DE102015000812A1 - Hydrous cleaning and personal care products with biocidal activity - Google Patents

Abstract

Hydrous cleaning and personal care products having a biocidal effect, comprising functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate nanoparticles of an average particle size of 1 nm to <1000 nm, process for their preparation and their use.

Description

Field of the invention

The present invention relates to hydrous cleansing and personal care products having a biocidal effect.

In addition, the present invention relates to the preparation of hydrous cleaning and personal care products having a biocidal effect.

Last but not least, the present invention relates to the use of hydrous cleaning and personal care products having a biocidal effect.

State of the art

The prior art cited in the present application is incorporated by reference into the present application.

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.

Usually, 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.

In addition to the regular cleaning of skin and hair, skin care, hair care, tooth and oral care as well as the cleaning and care of the fingernails (manicure) and feet (pedicure) are part of the body care. The influence of body odor by deodorants and fragrances such as perfumes and the use of decorative cosmetics such as make-up and lip care are also part of the body care. Other areas include shaving, beard care and hair removal (depilation).

• – Akarizide gegen Milben,
• – Algizide gegen Algen,
• – Bakterizide und Bakteriostatika gegen Bakterien und Bakterienfilme,
• – Fungizide gegen Pilze,
• – Insektizide gegen Insekten,
• – mikrobiozide Ausrüstung gegen Keime,
• – Molluskizide gegen Schnecken,
• – Nematizide gegen Fadenwürmer und
• – Viruzide gegen Viren,

zugesetzt.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 strictly adhered to, among other things by the body care. For this purpose, the cleaning and personal care products biocides, such as

• - acaricides against mites,
• - algicides against algae,
• - Bactericides and bacteriostats against bacteria and bacterial films,
• - fungicides against fungi,
• Insecticides against insects,
• - microbiocidal equipment against germs,
• - molluscicides against snails,
• - Nematicides against roundworms and
• - Virucides against viruses,

added.

Examples of known biocides are 10,10'-oxybisphenoxoarsine (OBPA), octylisothiazolinone (OIT), dichloroctylisothiazolinone (DCOIT), butylbenzisothiazolinone (BBIT), iodocarb (3-iodo-2-propynyl butylcarbamate), 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.

The known biocides have disadvantages such as a narrow range of applications, a comparatively high toxicity, the tendency to cause resistance and cross-resistance, and a still largely unexplained ecological long-term effect.

It is therefore the task of providing biocides that do not have these disadvantages.

Polyoxymetallates are inorganic polyacids with - in contrast to isopolyacids - at least two different central atoms. Heteropoly acids arise 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; Example: H ₃ [PM ₁₂ O ₄₀ ]: 12-molybdophosphoric acid (M = Mo) or 12-tungstophosphoric acid (M = W). Actinides or lanthanides can also act as the second central atom; The tungsten heteropolyacids are thermally much more stable than the analogous molybdenum compounds. Occasionally, Keggin acids are heteropolyacids of the general formula [(EO ₄ ) M ₁₂ O ₃₆ ] _n-8 with n = valence of the tetrahedrally coordinated element E (eg boron, silicon, zinc). With octahedral coordinated heteroatom, the heterohexametallate type [(EO ₆ ) M ₆ O ₁₈ ] _n-12 (Anderson-Evans anions) is frequently found [cf. Römpp Online, Version 3.47 »Heteropolyacids« ].

In your Article »Fabrication and Characterization of Antibacterial-active Multilayer Films Based on Keggin Polyoxometalates and Methylene Blue«, in Z. Naturforsch. 2010, 65b, pages 140-146, describe Dan Chen, Jun Peng, Haijun Pang, Pengpeng Zhang, Yuan Chen, Yan Shen, Chanyung Chen, and Huiyuan Ma , multilayer films based on the Keggin polyoxymetalates alpha- [SiW ₁₂ O ₄₀ ] ^4- / alpha [PMO ₁₂ O ₄₀ ] ^3- , which show antibacterial activity against Escherichia coli.

In your Antibiotic protection by [P2W18O62] 6-, [SiMo12O40] 4-, and [PTi2W10O40] 7- by methicillin-resistant and vacomycin-resistant Staphylococcus aureus «in Journal of Inorganic Biochemistry, 100 (2006 ), Pages 1225 to 1233, describe Miyauo Inue, Tokomo Suzuki, Yutaka Fujita, Mayumi Oda, Nobuhiro Matsumato and Thoshihiro Yamase increasing the antibacterial effect of beta-lactam antibiotics by the above-mentioned heteropolyacids.

