EP3247210A1 - Traitement biocide d'objets et d'agents de nettoyage et de soins corporels aqueux au moyen de micro- et/ou de nanoparticules de polyoxométallate - Google Patents

Traitement biocide d'objets et d'agents de nettoyage et de soins corporels aqueux au moyen de micro- et/ou de nanoparticules de polyoxométallate

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Publication number
EP3247210A1
EP3247210A1 EP16701243.4A EP16701243A EP3247210A1 EP 3247210 A1 EP3247210 A1 EP 3247210A1 EP 16701243 A EP16701243 A EP 16701243A EP 3247210 A1 EP3247210 A1 EP 3247210A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
micro
agglomerated
aggregated
functionalized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16701243.4A
Other languages
German (de)
English (en)
Inventor
Gregor Luthe
Wouter Bakker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Smartmaterialprinting BV
Original Assignee
Smartmaterialprinting BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102015000812.9A external-priority patent/DE102015000812A1/de
Priority claimed from DE102015000813.7A external-priority patent/DE102015000813A1/de
Priority claimed from DE102015000814.5A external-priority patent/DE102015000814A1/de
Application filed by Smartmaterialprinting BV filed Critical Smartmaterialprinting BV
Publication of EP3247210A1 publication Critical patent/EP3247210A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/244—Lanthanides; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/42—Phosphorus; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/0012—Galenical forms characterised by the site of application
    • A61K9/0014—Skin, i.e. galenical aspects of topical compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations

Definitions

  • the present invention relates to the biocidal finishing of articles and aqueous cleaning and personal care products with functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles.
  • the present invention relates to articles and hydrous cleansers and personal care products biocidized with functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles.
  • the present invention relates to the use of articles and hydrous cleansers and personal care products biocidal with functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles and / or catalytically equipped.
  • the present invention relates to methods of making articles and hydrous cleansers and personal care products comprising functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles biocidal and / or catalytic.
  • Nosocomial infections or hospital infections are infections that occur during hospitalization or treatment in hospitals or care facilities. To prevent these hospital infections, the rules of hygiene must be below Others are also strictly followed by the body care. For this purpose, the cleaning and personal care products biocides, such as
  • biocides are 10,10'-oxybisphenoxoarsine (OBPA), octylisothiazolinone (OIT), dichloroctylisothiazolinone (DCOIT), butylbenzisothiazolinone (BBIT), iodocarb (3-iodo-2-propynylbutylcarbamate), zinc pyrithione (zinc salt of pyridine-2-one). thiol-1-oxide), trichlosan (polychlorinated phenoxyphenols), silver ions and silver, especially in the form of silver nanoparticles.
  • OBPA 10,10'-oxybisphenoxoarsine
  • OIT octylisothiazolinone
  • DCOIT dichloroctylisothiazolinone
  • BBIT butylbenzisothiazolinone
  • iodocarb 3-iodo-2-propynylbutylcarbamate
  • cleansing and personal care products play an essential role in the prevention of nosocomial infections.
  • Detergents are consumables used to clean a wide variety of objects and objects. They effect or assist the removal of contaminants as a result of use or residues and buildup from the manufacturing process of the article of cleaning.
  • cleaning agents are used in combination with water, which as a polar solvent itself can contribute a significant part of the cleaning performance. At the same time, the dirt is carried away with the water. In contrast, in the dry-cleaning of textiles, cleaning is carried out in non-aqueous solvents.
  • Detergents are used to clean textiles, their precursors and leather. Cleaning agents are also detergents, but do not include, for example, detergents. Also, pharmaceutical or cosmetic body care products can be assigned to the detergents.
  • Body care is the care of the skin and its appendages such as hair and nails as well as the dental and oral care.
  • the aim is the prevention of diseases and the maintenance and strengthening of health through hygiene. In a broader sense, body care also serves to maintain and increase wellbeing.
  • Heteropoly acids are formed from weak, polybasic oxo acids of a metal (usually chromium, molybdenum, vanadium or tungsten) and a non-metal (usually arsenic, iodine, phosphorus, selenium, silicon or tellurium) as partial mixed anhydrides;
  • a metal usually chromium, molybdenum, vanadium or tungsten
  • a non-metal usually arsenic, iodine, phosphorus, selenium, silicon or tellurium
  • M 12-molybdophosphoric acid
  • Actinides or lanthanides can also act as the second central atom;
  • the tungsten heteropolyacids are thermally much more stable than the analogous molybdenum compounds.
  • E eg boron, silicon, zinc
  • Keggin acids With octahedrally coordinated heteroatom, the heterohexametallate type [( ⁇ 6) ⁇ 6 ⁇ ] / ⁇ - ⁇ 2 (Anderson-Evans anions) is frequently found [cf. Römpp Online, Version 3.47 "Heteropolyacids"].
  • HPPA pipemidic acid
  • European Patent EP 1 078121 B1 and European Patent Application EP 1439261 A2 disclose a process for the removal of harmful substances from the gas phase or the liquid phase, in which a Cellulosic fiber-based material with incorporated POM is brought into contact with the contaminated gas phase or liquid phase.
  • US Pat. No. 6,911,470 B1 discloses POM with antiretroviral activity.
  • US Pat. Nos. 5,824,706 and 6,020,369 disclose the prevention and treatment of respiratory viral infections in which a POM-containing aerosol spray is applied to the lungs.
  • topical POM-containing Compositions known by means of which pollutants, in particular warfare agents, are removed from the environment.
  • the topical compositions may also contain cerium, silver, gold or platinum compounds.
  • perfluoropolyethers PFPE
  • PFPE perfluoropolyethers
  • CEES 2-chloroethylethyl sulfide
  • CEESO 2-chloroethylethyl sulfoxide
  • microspheres of a particle size of 1 to 2000 ⁇ which contain a hydrophilic polymer such as oxidized cellulose with numerous pendant anionic groups and POM.
  • the microspheres are used for fixation and dosing of therapeutic radioisotopes.
  • Romanian Patent 122728 discloses a process for bleaching natural fibers with oxygen using POM as catalysts.
  • Moldavian patent MD 4014 B1 discloses anti-tumor POM.
  • US Pat. No. 6,387,841 B1 discloses catalysts for the conversion of alkanes into unsaturated compounds containing oxidic catalysts supported on polyoxometalates.
