabric; - The molding is a textile fiber;

- The molding is a filtration membrane;

- The molding is a film;

- The molding is a floor covering;

- The molded body is a furniture component, such as a table top or a cabinet door;

- The molding a component of a ship, such as the wall of a

Hull or a propeller is;

- The molding is a container for fluids, such as a water tank;

- The molding is a conduit element for fluids, such as a water pipe; and or

- The molding is a granule.

In a further embodiment, the invention relates to a coating composition consisting of a carrier material and a substance having the chemical composition

Cei_ _x M _x 02-y, where

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

Advantageous embodiments of the coating composition are characterized

marked that

- x 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 with the chemical composition Cei_ _x M _x 0 ₂ - _y

0.01 to 50 wt .-%, based on the total weight of the coating

Composition; the proportion of the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y

0.01 to 10 wt .-%, based on the total weight of the coating composition; the substance of chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles which are partly or wholly crystalline;

- the substance of chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles which are polycrystalline;

- The substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles having a dimension of <500 nm in one or more spatial directions; - the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles having an equivalent diameter of 2 to 5000 nm;

- the substance with the chemical composition Cei_ _x M _x O ₂ _ _y consists of particles having an equivalent diameter of 2 to 15 nm, 10 to 20 nm, 15 to 25 nm, 20 to 30 nm, 25 to 35 nm, 30 to 40 nm, 35 to 45 nm, 40 to 50 nm, 45 to 55 nm, 50 to 60 nm, 55 to 65 nm, 60 to 70 nm, 65 to 75 nm, 70 to 80 nm, 75 to 85 nm, 80 up to 90 nm, 85 to 95 nm,

90 to 100 nm, 100 to 200 nm, 150 to 250 nm, 200 to 300 nm, 250 to 350 nm, 300 to 400 nm, 350 to 450 nm, 400 to 500 nm, 450 to 550 nm or 500 to 600 nm ;

- The substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of stabfömigen particles with a length of 50 to 800 nm and a cross-sectional area of 20 to 40 nm ² ; - The substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of stabfömigen particles with 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 or - The particles with the chemical composition Cei_ _x M _x 0 ₂ - _y are dispersed in the coating composition such that their average area coverage 0.001 to 35%, 0.001 to 30%, 0.001 to 25%, 0.001 to 20%, 0.001 to 15%, 0.001 to 10%, 0.001 to 5% or 0.001 to 1%; - The carrier material of one or more polymers and one or more

Additives consists.

In a further embodiment, the invention relates to a molded body whose surface is coated partially or completely with a biocidal coating, consisting of a carrier material and a material having the chemical composition Cei_ _x M _x 0 ₂ - _y, wherein - M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

Advantageous embodiments of the biocidal shaped body are characterized in that

- x 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 with the chemical composition Cei_ _x M _x 0 ₂ - _y

0.01 to 50% by weight, based on the total weight of the biocidal coating;

- The proportion of the substance with the chemical composition Cei_ _x M _x 0 ₂ - _y

From 0.01% to 10% by weight, based on the total weight of the biocidal coating;

- the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles which are partly or wholly crystalline; - the substance with the chemical composition Cei_ _x M _x 02- _y consists of particles which are polycrystalline;

- the substance with the chemical composition Cei_ _x M _x 02- _y consists of particles having a dimension of <500 nm in one or more spatial directions; - the substance with the chemical composition Cei_ _x M _x 02- _y consists of particles having an equivalent diameter of 2 to 5000 nm;

- the substance with the chemical composition Cei_ _x M _x 02_ _y consists of particles having an equivalent diameter of 2 to 15 nm, 10 to 20 nm, 15 to 25 nm, 20 to 30 nm, 25 to 35 nm, 30 to 40 nm, 35 to 45 nm, 40 to 50 nm, 45 to 55 nm, 50 to 60 nm, 55 to 65 nm, 60 to 70 nm, 65 to 75 nm, 70 to 80 nm, 75 to 85 nm, 80 to 90 nm, 85 to 95 nm,

- The substance with the chemical composition Cei_ _x M _x 02- _y consists of stabfömigen particles with a length of 50 to 800 nm and a cross-sectional area of 20 to 40 nm ² ; - the substance with the chemical composition Cei_ _x M _x 02- _y consists of rod-shaped particles with 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;

- the particles with the chemical composition Cei_ _x M _x 02- _y are dispersed in the coating such that their average surface coverage of from 0.001 to 35%, from 0.001 to 30%, 0.001 to 25%, from 0.001 to 20%, 0.001 to 15%, 0.001 to 10%, 0.001 to 5% or 0.001 to 1%;

- The carrier material of the biocidal coating consists of one or more polymers and one or more additives;

- The carrier material of the biocidal coating consists of one or more polymers based on polydimethylsiloxane and one or more additives;

the carrier material of the biocidal coating contains one or more hydrolysable polymers with a polymeric backbone and functional groups, the polymeric backbone consisting of monomers selected from acryl, methacryl, acrylonitrile, acrylamide, methacrylamide, vinyl ester, vinyl ether, vinyl amide, vinyl ketone, Styrene, olefins, Monomers having reactive silicon-containing groups, halogen-containing monomers and mixtures thereof; the carrier material of the biocidal coating contains one or more hydrolyzable polymers with a polymeric backbone and functional groups, wherein the functional groups are selected from amines, amides, cyclic amides, acid groups and blocked acid groups; the carrier material of the biocidal coating contains one or more hydrolysable polymers with a polymeric backbone and functional groups, wherein the functional groups are selected from amines, amides, cyclic amides, acid groups and blocked acid groups, wherein the acid groups are blocked by means of quaternary ammonium groups; the carrier material of the biocidal coating one or more resins natural