In your "K27 [KAs4W40O140] and K18 [KSb9W21O86], and Keggin-structural polyoxotungstates agaist Helicobacter pylori", in Journal of Inorganic Biochemistry, 99 (2005), pp. 1023 to 1031, describe Miyao Inoue, "Antibacterial Activity of Highly Negatively Charged Polyoxotungstates. Keiko Segawa, Sae Matsunaga, Nobuhiro Matsumoto, Mayumi Oda and Toshihiro Yamase the antibacterial activity of these polyoxymetalates (POM) based on the determination of the minimum inhibitory concentration (MIC), and the fractional inhibitory concentration (FIC), the time of death of the bacteria, the bacterial morphology and the uptake of the POM into the bacterial cells.

In your Yuhua Feng, Zhangan Han, Jun Pen, Jun Lu, Bo Xue, Li Li, Describe Yuhua Feng, Jun Li, Huiyuan Ma and Enbo Wang multilayer films based on the Keggin-type polyoxymetalates alpha- [SiW ₁₂ O ₄₀ ] ^4- and alpha- [PMo ₁₂ O ₄₀ ] _3- and cationic chitosan.

In your In Carbohydrate Polymers, 64 (2006), pages 92-97, Shuiping Chen, Guozhong Wu, Dewu Long and Yaodang Liu describe the preparation, characterization and antibacterial activity of chitosan-Ca3V10O28 complex membrane a chitosan-Ca ₃ V ₁₀ O ₂₈ complex membrane with persistent antimicrobial activity. The membrane is made by the self-assembly of V ₁₀ O ₂₈ ^6- and chitosan using Ca ²⁺ as a linker.

In your Article "Studies of the first antibacterial agent of pipemidic acid modifying Keggin polyoxometalate" in Inorganic Chemical Communication, 14, pp. 1192-1195, 2011, C. Li et al. an adduct of POM with pipemidic acid (HPPA) of the formula {[Co (PPA) ₂ ] H ₂ [SiW ₁₂ O ₄₀ ]} · HPPA · 3H ₂ O and its antitumor effect on MCF-7 cells.

• – [Cu(II)(Enrofloxacin)₂(H₂O)₂]H₂[b-Mo₈O₂₆]·4H₂O,
• – [Cu(II)₂(Pipemidinsäure)₄][d-Mo₈O₂₆]·4H₂O,
• – [Cu(II)₂(Norfloxacin)₂(H₂O)₂][b-Mo₈O₂₆] und
• – [Cu(II)₂(Enoxazin)₂(H₂O)₄][b-Mo₈O₂₆]·2H₂O.

In your J.-Q., Polyhedron 31, pp. 422-430, 2012, describe J.-Q. "Study on the ligation of copper complexes of quinolone antibacterial drugs and octamolybdate". Sha et al. the antitumor activity of

• [Cu (II) (enrofloxacin) ₂ (H ₂ O) ₂ ] H ₂ [b-Mo ₈ O ₂₆ ] * 4H ₂ O,
• - [Cu (II) ₂ (pipemidic acid) ₄ ] [d-Mo ₈ O ₂₆ ] · 4H ₂ O,
• - [Cu (II) ₂ (norfloxacin) ₂ (H ₂ O) ₂ ] [b-Mo ₈ O ₂₆ ] and
• - [Cu (II) ₂ (enoxazine) ₂ (H ₂ O) ₄ ] [b-Mo ₈ O ₂₆ ] · 2H ₂ O.

In your "Studies on the interactions of Ti-containing polyoxometalates (POMs) with SARS-CoV 3Clpro by molecular modeling" in Journal of Inorganic Biochemistry, 101, pages 89 to 94, 2007, describe D. Hu et al. the SARS activity of the isomers of [a-PTi ₂ W ₁₀ O ₄₀ ] ^7-.

From the American patent application US 2004/0185078 A1, the American patent US 6,713,076 B1 , the European patent EP 1 078121 B1 and the European patent application EP 1439261 A2 discloses a method of removing gaseous phase or liquid phase contaminants by contacting a cellulosic fiber-based material with embedded POM with the contaminated gas phase or liquid phase.

From the American patent US 6,911,470 B1 POM are known to have antiretroviral activity.

From the American patents US 5,824,706 and US 6,020,369 are the prevention and treatment of respiratory viral infections known in which a POM-containing aerosol spray is applied to the lungs.