  • US Pat. No. 6,596,896 B2 discloses a process for the preparation of an aromatic carbonate by the reaction of an aromatic monohydroxy compound with carbon monoxide and oxygen. The reaction is carried out in the presence of a palladium compound, a redox catalyst, a polyoxometalate and a quaternary ammonium or phosphonium salt.
  • US Pat. No. 8,129,069 B2 discloses a composite fuel cell component which contains a proton-conducting polymer, a water-insoluble proton-conducting inorganic material and a polyoxometalate. That the particle size of the polyoxometalates (POM) could play a decisive role in problem solving can not be deduced from the prior art.
  • the magnetic and / or magnetizable, polymeric micro and / or nanocomposites for the production of complex, magnetic and / or magnetizable moldings using additive manufacturers is described.
  • the magnetic and / or magnetizable polymeric micro- and / or nanocomposites may also contain POM micro- and / or nanoparticles, which, however, are not specified in greater detail.
  • biocidal especially microbiocidal, especially antibacterial and / or bacteriostatic equipment for articles having a broad spectrum of use and, if at all, only a very low toxicity to humans, animals and plants, excluding pests, exhibit.
  • biocidal equipment should not cause resistance and cross-resistance, and should be ecologically safe and effective over the long term.
  • a further object of the present invention was to destroy medicaments and / or toxins and / or their metabolites in a simple manner, so that the medicaments and / or toxins and / or their metabolites which the patients use via the saliva, the respiratory air
  • the urine, through defecation and sweat excreted through the skin no longer enter the clothing, sheets, pillows, blankets, cushions and / or mattresses, and through contact with caregivers and other unwanted patients in hospitals, medical practices or the other environment.
  • the present invention the object of the invention to propose new hydrous cleaning and thoroughlynostinnittel with biocidal effect, which have a wide range of applications and - if at all - only a very low toxicity to humans, animals and plants, except pests.
  • the new hydrous body care products should not cause resistance and cross-resistance and be ecologically safe.
  • the biocidal equipments free of magnetic and / or magnetizable micro- and / or nanoparticles have been found to comprise at least one type of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or non-aggregated supported polyoxometalate micro- and / or nanoparticles having an average particle size of 1 nm to ⁇ 1000 [im contained and which are referred to below as "biocidal equipment according to the invention”.
  • the method has been found for the destruction of drugs and / or toxins and / or their metabolites, in which the drugs and / or toxins and / or their metabolites are contacted with at least one type of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles of average particle size from 1 nm to ⁇ 1000 ⁇ and which will be referred to hereinafter as "decontamination process according to the invention".
  • hydrous cleaning and personal care products having biocidal activity comprising at least one hydrous carrier and at least one type of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate nanoparticles of average particle size have been found from 1 nm to ⁇ 1000 nm and which are hereinafter referred to as "cleaning and personal care products according to the invention".
  • biocidal equipments according to the invention had a broad spectrum of use and, if at all, only a very low toxicity to humans, animals and plants, excluding pests. Furthermore, the biocidal equipment according to the invention did not cause any resistance or cross-resistance and was ecologically safe. They were using the inventive Method in a simple manner. They do not decompose and / or segregate even during prolonged storage and / or their transport at changing temperatures and changing humidity. They could be applied in a simple and safe way.
  • biocidal equipment according to the invention could be described as
  • micro- and / or nanoparticles to be used according to the invention also had a broad spectrum of biocidal applications and, if at all, only a very low toxicity to humans, animals and plants.
  • biocidal polyoxometalate micro- and / or nanoparticles to be used according to the invention did not cause any resistance and cross-resistance and were ecologically harmless. They do not decompose and / or segregate even during prolonged storage and / or their transport at changing temperatures and changing humidity.
  • polyoxometalate micro- and / or nanoparticles to be used according to the invention that they are also excellent in the prevention and therapy of nosocomial infections or hospital infections and in the context of the prevention of transmission of infections to objects indirectly or directly in contact with persons or animals could become.
  • appropriately treated dressings promoted wound healing and prevented scarring.
  • the cleansing and personal care products according to the invention had a broad spectrum of use and, if at all, only a very low toxicity to humans, animals and plants, excluding pests. Furthermore, the cleansing and personal care products according to the invention did not cause any resistance or cross-resistance and were ecologically safe. They were produced with the aid of the method according to the invention in a simple manner. They do not decompose and / or segregate even during prolonged storage and / or their transport at changing temperatures and changing humidity. They could be applied in a simple and safe way. If necessary, they or their remains could be easily removed from the objects to be cleaned and the cared for or maintained bodies.
  • the biocidal equipment according to the invention is free from magnetic and / or magnetizable micro- and / or nanoparticles, as described in the earlier German patent application DE 10 2014 006 519.7 from 3.5.2014.
  • the terms "solution” and "dissolved” refer to the fact that the substance in question is distributed in a molecularly disperse manner in the water-containing carrier.
  • nanoparticles denotes particles having an average particle size of 1 nm to ⁇ 1000 nm.
  • microparticles refers to particles having an average particle size of from 1 .mu.m to 1000 .mu.m.
  • objects are understood to mean more or less complex shaped parts and shape-neutral objects, such as tapes or plates, which stand out from informal objects such as gases, liquids or powders due to their three-dimensional design.
  • the essential constituent of the biocidal finishes according to the invention are heteropolyacids or polyoxometalates (POM) in the form of microparticles and / or nanoparticles having an average particle size of 1 nm to ⁇ 1000 pm, preferably 2 nm to 500 ⁇ m, preferably 5 nm to 250 pm, particularly preferably 5 nm to 150 ⁇ m and in particular 5 nm to 100 ⁇ m.
  • POM polyoxometalates
  • the average particle size of the POM micro- and / or nanoparticles to be used according to the invention which is measured by transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission electron microscopy (RTEM), atomic force microscopy (AFM) or scanning tunneling microscopy (TRM), can vary widely and excellently other components of the biocidal equipment according to the invention and their respective intended use.
  • TEM transmission electron microscopy
  • SEM scanning electron microscopy
  • RTEM scanning transmission electron microscopy
  • AFM atomic force microscopy
  • TRM scanning tunneling microscopy
  • the POM micro- and / or nanoparticles can have a wide variety of morphologies and geometric shapes, so that they can be perfectly adapted to the other components of the biocidal equipment according to the invention and their respective intended use.