Origin, such as tree resin; the carrier 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 (PBIL), polyacrylonitrile (PAN), polyacrylonitrile-polyvinyl chloride copolymer (PAN-PVC), polyacrylonitrile-methallylsulfonate copolymer, poly ( dimethylphenylene oxide) (PPO), polycarbonate, polyester, polytetrafluoroethylene (PTFE), poly (vinylidene fluoride) (PVDF), polypropylene (PP), polyelectrolyte complexes, poly (methylmethacrylate) PMMA, polydimethylsiloxane (PDMS), polyamideimides, aromatic polyamideimides, aliphatic polyamide-imides, polymers with phosphate acid and / or carboxylic acid groups; the shaped body is a textile structure; the shaped body is a textile fleece; the shaped body is a textile knitted fabric; the shaped body is a textile fiber; the shaped body is a filtration membrane; the shaped body is a film; the shaped body is a floor covering; the molded article is a furniture component such as a tabletop or a cabinet door; the shaped body is a component of a ship, such as the wall of a ship's hull or a propeller; the shaped body is a container for fluids, such as a water tank; the molding is a conduit member for fluids such as a water pipe; and / or the shaped body is a granulate.

In a further embodiment, the invention relates to a molded body composed of a base material and a material having the chemical composition Cei_ _x M _x 0 ₂ - is _y, wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

Advantageous embodiments of the shaped body are characterized in that - x 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 with the chemical composition Cei_ _x M _x 0 ₂ - _y

10 ^{~ 9} to 50 wt .-%, based on the total weight of the molding;

10 ^{"is 9} to 10% by weight, based on the total weight of the shaped body, - the proportion of the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y

0.01 to 10 wt .-%, based on the total weight of the molding;

- the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles which are partly or wholly crystalline;

- the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles which are polycrystalline;

- The shaped body particles having the chemical composition Cei_ _x M _x 0 ₂ - _y , wherein the particles in one or more spatial directions have a dimension of <500 nm;

- the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles having an equivalent diameter of 2 to 5000 nm;

- the substance with the chemical composition Cei_ _x M _x O ₂ _ _y consists of particles having an equivalent diameter of 2 to 15 nm, 10 to 20 nm, 15 to 25 nm, 20 to 30 nm, 25 to 35 nm, 30 to 40 nm, 35 to 45 nm, 40 to 50 nm, 45 to 55 nm, 50 to 60 nm, 55 to 65 nm, 60 to 70 nm, 65 to 75 nm, 70 to 80 nm, 75 to 85 nm, 80 to 90 nm, 85 to 95 nm, 90 to 100 nm, 100 to 200 nm, 150 to 250 nm, 200 to 300 nm, 250 to 350 nm, 300 to

400 nm, 350 to 450 nm, 400 to 500 nm, 450 to 550 nm or 500 to 600 nm;

- the substance with the chemical composition Cei_ _x M _x 0 ₂ - _y consists of rod-shaped particles having a length of 50 to 800 nm and a cross-sectional area of 20 to 40 nm ^2; - the substance with the chemical composition Cei_ _x M _x 0 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;

- Particles having the chemical composition Cei_ _x M _x 0 ₂ - _y are dispersed in the molding such that their average area coverage 0.001 to 35%, 0.001 to 30%, 0.001 to 25%, 0.001 to 20%, 0.001 to 15%, 0.001 to 10%, 0.001 to 5% or 0.001 to 1%;

- A surface of the shaped body particles with the chemical composition

Cei_ _x M _x 0 ₂ - _y contains, wherein the particles are non-positively connected to the molding; - A surface of the shaped body particles with the chemical composition

Cei_ _x M _x 0 ₂ - _y contains, wherein the particles are non-positively connected to the molding and a part of the particles protrudes from the surface of the molding;

- The base material consists of one or more polymers and one or more additives; the 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), polybenzimidazole ion (PBIL), polyacrylonitrile (P AN), polyacrylonitrile-polyvinyl chloride

Copolymer (PAN-PVC), polyacrylonitrile-methallylsulfonate copolymer, poly (dimethyl-phenylene oxide) (PPO), polycarbonate, polyester, polytetrafluoroethylene (PTFE), poly (vinylidene fluoride) (PVDF), polypropylene (PP), polyelectrolyte complexes, poly (methyl methacrylate) PMMA, polydimethylsiloxane (PDMS), polyamide-imides, aromatic polyamide-imides, aliphatic polyamide-imides, polymers with phosphate-acid and / or carboxylic acid-

Groups;

- The base material consists of one or more ceramic materials and one or more additives;

- The molded body is a textile structure; - The molded body is a textile nonwoven fabric;

- The molded body is a textile knitted fabric;

- The molding is a textile fiber;

- The molding is a filtration membrane; - The molding is a film;

- The molding is a floor covering;

- The molded body is a furniture component, such as a table top or a cabinet door; - The molding is part of a ship, such as the wall of a ship's hull or a propeller;

- The molding is a container for fluids, such as a water tank;

- The molding is a conduit element for fluids, such as a water pipe; and / or - the shaped body is a granulate.