From the American patent application US 2008/0187601 A1 and the American patents US 6,723,349 B2 and US Pat. No. 7,097,858 B2 are topical POM-containing compositions are known by means of which pollutants, in particular warfare agents, are removed from the environment. Additionally, the topical compositions may still contain cerium, silver, gold or platinum compounds. In particular, perfluoropolyethers (PFPE) can be used as the carrier. Thus, the warfare agent 2-chloroethylethyl sulfide (CEES) can be quantitatively oxidized to 2-chloroethylethyl sulfoxide (CEESO). These known topical compositions have the disadvantage that they can not be removed from the skin by water.

From the international patent application WO 2006/036269 A2 For example, microspheres of particle size from 1 to 2000 microns are known to contain a hydrophilic polymer such as oxidized cellulose having numerous pendent anionic groups and POM. The microspheres are used for fixation and dosing of therapeutic radioisotopes.

The Romanian Patent 122728 discloses a process for bleaching natural fibers with oxygen using POM as catalysts.

The Moldovan patent MD 4014 B1 discloses POM with antitumor effect.

The known compositions are not suitable as personal care products.

Object of the invention

It is an object of the present invention to propose novel water-borne personal care products with biocidal activity which have a broad spectrum of use and, if at all, only a very low toxicity to humans, animals and plants, pests excluded. Furthermore, the new hydrous body care products should not cause resistance and cross-resistance and be ecologically safe.

Inventive solution

Accordingly, the hydrous cleaning and personal care products having biocidal activity comprising at least one aqueous vehicle 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".

In addition, a process has been found for the preparation of the biocidal cleaning and personal care compositions of the present invention which comprises at least one type of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate nanoparticles of particle size from 1 nm to <1000 nm in at least one water-containing carrier and which is referred to hereinafter as the "preparation process according to the invention".

Last but not least, the use of hydrous cleansing and personal care products having a biocidal effect has been found in the cleaning of objects and in daily personal care and medical personal care, which is referred to below as "use according to the invention".

Advantages of the invention

In view of the prior art, it was surprising and unforeseeable for the skilled person that the object underlying the present invention could be achieved by means of the cleaning and personal care products according to the invention, the production process according to the invention and the use according to the invention.

In particular, it was surprising that 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.

It is a very particular advantage of the cleansing and personal care products according to the invention that they can be used excellently in the context of the prevention and therapy of nosocomial infections or hospital infections.

Detailed description of the invention

In the context of the present invention, 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.

In the context of the present invention, the term "nanoparticles" denotes particles having an average particle size of 1 nm to <1000 nm.

Furthermore, the term »microparticles refers to particles having an average particle size of from 1 .mu.m to 1000 .mu.m.

The essential constituent of the cleansing and personal care compositions according to the invention are heteropolyacids or polyoxymetalates (POM) in the form of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported nanoparticles having a mean particle size of 1 nm to <1000 nm, preferably 2 nm to 500 nm, preferably 5 nm to 250 nm, particularly preferably 5 nm to 150 nm and in particular 5 nm to 100 nm.

In addition to the functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate nanoparticles to be used according to the invention, dissolved POM and / or POM in the form of microparticles can also be present in minor amounts. "Subordinate amounts" means that the relevant materials are present only in such amounts in the cleansing and personal care products according to the invention that the properties of the cleansing and personal care products according to the invention that are essentially not characterized by the nanoparticles according to the invention are adversely affected.

Otherwise, the size, structure and elemental composition of the POM can vary widely.

• – das Lindquist-Hexamolybdatanion, Mo₆O₁₉ ^2–,
• – das Decavanadatanion, V₁₀O₂₈ ^6–,
• – das Paratungstatanion B, H₂W₁₂O₄₂ ^10–,
• – Mo36-Polymolybdate, Mo₃₆O₁₁₂(H₂O)^8–,
• – die Strandberg-Struktur, HP₂Mo₅O₂₃ ^4–,
• – die Keggin-Struktur, XM₁₂O₄₀ ^n–,
• – die Dawson-Struktur, X₂M₁₈O₆₂ ^n–,
• – die Anderson-Struktur, XM₆O₂₄ ^n–,
• – die Allman-Waugh-Struktur, X₁₂M₁₈O₃₂ ^n–,
• – die Weakley-Yamase-Struktur, XM₁₀O₃₆ ^n–, und
• – die Dexter-Silverton-Struktur, XM₁₂O₄₂ ^n–.