  • they can be compact and at least one cavity and / or a core-shell structure, wherein the core and the shell are constructed of different materials can exhibit. They may also have different geometric shapes such as spheres, ellipsoids, cubes, cuboids, pyramids, cones, cylinders, rhombuses, dodecahedra, truncated dodecahedra, icosahedra, truncated icosahedra, dumbbells, tori, platelets or needles with circular, oval, elliptical, square, triangular , quadrangular, pentagonal, hexagonal, heptagonal, octagonal, or star-shaped (tri-quad, quadrilateral, pentagonal, or polygonal) outline.
  • geometric shapes such as spheres, ellipsoids, cubes, cuboids, pyramids, cones, cylinders, rhombuses, dodecahedra, truncated dodecahedra, ico
  • micro- and / or nanoparticles of different morphology and / or geometric form may be assembled together.
  • spherical POM micro- and / or nanoparticles may have pointed outgrowths in the form of cones.
  • two or three cylindrical POM micro and / or nanoparticles may assemble to form a T-shaped or Y-shaped particle.
  • their surface may have pits so that the POM micro and / or nanoparticles have a strawberry, raspberry or blackberry morphology.
  • the dumbbells, tori, needles or plates can be bent in at least one direction of the room.
  • the diameter of the POM microparticles and / or nanoparticles may vary widely and, therefore, be well adapted to the other components of the biocidal equipment of the invention and to their particular application.
  • the diameter of the POM micro- and / or nanoparticles according to the invention that are not spherically shaped is the same as the longest distance traveled by the respective microparticles and / or nanoparticles.
  • the diameter of preferred nanoparticles according to the invention is preferably 1 nm to ⁇ 1000 ⁇ , preferably 2 nm to 500 ⁇ , preferably 5 nm to 250 [im, more preferably 5 nm to 150 ⁇ and in particular 5 nm to 00 ⁇ .
  • the elemental composition and structure of the POM micro- and / or nanoparticles may also vary widely.
  • n-prime number here is an integer from 3 to 20 denoting the valence of an anion that varies depending on the variables X and M.
  • TM is a divalent or trivalent transition metal ion such as Mn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Cu 2+ and Zn 2+ .
  • the superscript t is an integer and denotes the valence of an anion, which varies depending on the significance of the variable TM.
  • POM of general formula XIII come into consideration: (AxGa y NbaO b ) z - (XIII).
  • variable A stands for phosphorus, silicon or germanium and the index x stands for 0 or for an integer from 1 to 40.
  • the index y stands for an integer from 1 to 10
  • the index a stands for one integer from 1 to 8
  • the index b is an integer from 15 to 150.
  • the z factor varies depending on the nature and the degree of oxidation of the variable A.
  • the aqua complexes and the active fragments of the POM XIII are also suitable.
  • y is preferably 6-a, where the index a is an integer of 1 to 5 and the index b is 19.
  • variable A is silicon or germanium
  • the index x is 2
  • the index y is 18
  • the index a is 6
  • the index b is 77.
  • the index x is 2 or 4
  • the index y is 12, 15, 17 or 30
  • the index a is 1, 3 or 6
  • the index b is 62 or 123.
  • the anions I to XIII are applied in the form of salts with cations which are approved for cleansing and personal care and pharmaceutical use.
  • Suitable cations are - H + , Na + , K + and NH 4 + ,
  • Mono-, di-, tri- or tetra- (C 1 -C 20 -alkylammonium) such as pentadecyldimethyl-ferrocenylmethylammonium, undecyldimethylferrocenylmethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, didodecyldimethylammonium, ditetradecyldimethylammonium, dihexadecyldimethylammonium, dioctadecyldimethylammonium, dioctadecylviologen,
  • Mono-, di-, tri- or tetra- (Ci-C2o-alkanolammonium) such as ethanolammonium diethanolammonium and triethanolammonium
  • Monocations of naturally occurring amino acids such as histidinium (HISH + ), argininium (ARGH + ) or lysinium (LYSH + ) or oligo- or polypeptides with one or more protonated basic amino acid residues.
  • n number in particular integer, from 1 to 50.
  • the POM particles to be used according to the invention can be prepared by means of customary and known wet-chemical processes. However, it is also possible to dissolve the POM in water and to spray the resulting solution against a warm stream of air. In addition, it is possible to evaporate the solution under vacuum, being irradiated with IR radiation. Furthermore, it is possible to prepare solutions, in particular aqueous, solutions of POM on cold surfaces, such as frozen, smooth metal surfaces, dry ice, cryogenic organic solvents and liquefied gases, such as methane, ethane propane, butane, methylcyclohexane or benzine, liquid nitrogen or liquid helium spray on and evaporate the dry ice or the liquid substances.
  • solutions, in particular aqueous, solutions of POM on cold surfaces such as frozen, smooth metal surfaces, dry ice, cryogenic organic solvents and liquefied gases, such as methane, ethane propane, butane, methylcyclohexane or benzine, liquid nitrogen or liquid helium
  • the POM micro- and / or nanoparticles described above are functionalized, non-functionalized, aggregated, unaggregated, agglomerated, non-agglomerated, supported, and / or unsupported.
  • they may be functionalized, agglomerated and supported. But they can also not be functionalized and aggregated.
  • the aggregates are loose aggregates of particles that are held together by cohesion and can not be distributed by conventional and known dispersion methods. Their inner surface is smaller than the sum of the surfaces of the primary particles.
  • the agglomerates are aggregates of primary particles and their aggregates, which are bridged over edges and corners. Their inner surface corresponds approximately to the sum of the surfaces of the primary particles.
  • the POM micro- and / or nanoparticles to be used according to the invention may be present "naked", that is to say that their surface is not surrounded by a shell and / or is not functionalized.
  • the POM micro- and / or nanoparticles to be used according to the invention can be surrounded by a shell and / or carry at least one functional group.
  • the material of the shells may carry the functional groups or else the functional groups may be present directly on the surface of the POM micro- and / or nanoparticles.
  • the material of the shell and / or the functional groups are selected so that the POM micro- and / or nanoparticles to be used according to the invention are particularly rapidly and homogeneously in an organic and / or inorganic matrix, in particular an organic and / or inorganic polymer Spread matrix and inorganic ceramic matrix, which acts as a carrier material and / or binder, and / or modify or mask the physical and / or chemical properties of the POM micro- and / or nanoparticles in a certain desired manner.
  • the sheaths and / or the functional groups may be attached to the surface of the POM micro- and / or nanoparticles via covalent and / or ionic bonds and / or electrostatic and / or van der Waals forces.