In another embodiment, the invention relates to a mortar or a material based on silicone polymer, a substance having a chemical composition Cei_ _x M _x 0 ₂ - contains _y, wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd; - x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

Advantageous embodiments of the mortar or the material based on silicone polymer are characterized in that

- x 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;

0.001 to 10% by weight, based on the total weight of the mortar or the silicone;

- the substance with the chemical composition Cei_ _x M _x 0 ₂ - _y consists of particles which

partially or completely crystalline; - the substance with the chemical composition Cei_ _x M _x 0 ₂ - _y consists of particles which

are polycrystalline;

- The substance with the chemical composition Cei_ _x M _x 0 ₂ - _y consists of particles having a dimension of <500 nm in one or more spatial directions;

- the substance of chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles containing

have an equivalent diameter of 2 to 5000 nm;

an equivalent diameter of 2 to 15 nm, 10 to 20 nm, 15 to 25 nm, 20 to 30 nm, 25 to 35 nm, 30 to 40 nm, 35 to 45 nm, 40 to 50 nm, 45 to 55 nm, 50 to 60 nm, 55 to 65 nm, 60 to 70 nm, 65 to 75 nm, 70 to 80 nm, 75 to 85 nm, 80 to 90 nm, 85 to 95 nm, 90 to 100 nm, 100 to 200 nm, 150 up to 250 nm, 200 to 300 nm, 250 to 350 nm, 300 to

400 nm, 350 to 450 nm, 400 to 500 nm, 450 to 550 nm or 500 to 600 nm;

- The substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of stab-colored particles with a length of 50 to 800 nm and a cross-sectional area of 20 to 40 nm ² ;

- The substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of stab-colored particles with 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;

- Particles with the chemical composition Cei_ _x M _x 0 ₂ _ _y in the mortar or

Material based on silicone polymer are dispersed in such a way that their average

Area coverage is 0.001 to 35%, 0.001 to 30%, 0.001 to 25%, 0.001 to 20%, 0.001 to 15%, 0.001 to 10%, 0.001 to 5% or 0.001 to 1%; and or

the silicone polymer based material is an RTV silicone based material

Vulcanizable silicone-based one-component material or a vulcanizable

Silicone-based two-component material is. Another object of the present invention is to provide microbial attack

To prevent or reduce surfaces of moldings and household goods.

This problem is solved by the use of a substance with the chemical

Composition Cei_ _x M _x 0 ₂ - _y for the production of moldings, moldings, mortars or materials based on silicone polymer, wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

Advantageous uses of the substance with the chemical composition Cei_ _x M _x 0 ₂ - _y for the production of Foirnköi em, Fonnkörperbeschichtungen, mortars or materials based on silicone polymer are characterized in that

- x 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 with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles which

partially or completely crystalline; - the substance with the chemical composition Cei_ _x M _x 0 ₂ - _y consists of particles, which are polycrystalline;

- The substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles having a dimension of <500 nm in one or more spatial directions;

- the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y consists of particles having an equivalent diameter of 2 to 5000 nm; - the substance with the chemical composition Cei_ _x M _x 02- _y consists of particles having an equivalent diameter of 2 to 15 nm, 10 to 20 nm, 15 to 25 nm, 20 to 30 nm, 25 to 35 nm, 30 to 40 nm, 35 to 45 nm, 40 to 50 nm, 45 to 55 nm, 50 to 60 nm, 55 to 65 nm, 60 to 70 nm, 65 to 75 nm, 70 to 80 nm, 75 to 85 nm, 80 to 90 nm, 85 to 95 nm, 90 to 100 nm, 100 to 200 nm, 150 to 250 nm, 200 to 300 nm, 250 to 350 nm, 300 to

400 nm, 350 to 450 nm, 400 to 500 nm, 450 to 550 nm or 500 to 600 nm;

- the substance with the chemical composition Cei_ _x M _x 02- _y consists of rod-shaped particles with a length of 50 to 800 nm and a cross-sectional area of 20 to 40 nm ² ;

- the substance with the chemical composition Cei_ _x M _x 02- _y consists of rod-shaped particles with 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 or

- Particles having the chemical composition Cei_ _x M _x 02- _y in the molding, the

The body coating, the mortar or the silicone polymer-based material are dispersed so that their average area coverage 0.001 to 35%, 0.001 to 30%, 0.001 to 25%, 0.001 to 20%, 0.001 to 15%, 0.001 to 10%, 0.001 to 5% or 0.001 to 1%.

Furthermore, the object of the invention is to provide a process for the production of biocidal moldings. This object is achieved by a method comprising the steps

- Providing a shaped body;

Providing a coating composition comprising a chemical

Composition Cei_ _x M _x 02_ _y in the form of nanoscale particles contains, wherein

- y is a real number with 0 <y <0.4;

- coating the shaped body with the coating composition; and

- Fixing the coating composition on the molding.

Preferably, the coating composition is fixed on the molding by - Dry;

- melting;

- thermal crosslinking; or

- crosslinking by means of UV radiation.

Another useful method for producing a biocidal shaped article comprises the steps

(a) providing a shaped body;

(B) providing a substance having the chemical composition Cei_ _x M _x 0 ₂ - _y in the form of a nanoscale particulate powder, wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x 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 nanoscale particulate powder by means of

Powder coating or spraying; and

(D) fixing the nanoscale particulate powder on the molding.

Preferably, a surface of the shaped body is coated with an adhesive layer, before the shaped body is coated with the nanoscale particulate powder in step (c).

Suitably, in step (d) the nanoscale particulate powder is fixed on the molding by

- Dry;

- melting;

- thermal crosslinking; or

- crosslinking by means of UV radiation.