  • the bond between the surface of the POM micro- and / or nanoparticles and the shell and / or the functional groups may be permanent or reversible, ie releasable again.
  • the shells may be constructed of organic, inorganic and organometallic, polymeric, oligomeric and low molecular weight materials or combinations of at least two of these materials. Examples of suitable functional groups and materials for the shells and / or matrices of the POM micro- and / or nanoparticles to be used according to the invention are listed below. The person skilled in the art can select the functional groups and materials which are particularly suitable for the particular case on the basis of the property profiles known to him.
  • suitable additives are thermally and / or actinic-curable reactive diluents, low-boiling organic solvents and high-boiling organic solvents ("long solvents"), water, UV absorbers, light stabilizers, free-radical scavengers, thermolabile free-radical initiators, photoinitiators and co-initiators, crosslinking agents, as used in one-component systems, catalysts for thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and dispersing agents and surfactants, adhesion promoters, leveling agents, film-forming auxiliaries, sag control agents (SCA), rheology control additives (thickeners), Flame retardants, desiccants, drying agents, skin preventatives, Corrosion inhibitors, waxes, matting agents, reinforcing fibers or precursors of organically modified ceramic materials.
  • SCA sag control
  • thermally curable reactive diluents are positionally isomeric diethyloctanediols or hydroxyl-containing hyperbranched compounds or dendrimers, as described, for example, in German patent applications DE 198 05 421 A1, DE 198 09 643 A1 or DE 19840405 A1.
  • actinic radiation is understood as meaning corpuscular radiation such as electron radiation, alpha radiation, beta radiation and proton radiation, as well as electromagnetic radiation such as infrared, visible light, UV radiation, X-radiation and gamma radiation.
  • UV radiation is used.
  • Suitable low-boiling organic solvents and high-boiling organic solvents are ketones such as methyl ethyl ketone, methyl isoamyl ketone or methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate, ethyl ethoxypropionate, methoxypropyl acetate or butyl glycol acetate ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol , Butylene glycol or Dibutylenglykoldimethyl-, diethyl or -dibutylether, N-methylpyrrolidone or xylenes or mixtures of aromatic and / or aliphatic hydrocarbons such as Solventnaphtha®, gasoline 135/180, Dipentene or Solvesso®.
  • ketones such as methyl ethyl ketone,
  • thermolabile radical initiators are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxycarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.
  • Suitable catalysts for the crosslinking are dibutyltin dilaurate, dibutyltin dioleate, lithium decanoate, zinc octoate or bismuth salts, such as bismuth lactate or dimethylolpropionate.
  • suitable photoinitiators and coinitiators are described in Rompp Lexikon Lacke and Druckmaschine, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446.
  • Suitable additional crosslinking agents are aminoplast resins, as described, for example, in Rompp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, page 29, “Aminoharze”, the textbook “Lackadditive” by Johan Bieleman, Wiley- VCH, Weinheim, New York, 1998, pages 242 et seq., The book “Paints, Coatings and Solvents”, secondly revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pp. 80 et seq., Patents US 4,710,542 A1 or EP-B-0 245 700 A1, and in the article by B.
  • Suitable deaerating agents are diazadicycloundecane or benzoin.
  • Suitable emulsifiers, wetting and dispersing agents or surfactants are the customary and known anionic, cationic, nonionic and zwitterionic wetting agents, as described in detail in, for example, Rompp Online, April 2014, Georg Thieme Verlag, "wetting agents".
  • An example of a suitable coupling agent is tricyclodecanedimethanol.
  • suitable film-forming auxiliaries are cellulose derivatives such as cellulose acetobutyrate (CAB).
  • suitable transparent fillers are those based on silica, alumina or zirconia; in addition, reference is made to the Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.
  • Suitable sag control agents are ureas, modified ureas and / or silicas, as described, for example, in the publications EP 0 192 304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968, DE 2751 761 C 1, WO 97/12945 or "Dye + Varnish", 1 1/1992, pages 829 et seq.
  • rheology control additives are those disclosed in the patents WO 94/22968, EP 0 276 501 A 1, EP 0 249 201 A 1 or WO 97/12945, crosslinked polymeric microparticles, as disclosed, for example, in EP 0 008 127 A1, inorganic phyllosilicates such as aluminum-magnesium silicates, sodium-magnesium and sodium-magnesium-fluorine Montmorillonite-type lithium phyllosilicates; silicas such as aerosils; or synthetic polymers having ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copol ymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates.
  • An example of a suitable matting agent is magnesium ste
  • suitable reinforcing fibers are basalt fibers, boron fibers, glass fibers, ceramic fibers, silica fibers, metallic reinforcing fibers such as steel fibers, aramid fibers, Kevlar fibers, polyester fibers, nylon fibers, Teflon fibers, polyethylene fibers, polypropylene fibers, PMMA fibers, lignin fibers and cellulose fibers.
  • suitable precursors for organically modified ceramic materials are hydrolyzable organometallic compounds, in particular of silicon and aluminum.
  • suitable UV absorbers, radical scavengers, leveling agents, flame retardants, siccatives, drying agents, skin preventatives, corrosion inhibitors and waxes (B) are described in the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, described in detail.
  • Further examples of additives are dyes, colored pigments, white pigments, fluorescent pigments and phosphorescent pigments (phosphors) and the materials described below.
  • Carbohydrates are examples of the additives listed above, as well as examples of suitable UV absorbers, radical scavengers, leveling agents, flame retardants, siccatives, drying agents, skin preventatives, corrosion inhibitors and waxes (B) and the materials described below.
  • phosphors phosphorescent pigments
  • Glyceraldehyde erythrose, threose, ribose, arabinose, xylose, lyxose, fructose, allose, altrose, glucose, mannose, idose, galactose talose, rhamnose, amino sugars such as neuraminic acid, muramic acid, glucosamine, mannosamine, aldonic acids, ketoaldonic acids, aldaric acids, pyranoses, sucrose , Lactose, raffinose, panose and homopolysaccharides and heteropolysaccharides and proteoglycans, wherein the polysaccharide portion outweighs the protein portion, such as starch, dextran, cyclodextrin, arabinogalactan, celluloses, modified celluloses, lignocelluloses, chitin, chitosan, carageen and glycosaminoglycans.
  • Glycerol trimethylolpropane, pentaerythritol, alditols, cyclitols, dimers and oligomers of glycerin, trimethylolpropane, pentaerythritol, alditols and cyclitols; preferably tetritols, pentitols, hexitols, heptitols and octitols; preferably arabinitol, ribitol, xylitol, erythritol, threitol, galactitol, mannitol, glucitol, allitol, altritol, iditol, maltitol, isomaltitol, lactitol, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, Deca
  • Polyhydroxy carboxylic acids Glycerol, citric, tartaric, threonine, erythron, xylon, ascorbic, glucone, galacturon, iduron, mannuron, glucuron, guluron, glycuron, glucar, uluson, diketogulone, and lactobionic.
  • Polyhydroxyphenols and -benzenecarboxylic acids are examples of polyhydroxy carboxylic acids:
  • Ammonia ammonium, mono-, di- and trialkyl-, -aryl-, cycloalkyl-, -alkylaryl-, - alkylcycloalkyl, -cycloalkylaryl- and -alkylcycloalkylarylamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert.
  • thiols :
  • Polymers and oligomers with functional groups Poly (trimethylammonium ethylacrylate), polyacrylamide, poly (D, L-lactide-co-ethylene glycol), Pluronic®, Tetronic®, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), poly (alkyl cyanoacrylate), poly (lactic acid), poly (epsilon-) caprolactone), polyethylene glycol (PEG), poly (oxyethylene-co-propene) bisphosphonate, poly (acrylic acid), poly (methacrylic acid), hyaluronic acid, alginic acid, pectic acid, poly (ethyleneimine), poly (vinylpyridine), polyisobutene, poly (styrenesulfonic acid) , Poly (glycidyl methacrylate),
  • Poly (methacryloyloxyethyltrimethylammonium chloride) (ATAC), poly (L-lysine) and poly (3- (trimethoxysilyl) propylmethacrylate-r-PEG-methylethermethacrylate), proteins such as treptavidin, trypsin, albumin, immunoglobulin, oligo- and polynucleotides such as DNA and RNA, Peptides such as arginylglycylaspartic acid (RGD), AGKGTPSLETTP peptide (A54), HSYHSHSLLRMF peptide (C10) and glutathione, enzymes such as glucose oxidase, dendrimers such as polypropylenimine tetrahexacontaamine dendrimer generation 5 (PPI G5), poly (amidoamine) (PAMAM) and guanidine Dendrimers, phosphonic acid and dithiopyridine functionalized polystyrenes, functionalized polyethylene
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • phosphonic acids such as [(2-aminoethyl) hydroxymethylene] - and [(5-
  • wetting agents or surfactants are used as additives since this prevents aggregation and / or agglomeration of the POM micro- and / or nanoparticles and a homogeneous distribution in an organic and / or inorganic matrix is achieved.
  • the above-listed functional groups and materials for the shells of the POM micro- and / or nanoparticles are given by way of example only and not exhaustively. The enumeration is therefore intended to illustrate the variety of possibilities, and the expert can readily specify other possibilities due to his general expertise.
  • the content of the biocidal equipment according to the invention in the POM micro- and / or nanoparticles to be used according to the invention can vary widely and depends in particular on the respective intended use.
  • the content is 0.1 to 100 wt .-%, preferably 0.5 to 99.9 wt .-%, particularly preferably 1 to 99 wt .-% and in particular 1 to 90 wt .-%, each based on the total amount of biocidal equipment of the present invention.
  • Another preferred component of the biocidal equipment of the invention is water.
  • the water content of the biocidal equipment according to the invention can vary widely and also depends essentially on the respective intended use.
  • the water may be present as water of crystallization and / or be adsorbed on the surface of the POM micro- and / or nanoparticles to be used according to the invention.
  • the POM micro- and / or nanoparticles to be used according to the invention can be added to or mixed with other diamagnetic, non-magnetizable micro- and / or nanoparticles, but preferably nanoparticles.
  • the POM micro- and / or nanoparticles and the diamagnetic micro- and / or nanoparticles may be bound together by covalent and / or ionic bonds, hydrogen bonds, electrostatic attraction and / or Van der Waals forces.
  • Phosphates such as hydroxyapatite or calcium phosphate
  • Sulfides, selenides and tellurides from the group consisting of arsenic, antimony, bismuth, cadmium, zinc, iron, silver, lead and copper sulfide, cadmium selenide, tin selenide, zinc selenide, cadmium telluride and lead telluride;
  • Nitrides such as boron nitride, silicon nitride, aluminum nitride, gallium nitride and titanium nitride;
  • Phosphides, arsenides and antimonides selected from the group consisting of aluminum phosphide, gallium phosphide, indium phosphide, aluminum arsenide, gallium arsenide, indium arsenide, aluminum antimonide, gallium antimonide, indium antimonide;
  • Zintl phases such as Na 4 Sn 9 , Na 4 Pb 9 , Na 2 Pbi 0 , Na 3 [Cu @ Sn 9 ], Na 7 [Ge 9 CuGe 9 ] or
  • Carbides such as boron carbide, silicon carbide, tungsten carbide, titanium carbide or cadmium carbide; Borides such as zirconium boride; such as
  • Silicides such as molybdenum silicide.
  • micro- and / or nanoparticles of physiologically inert materials are used.
  • the POM micro- and / or nanoparticles to be used according to the invention are preferably distributed homogeneously or inhomogeneously in an organic and / or inorganic matrix, in particular an organic and / or inorganic polymeric matrix and / or in an inorganic ceramic matrix ,
  • the content of POM micro- and / or nanoparticles in the matrix is a function of the distance from the surface of the articles to be finished or finished.
  • the concentration of POM micro- and / or nanoparticles may increase or decrease continuously or discontinuously with the distance to the surface.
  • a particular advantage of this embodiment of the biocidal equipment according to the invention is that during the mechanical, physical and / or chemical removal of the material of the object in question, a fresh biocidal surface is repeatedly exposed.
  • biocidal finish of the present invention may also be present as a separate layer on the surface of the article to be finished.
  • This embodiment has the advantage of saving material.
  • both embodiments of the biocidal equipment according to the invention can be combined.
  • the organic polymeric matrix may be constructed of conventional and known 'thermoplastic' or thermoset polymers.
  • Suitable thermoplastic polymers are customary and known linear and / or branched and / or block-like, comb-like and / or random polyaddition resins, polycondensation resins and / or (co) polymers of ethylenically unsaturated monomers.