Another method of making a biocidal shaped article comprises the steps

(e) providing a base material; (F) providing a substance having the chemical composition Cei_ _x M _x 0 ₂ - _y in the form of a nanoscale particulate powder, wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd; 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 chemical composition substance

(h) molding a molded article from the mixture obtained in step (g).

In an expedient 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 materials and one or more additives.

In a further expedient embodiment of the method, the base material provided in step (e) consists of a mortar.

In a further expedient embodiment of the method, the base material provided in step (e) consists of a material based on silicone polymers.

Preferably, the mixture obtained in step (g) is plasticized prior to molding in step (h) by means of a gelling aggregate or extruder. Preferably, the molding in step (h) is carried out by means of

- Extrusion through a slot die;

- Extrusion through a profile nozzle;

- injection molding;

- melt spinning; - solution spinning; and or

- Phase inversion in a precipitation bath. In an expedient embodiment of the method, a shaped body produced in step (h) is sintered.

In the present invention, the term "substance having the chemical composition Cei_ _x M _x 0 ₂ - _{y" is} a preferably crystalline or polycrystalline compound in which M is calcium (Ca), titanium (Ti), vanadium (V), iron ( Fe), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), lanthanum (La), praseodymium (Pr), indium (In), bismuth (Bi), terbium (Tb), europium ( Eu) or neodymium (Nd) and the atoms Cer (Ce), M and oxygen (O) in the ratio (1-x): x: (2-y) are present with 0 <x <0.5 and 0 <y <0.4. The invention is based on the finding that a substance with the chemical composition Cei_ _x M _x O ₂ -y the oxidation of halide anions X ^~ , such as Γ, Br ^~ and Cl ^~ to

Hypohalogenic acid HOX catalyzes, according to the reaction equation:

H ₂ 0 ₂ + X ^" + H ⁺ -» ^■ HOX + H ₂ 0

Accordingly, the produced according to the invention, a material having the chemical composition Cei_ _x M _x 0 ₂ - _y broad form body and commodities preferably used in a medium containing hydrogen peroxide (H ₂ O _2), or organic peroxides and / or halide anions, such as Γ, Br ^{contains ~} and Cl ^~ .

The inventors have also found that for the catalytic activity of the substance

Cei_ _x M _x 0 ₂ -y a certain oxygen deficit, ie y> 0 is required. The invention is further based on the finding that halide anions, such as Γ, Br ^~ and Cl ^~ , and hydrogen peroxide in seawater, inland waters and the flow or

Raw water and the permeate of desalination and treatment plants are included or

is formed continuously. In particular, hydrogen peroxide is continuously formed in water exposed to the sun light or the light of UV lamps. UV lamps are u.a. used in desalination and purification plants for disinfection.

In several of the invention intended uses it is important that the equivalent diameter of the nanoscale particles of Cei_ _x M _x 0 ₂ _ _y, preferably <100 nm, especially <50 nm and <200 nm, the nanoscale particles of Cei_ _x M _x 0 ₂ _ _y also largely deagglomerated and dispersed as homogeneously as possible so that their average surface coverage 0.001 to 35%, 0.001 to 30%, 0.001 to 25%, 0.001 to 20%, 0.001 to 15%, 0.001 to 10%, 0.001 to 5% or 0.001 to 1%. The size and dispersion of the nanoscale particles of Cei_ _x M _x 0 ₂ - _y influences the scattering of visible light and thus the visual appearance of a molded article according to the invention, a coating of a mortar or of a material based on silicone polymer in a controlling manner. For the visual appearance, it is advantageous, the equivalent diameter of the nanoscale particles of Cei_ _x M _x 0 ₂ - _y to decrease below a value of 200 nm, and to deagglomerate the particles substantially. Furthermore, by reducing the equivalent diameter and as homogeneous a dispersion of the particles, the bactericidal effect is increased.

The invention will be explained in more detail with reference to figures and examples. It shows

1 shows a molded body with a biocidal coating of a carrier material and

Particles from Cei_ _x M _x 02_ _y ;

Fig. 2 is a molding, the particles of Cei_ _x M _x 0 ₂ - _y contains;

3 shows a shaped body whose surface is coated with particles of Cei_ _x M _x O ₂ _ _y ;

Fig. 4 shows the bacterial attack on polymeric coatings with a Ce0 ₂ _ _y content of

0% by weight, 5% by weight and 10.0% by weight;

5 shows the algae attack on Ce0 ₂ _ _y- containing, weathered in sea water ship paints;

6 shows the size distribution of a nanoscale powder of Ce0 ₂ _ _y ;

Figure 7 shows the catalytic Bromierungsaktivität of Cei_ _x La _x 0 ₂ -. _Y nanoparticles.

1 shows a schematic sectional view of a surface of a shaped body 1 made of a base material 5 with a region 4 near the surface and a coating 6

Coating 6 comprises a carrier material 7 and particles 8 with the chemical

Composition Cei_ _x M _x 0 ₂ _ _y . The particles 8 are embedded in the carrier material 7, wherein a part of the particles 8 protrudes from the surface of the shaped body 2 or from the coating 6 and is in direct contact with a medium surrounding the shaped body 2.

2 shows a schematic sectional view of a surface of a shaped body 2 made of a base material 5 with a region 4 close to the surface. The shaped body 2 comprises particles 8 with the chemical composition Cei_ _x M _x 0 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 shaped body 2 and is in direct contact with a medium surrounding the shaped body 2.