  • suitable (co) polymers are (meth) acrylate (co) polymers and / or polystyrene, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinylamides, polyacrylonitriles, polyethylenes, polypropylenes, polybutylenes, polyisoprenes and / or copolymers thereof.
  • suitable polyaddition resins or polycondensation resins are polyesters, alkyds, polylactones, polycarbonates, polyethers, proteins, epoxy resin-amine adducts, polyurethanes, alkyd resins polysiloxanes, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, cellulose, polysulfides , Polyacetals, polyethylene oxides, polycaprolactams, polylactones, polylactides, polyimides, and / or polyureas.
  • thermosets are prepared from polyfunctional, low molecular weight and / or oligomeric compounds by (co) polymerization initiated thermally and / or with actinic radiation.
  • Suitable functional low molecular weight and / or oligomeric compounds are the reactive diluents, catalysts and initiators listed above.
  • thermoplastics and thermosets listed above is not exhaustive, but in particular to illustrate the variety of possibilities.
  • Other suitable materials for the polymeric matrix can be readily selected by those skilled in the art, based on their general knowledge.
  • thermoplastics Once the polymeric matrix is built up from thermoplastics, the POM micro- and / or nanoparticles are incorporated into the thermoplastics by conventional and well known methods of making polymer blends.
  • the polymeric matrix is composed of thermosetting plastics
  • the POM micro- and / or nanoparticles are converted into the starting materials of the thermosets by means of customary and known methods Incorporated mixing methods, after which the resulting mixtures are polymerized and thereby crosslinked.
  • mixing units such as high-speed stirrers, Ultraturrax, inline dissolvers, homogenizing nozzles, static mixers, microfluidizers, extruders or kneaders.
  • the inorganic ceramic matrix may be composed of conventional and known glasses and / or ceramic materials.
  • the ceramic may be constructed of an oxide ceramic and / or non-oxide ceramic.
  • suitable ceramics are aluminum oxide, boron carbide, boron nitride, boron nitride carbide, calcium silicate, hafnium carbide, silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, silicon oxide carbide, silicon nitride carbide, silicon oxynitride carbide, glass ceramic, tantalum carbide, zinc carbide or zirconia ceramics composed of alumina, boron carbide, boron nitride, boron nitride carbide, calcium silicate, hafnium carbide, silica, silicon carbide, silicon nitride, silicon oxynitride, silicon oxide carbide, silicon nitride carbide, silicon oxynitride carbide, silicon aluminum oxynitride, glass ceramic, tantalum carbide, zinc carbide and / or zirconia.
  • the raw materials In contrast to all other materials that ceramic products, especially oxide ceramics, first formed from the raw materials and then (ie after molding) in a high-temperature process or sintering process with the goal of material conversion to produce cohesive connections between the raw material grains in the ceramic material be transferred.
  • the raw materials In contrast to the other materials, the raw materials have two fundamental tasks: on the one hand they must guarantee the chemical composition of the desired ceramic materials and on the other hand they must first allow their shaping.
  • the ceramic blank thus has a significantly lower mechanical strength than, for example, a metallic blank. Therefore bears the name Grünling, which has nothing to do with the color.
  • the manufacture of the ceramic products irrespective of the composition, always comprises the following steps: 1. Production of raw materials, 2. Preparation of the ceramic mass,
  • Non-oxide ceramics do not contain oxygen.
  • the anions are instead carbon, nitrogen, boron and silicon. Exceptions are a few mixed ceramics which, in addition to the said anion, also contain some oxygen, e.g. Siliciumaluminiumoxidnitrid.
  • the cations also differ significantly from the oxide ceramics.
  • silicon and where as cations occur the homeopolar bond prevails, so that one can not speak chemically exactly of cation and anion.
  • titanium, zirconium, niobium or tungsten are present in the crystal lattice, then these form layers with metallic bonds in the material which are heteropolar with the homopolar bonded carbon, nitrogen, boron or silicon layers.
  • non-oxide ceramics examples include Thieme Römpp Online 2014 Version 3.45, "Non-oxide Ceramics”. Examples of suitable non-oxide ceramics are the Further from US patent application US 2014/0206525 A1 and German patent applications DE 102 07 860 A1 and DE 10 2012 021 906 A1.
  • Glass-ceramics are polycrystalline solids with more than 30% glass phase which are produced by controlled crystallization of glasses.
  • the crystals are usually colorless by heat treatment of a suitable glass and cause a spatial dispersion of the light entering the material.
  • glass ceramics can be found in Thieme Römpp Online 2014 Version 3.45, "Glass Ceramics", International Patent Application WO 2010/081561 A1, "Optically Permeable Glass and Glass Ceramic Foams, Process for their Production and their Use” and in the article by AM Marques and AM Bernardin, "Ceramic Foams made from Piain Glass Cullets", Qualicer 2008, pages 89 to 93.
  • calcium silicates are used.
  • the calcium silicates are common and known products available on the market and can be prepared by a hydrothermal process from sensibly ground raw materials lime and sand in a water suspension with low solids content and additives.
  • the mineralogical transformations the main phases tobermorite 5CaOx6Si02x5.5 H 2 0 (about 10% water, resistant to 650 ° C) and xonolite 6CaOx6Si0 2 xH 2 0 (about 3% water, up to 850 ° C resistant) are carried out in autoclaves.
  • the anhydrous phase wollastonite 3CaOx3Si0 2 increases the temperature resistance as an additive.
  • the dewatering reactions determine the degree of shrinkage and thus the application limits of the material.
  • biocidal equipment of the invention described above has the further significant advantages of being compatible with many other materials different materials of the matrices can be combined.
  • suitable materials of this type are glass, wood, metal, ceramic, porcelain and / or polymers.
  • the biocidal equipment of the invention and the articles which are hereby equipped can be produced by means of customary and known shaping methods. Preferably, they are fixed by means of the production method according to the invention, in which at least one type of the above-described POM micro- and / or nanoparticles to be used according to the invention are fixed on and / or in the biocidal articles.
  • additive i. accumulating, building factory, especially digitally controlled, additive manufacturers, accomplished.
  • 3D printers are used as digitally controlled additive manufacturers, the geometry of the objects being predetermined by CAD / CAM programs.
  • 3D printers designed for selective laser melting, selective electron beam melting, selective laser sintering, stereolithography, digital light processing, polyjet modeling, cold gas spraying or melt layers are used.