FIG. 3 shows a schematic sectional view of a surface of a shaped body 3 made of a base material 5 with a region 4 close to the surface. Particles 8 with the chemical composition Cei_ _x M _x 0 ₂ - _y are arranged on the surface of the shaped body 3. The particles 8 are positively connected to the surface of the shaped body 3 and are in direct contact with a medium surrounding the shaped body 3. The frictional adhesion of the particles 8 to the surface of the molded body 3 is mediated by three alternative measures or mechanisms (i) to (iii):

(i) The surface of the molded body 3 is provided with an adhesive layer not shown in FIG

coated;

(ii) the particles 8 are coated with an adhesive layer not shown in Fig. 3;

(iii) The particles 8 are partially in the near-surface region 4 of the molding 3

embedded (not shown in Fig. 3);

The adhesive layer listed under items (i) and (ii) consists of a solvent-based, a thermoplastic or a chemically, thermally or by means of light, in particular UV-light crosslinkable adhesive. 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 in item (iii), the base material 5 of the

Shaped body 3 thermoplastic. After deposition of the particles 8 on the surface of the molded body 3 by means of powder coating or spraying, the near-surface region 4 is softened or fused by means of a suitable heat source, such as an infrared lamp or a hot air blower, so that the particles 8 are partially enclosed by the base material 5 and after the cooling are mechanically anchored in this.

The powder coating of moldings with particulate Cei_ _x M _x 0 ₂ - _y is preferably carried out using well-established in the prior art methods, such as electrostatic or

tribo electric powder coating. Example 1: Synthesis of Ce0 _2-y nanorods

For the preparation of nanoscale Ce0 ₂ _ _y an aqueous solution of NaOH (100 mL, 9 M, 37.8 g) was directly an intensively stirred solution of cerium (III) nitrate hexahydrate in ultrapure water (MilliQ water according to ISO 3696) added (5.2 g of Ce (NO ₃ ) ₃ '6 H ₂ O in 20 mL, corresponding to 0.6 M). After stirring for 30 minutes, the purple mixture was transferred to a 270 mL steel autoclave and maintained at 100 ° C for 24 hours. Thereafter, the purple product contained in the cloudy solution was separated by centrifugation (3000 rpm, 10 minutes) and washed five times with MilliQ water (15 ml each). After 12 hours of drying at 60 ° C, the product obtained was carefully ground to those formed in the precipitation

To crush agglomerates. The gravimetrically determined yield was greater than 70%. The powdery product was finally ultrasonicated in a concentration of

1 mg / mL suspended in MilliQ water, applied to a sample grid for a high-resolution transmission electron microscope (MRI EM) and dried under standard conditions in guan en. The structure of the obtained Ce0 ₂ _ _y powder was (HRTEM) by means of a high-resolution transmission electron microscope examined. The Ce0 ₂ _ _y powder is composed of polycrystalline rod having a length of 100 to 800 nm, wherein the average length is about 200 nm and a few rods have a length of more than 500 nm. The diameter of the rods is 5 to 20 nm. The stripes caused by electron diffraction into the

HRTEM images can be assigned to cubic phase lattices of Ce0 ₂ . The surface of the rods comprises regions or crystal facets with crystal lattice orientations of the type [110], [1 1 0] and [1 1 1].

Example 2: Quantitative synthesis of nanoscale Ce0 _2-y powder

To produce a larger amount, in this case about 300 g nanoscale Ce0 ₂ _ _y powder Ceriumcarbonathydrat Ce are first ₂ (C0 ₃₎ ₃ · 8H ₂ 0 and sodium carbonate hydrate

Na ₂ CO ₃ - 10H ₂ O mixed in a molar ratio of 2: 3 and milled in a ball mill with a ball-to-weight ratio of 5: 1 at 300 rpm for one hour (60 minutes). The millbase is then calcined for 60 minutes at a temperature of 900 ° C. After cooling, the calcined powder is washed three times with a mixture of hot deionized water and ethanol to remove by-product NaCl and suspended in deionized water in an amount of about 15% by weight. The suspension obtained is determined by means of a high-pressure fluidizer type M-110P Micro Fludics Corp. homogenized at a pressure of 2500 bar and dried for three hours (180 min) in an oven at a temperature of 80 ° C. FIG. 6 shows the size distribution, measured by dynamic light scattering, of the nanoscale powder of CeO _2- _y produced in this way on the homogenized suspension.

Example 3: Antibacterial membrane coatings A solution consisting of 32 g of polyethersulfone (Ultrason E6020P, BASF SE), 12 g of polyvinylpyrrolidone (K30 Luvitec®, BASF SE) and 1.6 g of nanoscale Ce0 ₂ _ _y - stick (with an average length of about 100 nm) in 156 g of dimethylacetamide (99% purity, Sigma-Aldrich) is heated to 60 ° C and degassed. The degassed solution is applied at a temperature of 25 ° C and a relative humidity of 50% on a Teflon disk and streaked by means of a rubber squeegee to a about 200 μιη thick film. The coated with the solution Teflon disk 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) heated to 60 ° C. Thereafter, the membrane is washed with deionized water and stored in deionized water.

To demonstrate the antibacterial activity of Ce0 ₂ _ _y before the three samples were coated carrier of stainless steel having a surface area of 2x2 cm ² in each case with a polymer matrix mixture, wherein the mixture for the first sample does not Ce0 ₂ _ _y contained. In contrast, the mixtures for the second and third sample nanoscale Ce0 ₂ _ _y particles with a

Weight proportion of 5 wt .-% and respectively 10.0 wt .-% added. The samples thus prepared were stored for 96 hours in a bacterial suspension of 200 chemically competent Shot® TOP 10 Eschericia coli cells (ThermoFischer Scientific) in 15 mL LB medium at a temperature of 37 ° C. Initially and at regular intervals of 3 hours, 150 aqueous KBr solution (100 mM) and H ₂ O ₂ solution (10 mM) were added to the bacterial suspension. At the end of the 96 hours, the samples were removed from the bacterial suspension, washed in LB medium, with

4 ', 6-diamidino-2-phenylindole (1 μg / mL DAPI in a sterile mixture of water and Glycerol in the volume ratio 1: 1) stained and imaged by means of a fluorescence microscope (Olympus AHBT3 with AH3 -RFC addition for incident light fluorescence). The with the

Fluorescence microscope images of the three samples with a Ce0 ₂ - _y content of 0 wt .-%, 5 wt .-% and 10.0 wt .-% are shown in Fig. 4a, 4b and respectively 4c, with white spots areas correspond to strong E. coli infestation. From Fig. 4a and 4b is immediately apparent that the polymer coating with a Ce0 ₂ - _y content of 5 wt .-% already has a high antibacterial activity.

Example 4: Antifouling Ship Varnish In order to investigate the antifouling effect of Ce0 ₂ _ _y in shipping,

Coatings based on two common antifouling ship paint formulations prepared and exposed to weathering in seawater over a period of 51 days (Ophoven-Kinrooi, Marina De Spaanjerd, Maas, Belgium). As sample substrates or

Coating carriers served stainless steel plates each having an area

2x2 cm ² . Several steel flakes were not coated before weathering and served as reference. One of the antifouling ship paint formulations used in the tests (Toplac International®, AkzoNobel) is based on silicone alkyd. Varnishes based on silicone or polydimethylsiloxane are hydrophobic, which reduces the adhesion of bacteria and algae. The second used in the experiments antifouling Schiffslackformulierung is referred to in the art as "abrasive" and contains as essential components resins with soluble and / or swelling ingredients, in particular tree resin of natural origin, and zinc oxide and / or copper oxide. Abrasive ship's paints are produced in seawater as well as in inland waters due to hydrolysis and the shear force exerted by the water flow

eroded continuously, wherein the contained zinc or copper oxide is exposed and finally flushed out. Zinc and copper oxides are highly toxic to many marine organisms and thus counteract the infestation of algae and mussels. On the other hand, the zinc and copper oxide released from abrasive marine coatings causes massive environmental damage in the vicinity of heavily frequented shipping routes. In the experiments carried out in the context of the present invention, the antibacterial activity of the in commercial

To eliminate lake coatings containing zinc and / or copper oxide, a specially prepared, purely polymeric Abrasivformulierung based on polyether resins was used. Fig. 5 shows photographs of the surfaces of six samples after 51 days of weathering in seawater, with dark areas indicating heavy algal and / or other marine organisms. In contrast, bright areas correspond to areas with low infestation. Figures 5a and 5b show uncoated stainless steel sample carriers. Figures 5c and 5d show samples having a coating of the marine paints described above (5c Toplac International®, 5d abrasive marine paint). The coatings of the samples shown in Figures 5c and 5d are purely polymeric and contain no metal oxide. By contrast, the coatings shown in FIGS. 5e and 5f 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 Fig. 5c and 5e consists of Toplac International® based on silicone alkyd, respectively from Toplac

International® with 2% by weight of nanoscale CeO ₂ - _y particles, based on the total weight of the coating. The antifouling effect of the Ce02- _y particles is readily apparent from the samples shown in FIGS. 5c and 5e. The same applies to the samples shown in FIGS. 5d and 5f, whose coating consists of abrasive ship paint without metal oxide and respectively abrasive ship paint with 2% by weight of nanoscale Ce0 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 ImageJ (Fiji) on the basis of the number of image pixels whose gray value lies below a predetermined gray value threshold, relative to the

Total number of image pixels. On the basis of the gray value histogram of each of the images 5a to 5f, the gray value threshold was set in such a way that when the gray value threshold changes by

± 10 gray values, the ratio of image pixels is practically constant. The following values were found for the algal infestation or area fraction determined by image analysis: 5a: 99.5%; 5b: 98.9%; 5c: 94.9,%; 5d: 85.5%; 5e: 50.5%; 5f: 45.9%.

Example 5: Catalytic activity of Cei _-x La _x 0 _2-y

Analogous to the synthesis method described in Example 1 were nanoscale rods from Cei_ _x La _x 02- _y by addition of cerium (III) nitrate hexahydrate (Ce (N0 ₃ ) ₃ '6 H ₂ 0) and

Lanthanum (III) nitrate hexahydrate (La (NO ₃ ) ₃ .6H ₂ O) in various mixing ratios to produce an aqueous solution of NaOH. The catalytic activity of the obtained nanoparticles was determined spectrophotometrically by means of a phenol red assay. The reaction of phenol red (phenolsulfonephthalein) too Bromophenol blue (3,3,5,5'-tetrabromophenolsulfonephthalein) was measured by emission of bromophenol at 590 nm (ε (590 nm) ~ 72.2 mM ^-1 cm ^-1 ). The measurements were performed using a Cary 5G UV-vis NIR spectrophotometer (Varian Inc., Palo Alto, CA) and a Cary 300 spectrophotometer (Agilent) with magnetic stirrer and an integrating sphere placed in the beam path after the sample cuvette. The catalytic conversion of phenol red to bromophenol blue is shown below.