  • the choice of the construction technique depends in particular on the physico-chemical properties of the POM micro- and / or nanoparticles and matrix materials or their precursors to be used according to the invention.
  • the starting materials are added separately or as a mixture of at least two starting materials as informal fluids to at least one additive, in particular digitally controlled, additive, factory, and with the aid of the at least one additive, in particular digitally controlled, additive, factory simultaneous solidification of the starting materials to the provided with the biocidal equipments objects according to the invention in particular digitally piled in layers accumulated until at least one predetermined, in particular digitally predetermined, molded part is constructed.
  • This variant of the method according to the invention is particularly suitable for the production of complex, molded parts based on thermosets.
  • the starting materials are mixed together so that at least one solid, shape-neutral, provided with a biocidal finish of the invention article results.
  • the object is converted into an informal, fluid state and added in this state at least one additive, in particular digitally controlled additive, factory and using the at least one additive, in particular digitally controlled, additive, factory with simultaneous solidification of the fluid in particular digitally piled layer by layer is until at least a predetermined, in particular digitally predetermined, molded part is constructed.
  • the starting materials are mixed together so that at least one solid, formless powder provided with the biocidal finish according to the invention results.
  • the at least one powder is added to an additive, in particular digitally controlled additive, factory and added digitally piled using the at least one additive, in particular digitally controlled additive, factory, until at least one predetermined, in particular digitally predetermined, molded part results.
  • a biocidal equipped molding is constructed such that it alternately areas with high concentration of POM micro- and / or nanoparticles and areas with low concentration and / or areas without POM micro and / or nanoparticles.
  • This can be achieved by interrupting the supply of the starting materials containing POM micro- and / or nanoparticles and, instead, a layer of a thermoplastic polymer or the starting materials for a region containing no POM micro- and / or nanoparticles or a different concentration of POM micro- and / or - nanoparticles, are applied, after which again a layer of the first POM micro- and / or nanoparticles-containing starting materials is applied. This process can be repeated several times.
  • informal means that the material in question does not have a defined shape but adapts to the shapes of a container, so that informal materials are liquid or gaseous.
  • the abovementioned methods can also be supplemented by so-called flip-up manufacturing techniques, in which first two-dimensional structures are produced on a stretched, elastic material, which automatically unfold upon relaxing into the desired three-dimensional structure (see Sheng Xu et al micro / nanomaterials into complex, three-dimensional architectures by compressive buckling ", Science Vol. 347, no. 6281 pp., pages 154-159).
  • shape-neutral means that the material in question is plate-shaped, ribbon-shaped or wire-shaped.
  • biocidal equipment according to the invention is suitable for all objects that come into direct or indirect contact with humans or animals. This means that applications are virtually unlimited. To name just a few examples, you can
  • Nanoparticle-containing aerosols are applied,
  • Heaters in particular ovens and block heaters
  • Fillers in particular fillers for cushions, upholstery or mattresses,
  • the POM micro- and / or nanoparticles to be used according to the invention are preferably distributed homogeneously or inhomogeneously on and in the clothing and / or laundry and / or the filling material of pillows, duvets and / or mattresses. They may be fixed, for example, on the fibers and the fabric of the clothing and / or the laundry and / or the filling material of pillows, duvets and / or mattresses.
  • fibers are natural fibers such as cellulose, cotton, wood fibers, flax fibers, hemp fibers, textile fibers and subtropical and tropical fibers such as cotton fibers, bamboo fibers, jute fibers, ramie fibers and sisal fibers into consideration.
  • plastic fibers examples include aramid fibers, Kevlar fibers, polyamide fibers, polyester fibers, polyolefin fibers and Teflon fibers.
  • the fabrics may contain the pure fibers or mixtures of fibers.
  • liquid mixtures of the above-described POM micro- and / or nanoparticles to be used according to the invention are incorporated into and into the fibers, fabrics and / or fillers of the clothing, bedding, pillows, blankets, upholstery and / or mattresses applied to the aforementioned additives.
  • the customary and known mixing units such as high-speed stirrers, Ultraturrax, inline dissolvers, homogenizing nozzles, static mixers, microfluidizers, extruders or kneaders.
  • the clothing, bedding, pillows, blankets, cushions and / or mattresses and / or fillers are soaked in the resulting liquid mixtures or the liquid mixtures are sprayed on it.
  • the volatile constituents in particular water and / or low-boiling solvents, are removed from the applied liquid mixtures so that the POM micro- and / or nanoparticles remain behind.
  • toxins and their metabolites are basically all drugs and / or toxins and / or metabolites into consideration, as for example in the textbook "General and special pharmacology and toxicology," seventh edition, 1998, Spektrum Akademischer Verlag Heidelberg, publisher W Förth, D. Henschler, W. Rummel and K. Strong.
  • the medicaments are chemotherapeutic agents such as
  • BCNU Carmustine
  • Hormonal anti-neoplastic compounds are Hormonal anti-neoplastic compounds:
  • Antibiotic natural neoplastic compounds bleomycin
  • these and other medicaments and / or toxins and / or their metabolites are destroyed by contact with the POM micro- and / or nanoparticles to be used according to the invention. It is advantageous if the contact takes place in the presence of oxygen. This can be accomplished by treating the contaminated clothing, bedding, pillows, blankets, cushions and / or mattresses in a confined space, preferably a climatic cabinet, through which air or oxygen-enriched air passes. Preferably, this treatment is carried out with dried air. This is preferably done at elevated temperature, in particular at 30 to 70 "Celsius.
  • the content of the cleaning and personal care compositions according to the invention to the POM nanoparticles to be used according to the invention can vary widely and depends in particular on the respective intended use.
  • the content is from 0.1 to 50 wt .-%, preferably 0.5 to 40 wt .-%, particularly preferably 1 to 30 wt .-% and in particular 1 to 20 wt .-%, each based on the total amount of the cleaning or personal care product in question.
  • Another essential component of the cleaning and personal care products according to the invention is water.
  • the water content of the cleansing and personal care products according to the invention can vary widely and likewise depends essentially on the respective intended use.
  • the cleaning and personal care products of the invention may contain ingredients that are common and well-known in these areas and therefore need not be described here. These include in particular surfactants, abrasives, acids, bases, bleaches, enzymes, fragrances, dyes, antiperspirants, odor absorbers, enzyme inhibitors, antioxidants, brighteners or ingredients that help prevent or reduce re-pollution.