A weighed amount of Cei_ _x La _x 02- _y nanoparticles was assayed from MilliQ water, phenol red, potassium bromide (KBr, cat. No. P0838 BioXtra,> 99.0%, Sigma-Aldrich) or ammonium bromide (NH ₄ Br , Cat. No. AB203189, Puratronic®, 99.999%) and

Hydrogen peroxide (H ₂ 0 ₂ , Cat. No. 8070.1, ROTIPURAN®, Carl Roth GmbH & Co. KG Karlsruhe, Germany) was added. The concentration of the components of the assay solution was:

Phenol red 10 or 50 μΜ

KBr or NH ₄ Br 25 mM

H ₂ 0 ₂ 300 μΜ

The concentration of H ₂ O ₂ was determined by the absorption of the assay solution at

Wavelength of 240 nm verified, with a molar absorption coefficient of 43.6 M ^"1 -cm ^{" 1} was used for the calculation. The amount of added Cei _x La _x O ₂ _ _y nanoparticles was varied in the range of 0 to 0.05 mg / mL. The Cei _x La _x 0 ₂ _ _y nanoparticles were added continuously to the assay solution at a temperature of 24 ± 2 ° C over a period of 5 minutes.

As a control, measurements were carried out on assays which (i) did not contain KBr, NH ₄ Br or H ₂ O ₂ and (ii) contained KBr or NH ₄ Br and H ₂ O ₂ in the above concentration ranges and those commercially available, quasi stoichiometric ceria (CeO ₂ , Cat. No. 221899, Sigma Aldrich, Steinheim, Germany) in an amount of

0.025 mg / ml was added. In the control measurement (i), no activity was observed become. In the control measurement (ii), a low activity was measured because the quasi-stoichiometric ceria has a comparatively small number of defects.

Fig. 7 shows the result of the assays, i. the catalytic bromination activity of

Cei_ _x La _x 0 ₂ - _y nanoparticles as a function of the substitution number x. With a substitution number of x = 0.2, the catalytic activity assumes a maximum value.

measurement methods

According to the invention, the term "equivalent diameter" refers to a particle ensemble in which 50% by volume of the particles have a volume equivalent spherical diameter of less than or equal to the "equivalent diameter" and 50% by volume of the particles have a volume equivalent spherical diameter greater than or equal to have "equivalent diameter". The term "equivalent diameter" used according to the invention is often referred to in the art as "d5o". With volume equivalent ball diameter is meant, depending on the measuring method used, the diameter of a sphere, which the same surface, same

Projection area or the same light scattering (diffraction disc) as the examined particles.

The dimensions of nano-scale particles of Cei_ _x M _x 0 ₂ - _y According to the invention analysis software by means of a scanning electron microscope or a transmission electron microscope and an image, such as ImageJ (http://imagej.nih.gov/ij) determined. In this case, at least 100, preferably at least 1000 nanoscale particles are digitally measured by means of the image analysis software using digitized electron micrographs. Due to the high lateral resolution of transmission electron microscopes and scanning electron microscopes of the prior art, which is up to 10 nm depending on the adjustment of the electron optics and beam parameters in the range of several angstroms, the volume-equivalent sphere diameter of the nanoscale particles of Cei_ _x M _x 0 ₂ may - _y be determined with high reliability.

If the electron microscopic contrast of the nanoscale particles from Cei_ _x M _x 0 ₂ - _y is insufficient compared to the surrounding matrix, imaging is performed using a

Silicon Drift Detector (SDD) for Energy Dispersive X-Ray Spectroscopy (EDS or EDX) equipped with a transmission scanning electron microscope or ordinary scanning electron microscope.

To determine the volume-equivalent spherical diameter of nanoscale particles from Cei_ _x M _x 02-y, the powder to be analyzed is suspended in demineralized water in a concentration of about 0.5 mg / ml by means of ultrasound and a drop of this suspension, ie about 40 μΐ on a plane , preferably circular graphitized copper grid (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 for about 30 minutes in a horizontal position under clean room conditions until the water has evaporated and transferred to the scanning electron microscope. The sample preparation described above ensures that adjacent nanoparticles on the grid are sufficiently far apart and are imaged as separate objects in the scanning electron microscope.

Software-assisted methods for the evaluation of digital images of nanoparticles recorded by means of a transmission electron microscope or scanning electron microscope are known in the art and comprise the following steps:

- algorithmic creation of a gray value histogram;

interactive definition of a suitable threshold value in the gray value histogram in order to classify each image pixel as belonging to the background or to the matrix or to a nanoparticle, depending on whether the gray value of the image pixel lies above or below the threshold value;

Algorithmic binarization of the image, d. H. Conversion of the gray value image into a black and white image;

optionally algorithmic binary dilation and erosion (closing) to close gaps or binary erosion and dilation (opening) to eliminate artifacts caused by image noise, such as pseudoparticles less than 1 nm in size; and

- Algorithmic identification of contiguous areas of adjacent (black) image pixels, which are associated with nanoscale particles and determination of the size or the number of image pixels contained in the respective area.

Software algorithms or programs, of the type described above, are usually included in the scope of delivery of modern transmission and scanning electron microscopes. or as an option. Alternatively, generic image analysis programs such as ImageJ (http://imagej.nih.gov/ij) may be used.

Alternatively or concomitantly, the volume-equivalent spherical diameters of the nanoscale particles from Cei_ _x M _x 02- _{y are} measured by means of light scattering or photon correlation spectroscopy. A suitable measuring device for particle sizes from 0.3 nm to 8 μm is used, inter alia, by Horiba Ltd. (Kyoto, Japan) under the product name "nano partica SZ-100" commercially offered.