  • the cleaning and personal care products according to the invention serve for the use according to the invention.
  • cleaning includes in particular the cleaning of laundry and textiles with detergents, in particular with heavy duty detergents, color detergents or fabric softeners, and gall soaps, the cleaning of dishes, especially cookware, dishes and cutlery with dishwashing detergents, machine dishwashing and rinsing agents, the cleaning of surfaces in residential areas with neutral detergents, abrasives, scouring sand or window cleaning agents, cleaning of kitchen and bath utensils with descaler and limescale cleaner and cleaning of other objects with pipe cleaners, brake cleaners, alcohol cleaners, all-purpose cleaners, glass cleaners, sanitary cleaners, toilet cleaners, carpet cleaners, Car care products or in diluents.
  • body care includes the regular cleaning of skin and hair, skin care, hair care, tooth and oral care, cleaning and care of fingernails (manicure) and feet (pedicure), affecting the body odor by deodorants and Fragrances such as perfumes and decorative cosmetics such as make-up and lip care as well as shaving, beard care and hair removal (depilation).
  • personal care products includes cleansers for skin and hair such as lotions, creams, ointments, shower gels, shampoos, fluid and solid soaps, hand washing pastes, moisturizers (Moisterizer), bath water additives, tooth and mouth care products such as toothpastes and mouthwashes, skin care products Manicures and pedicures, body odor control agents such as deodorants, fragrances and perfumes, facial make-up such as eyelash pencils, lipsticks and lip balm, shaving cream and shaving soap, beard care and depilatories. This list is not exhaustive, but the nanoparticles to be used according to the invention can be added to other body care products not mentioned here.
  • the cleaning and personal care products according to the invention are expediently prepared by means of the preparation process II according to the invention.
  • the ingredients of the cleaning and personal care compositions according to the invention are mixed simultaneously or sequentially together, and the resulting mixture is homogenized.
  • customary and known mixing units such as stirred tanks, inline dissolvers, counterflow mixers, extruders or kneaders can be used.
  • the resulting cleaning and personal care products according to the invention for use according to the invention are filled into containers.
  • the uncoated PDMS films and the coated PDMS films of series 1 and 2 either Staphylococcus aureus (gram positive bacterium, series 1.1 and 1.2) or Escherichia coli (gram negative bacterium, series 2.1 and 2.2) were applied by means of inoculating loops.
  • Staphylococcus aureus gram positive bacterium, series 1.1 and 1.2
  • Escherichia coli gram negative bacterium, series 2.1 and 2.2
  • Example 3 The biocidal equipment of complex three-dimensional exhibits
  • the contaminated bedsheets Series 1 and Comparative Series 1 were each treated with air in a climate-controlled cabinet at 35 ° Celsius for 1 hour. Subsequently, the sheets were removed from the climate cabinets and washed separately, dried and ironed. Thereafter, GC-MS coupling was used to determine if any remaining doxorubicin could be detected. It was found that no more doxorubicin could be detected in the bedsheets of the series 1, whereas in the bedsheets of the comparative series 1 persistently adhering doxorubicin could still be detected.
  • Two nano-fluid cleaners for laboratories were made up of 60 parts by weight of distilled water, 37 parts by weight of a mixture of ethanol and isopropanol (1: 1).
  • the three liquid cleaners were filled into one spray bottle each.
  • three planar glass sheets 1 to 3 heavily soiled with oil, fat, microorganisms and loam were provided.
  • a soiled glass sheet 3 was sprayed with the mixture 3.
  • the glass sheet 3 was cleaned by stripping the dirt cover with a wet stripper and wiping with a soaked with the mixture 3 sponge and then dried.
  • the two other soiled glass panes 1 and 2 were each sprayed with the mixture 1 or the mixture 2.
  • the glass panes 1 and 2 were also cleaned by stripping the dirt cover with a wet stripper and wiping with a soaked with the mixture 1 or 2 sponge and then dried.
  • the re-colonization of the glass sheets 1 to 3 was determined by microorganisms in the usual and known manner: while the glass sheets 1 and 2 was only very slightly colonized again, corresponded to the glass sheet 3, the deposit of microorganisms before that of cleaning.
  • Kiehl's® ULTRA FACIAL CLEANERS FOR ALL SKIN TYPES Kiehl's® ULTRA FACIAL CLEANERS FOR ALL SKIN TYPES
  • compositions of series 1 and 2 had a better bactericidal effect than the original products and significantly delayed the re-colonization of the treated areas with microorganisms.

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Abstract

L'invention concerne des traitements biocides d'objets, exempts de micro- et/ou nanoparticules magnétiques et/ou magnétisables, contenant au moins un type de micro- et/ou de nanoparticules de polyoxométallate fonctionnalisées, non fonctionnalisées, agrégées, non agrégées, agglomérées, non agglomérées, supportées et/ou non supportées, présentant une dimension particulaire moyenne de 1 à < 1000 μm, des procédés de fabrication de ceux-ci et leur utilisation, des agents de nettoyage et de soins corporels contenant ces micro- et/ou nanoparticules de polyoxométallate, ainsi que des procédés d'élimination de médicaments et de substances toxiques et de leurs métabolites à l'aide de ces micro- et/ou nanoparticules de polyoxométallate.
EP16701243.4A 2015-01-21 2016-01-13 Traitement biocide d'objets et d'agents de nettoyage et de soins corporels aqueux au moyen de micro- et/ou de nanoparticules de polyoxométallate Withdrawn EP3247210A1 (fr)

Applications Claiming Priority (4)

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DE102015000812.9A DE102015000812A1 (de) 2015-01-21 2015-01-21 Wasserhaltige Reinigungs- und Körperpflegemittel mit biozider Wirkung
DE102015000813.7A DE102015000813A1 (de) 2015-01-21 2015-01-21 Verfahren zur Vernichtung von Medikamenten und Giftstoffen und ihren Metaboliten mithilfe von Polyoxometallat-Mikro-und/oder -Nanopartikeln
DE102015000814.5A DE102015000814A1 (de) 2015-01-21 2015-01-21 Biozide Ausrüstung von Gegenständen mit Polyoxometallat-Mikro- und/oder -Nanopartikeln
PCT/EP2016/000048 WO2016116259A1 (fr) 2015-01-21 2016-01-13 Traitement biocide d'objets et d'agents de nettoyage et de soins corporels aqueux au moyen de micro- et/ou de nanoparticules de polyoxométallate

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