The average surface coverage of the nanoscale particles from Cei_ _x M _x 02- _y is measured on a

Surface sample or on a cut sample of a shaped article according to the invention, a coating, an optionally cured coating composition, a dried mortar or a crosslinked material based on silicone polymer. For this purpose, as described above, the surface or cut sample is imaged by means of an electron microscope and the image obtained by means of an image analysis software such

for example, ImageJ (http://imagej.nih.gov/ij) evaluated. The average area occupation corresponds to the quotient of the number of (black) image pixels, which are assigned to nanoscale particles from Cei_ _x M _x 02_ _y , and the total number of image pixels (particles plus surrounding matrix).

According to the stereological principle or the Delesse principle (see, for example, US 5,754,688 A), in a section through a body containing inclusions or particles, the area ratio of the inclusions / particles is equal to their volume fraction. The from electron microscopic

Section images determined area or volume fraction of the nanoscale particles

Cei_ _x M _x 02- _y is in good agreement with values obtained from the weight fraction, equivalent diameter and specific gravity of the particles and the matrix.

The ratio of Ce (III) / Ce (IV) of the substance used according to the invention with the chemical composition Cei_ _x M _x 02- _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-radiation (for example: Al-Κα radiation (1486 eV at 250.0 W)), the Ce (III) / Ce (IV ) Ratio, from the relative area proportions of the unfolded signals according to the following formula, at the surface. For the spin-orbit coupling state 3d _(5/2) then the ratio of Ce ³⁺ results to.

As sample carriers, glass slides (standard slides, Carl-Roth) are cut into 1.5 cm x 1.5 cm glass slides and with a gold layer of about 15 nm by means of a coating system (Med 020, BAL-TEC) using a quartz microbalance Coated (QSG 070, Bal-TEC).

Before the XPS measurement, the samples are heated to about 900-1000 ° C to remove any existing water of crystallization. The fabric used in the invention having the chemical composition Cei_ _x M _x 02- _y is present as a particulate powder, which is pressed with a smooth surface into a pellet prior to 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 several mutually different sample positions and the derived elemental ratios are averaged.

The relative proportions of the components of the inventively used substance, with the chemical composition Cei_ _x M _x 02- _y (here based on proportions Ce and M in the substance used), can be determined by energy dispersive X-ray spectroscopy (EDX: energy dispersive X-ray spectroscopy) , 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 by quantifying the component signals the relative Share accessible.

Before the EDX measurement, the substance used according to the invention is mixed with the chemical

Composition Cei_ _x M _x 02_ _y suspended and / or dispersed in aqueous and / or organic solvents. The suspension and / or dispersion is applied to a silicon wafer

7.5 mm x 7.5 mm) and this fixed on a carbon guide tab (for example: PLANO guide tabs 12 mm 0). The solvent is evaporated (drying under normal conditions and / or at elevated temperatures (20 ° C <temperature <1000 ° C) and / or under vacuum). Optionally, the sample is coated with a 5 nm to 15 nm thick gold or silver layer using a coating equipment (for example: Med 020 (BAL-TEC) with quartz microbalance (QSG 070, BAL-TEC)).

Claims

claims

1. biocidal coating composition consisting of a carrier material and a substance with the chemical composition Cei_ _x M _x 0 ₂ - _y , wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

2. biocide coating composition according to claim 1, characterized in that the proportion of the substance having the chemical composition Cei_ _x M _x 0 ₂ - _y

0.01 to 10 wt .-%, based on the total weight of the biocidal

Coating composition.

3. biocidal coating composition according to claim 1 or 2, characterized

in that the substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y comprises particles which in one or more spatial directions have a dimension of

<500 nm.

4. biocidal coating composition according to one or more of claims 1 to 3, characterized in that the carrier material consists of one or more polymers and one or more additives.

5. Shaped body with a coating of a biocidal coating composition according to one or more of claims 1 to 4.

6. biocidal shaped body whose surface is partially or completely equipped with particles having the chemical composition Cei_ _x M _x 0 ₂ _ _y , wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

7. biocidal shaped body according to claim 6, characterized in that the biocidal

Shaped body of a base material and a substance with the chemical

Composition Cei_ _x M _x 0 ₂ _ _y , where the proportion of the substance with the chemical composition Cei_ _x M _x 0 ₂ - _y 10 ⁹ to 10 wt .-%, is ^"based on the total weight of the molding.

8. Shaped body according to claim 6 or 7, characterized in that the shaped body particles having the chemical composition Cei_ _x M _x 0 ₂ - _y , wherein the particles in one or more spatial directions have a dimension of <500 nm.

9. Shaped body according to one or more of claims 6 to 8, characterized in that a surface of the shaped body contains particles having the chemical composition Cei_ _x M _x 0 ₂ -y, wherein the particles are non-positively connected to the shaped body.

10. Shaped body according to claim 9, characterized in that a part of the particles protrudes from the surface of the shaped body.

11. Use of a substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y for the preparation of a biocidal coating composition, wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

12. Use of a substance with the chemical composition Cei_ _x M _x 0 ₂ _ _y for the

Production of biocidal moldings or moldings, wherein

M is selected from Ca, Ti, V, Fe, Sr, Y, Zr, Nb, La, Pr, In, Bi, Tb, Eu and Nd;

- x is a real number with 0 <x <0.5;

- y is a real number with 0 <y <0.4.

13. Use of a substance with the chemical composition Cei_ _x M _x 0 ₂ - _y

comprehensive molding in a medium containing H ₂ O ₂ or organic peroxides and / or halide anions, such as Γ, Br ^~ and Cl ^~ .