For example, the classification of the POM into the following structures is known:

• The Lindquist hexamolybdate anion, Mo ₆ O ₁₉ ^2- ,
• The decavanadate anion, V ₁₀ O ₂₈ ^6- ,
• The paratization stat B, H ₂ W ₁₂ O ₄₂ ^10- ,
• Mo36 polymolybddate, Mo ₃₆ O ₁₁₂ (H ₂ O) ^8- ,
• - the Strandberg structure, HP ₂ Mo ₅ O ₂₃ ^4- ,
• The Keggin structure, XM ₁₂ O ₄₀ ^n- ,
• The Dawson structure, X ₂ M ₁₈ O ₆₂ ^n- ,
• The Anderson structure, XM ₆ O ₂₄ ^n- ,
• The Allman Waugh structure, X ₁₂ M ₁₈ O ₃₂ ⁿ ,
• The Weakley-Yamase structure, XM ₁₀ O ₃₆ ⁿ , and
• - the Dexter-Silverton structure, XM ₁₂ O ₄₂ ^n- .

The 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.

• – (BW₁₂O₄₀)^5– (I),
• – (W₁₀O₃₂)^4– (II),
• – (P₂W₁₈O₆₂)^6– (III),
• – (PW₁₁O₃₉)^7– (IV),
• – (SiW₁₁O₃₉)^8– (V),
• – (HSiW₉O₃₄)^9– (VI),
• – (HPW₉O₃₄)^8– (VII),
• – (TM)₄(PW₉O₃₄)^t– (VIII),
• – (TM)₄(P₂W₁₅O₅₆)₂ ^t– (IX),
• – (NaP₅W₃₀O₁₁₀)^14– (X)
• – (TM)₃(PW₉O₃₄)₂ ^12– (XI) und
• – (P₂W₁₈O₆)^6– (XII).

As a further principle of order for POM the formulas I to XIII can serve:

• - (BW ₁₂ O ₄₀ ) ^5- (I),
• - (W ₁₀ O ₃₂ ) ^4- (II),
• - (P ₂ W ₁₈ O ₆₂ ) ^6- (III),
• - (PW ₁₁ O ₃₉ ) ^7- (IV),
• - (SiW ₁₁ O ₃₉ ) ^8- (V),
• - (HSiW ₉ O ₃₄ ) ^9- (VI),
• - (HPW ₉ O ₃₄ ) ^8- (VII),
• - (TM) ₄ (PW ₉ O ₃₄ ) ^t- (VIII),
• - (TM) ₄ (P ₂ W ₁₅ O ₅₆ ) ₂ ^t- (IX),
• - (NaP ₅ W ₃₀ O ₁₁₀ ) ^14- (X)
• - (TM) ₃ (PW ₉ O ₃₄ ) ₂ ^12- (XI) and
• - (P ₂ W ₁₈ O ₆ ) ^6- (XII).

In formulas I to XII, 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.

• – (A_xGa_yNb_aO_b)^z– (XIII).

Furthermore, POM of general formula XIII come into consideration:

• - (A _x Ga _y Nb _a O _b ) ^z- (XIII).

In the formula XIII the 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 and 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.

When the index x is 0, y is preferably 6-a, where the index a is an integer of 1 to 5 and the index b is 19.

When the variable A is silicon or germanium, the index x is 2, the index y is 18, the index a is 6 and the index b is 77.

When the variable A is P, the index x is 2 or 4, the index y is 12, 15, 17 or 30, the index a is 1, 3 or 6 and the index b is 62 or 123.

Preferably, 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.

• – H⁺, Na⁺, K⁺ und NH₄ ⁺,
• – Mono-, Di-, Tri- oder Tetra-(C₁-C₂₀-alkylammonium) wie Pentadecyldimethylferrocenylmethylammonium, Undecyldimethylferrocenylmethylammonium, Hexadecyltrimethylammonium, Octadecyltrimethylammonium, Didodecyldimethylammonium, Ditetradecyldimethylammonium, Dihexadecyldimethylammonium, Dioctadecyldimethylammonium, Dioctadecylviologen, Trioctadecylmethylammonium und Tetrabutylammonium,
• – Mono-, Di-, Tri- oder Tetra-(C₁-C₂₀-alkanolammonium) wie Ethanolammonium Diethanolammonium und Triethanolammonium
• – Monokationen natürlich vorkommender Aminosäuren wie Histidinium (HISH⁺), Argininium (ARGH⁺) oder Lysinium (LYSH⁺) oder Oligo- oder Polypeptide mit einem oder mehreren protonierten basischen Aminosäurerest(en).

[Vgl. US 6,020,369 , Spalte 3, Zeile 6, bis Spalte 4, Zeile 29)Examples of suitable cations are

• H ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ ,
• Mono-, di-, tri- or tetra- (C ₁ -C ₂₀ -alkylammonium) such as pentadecyldimethylferrocenylmethylammonium, undecyldimethylferrocenylmethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, didodecyldimethylammonium, ditetradecyldimethylammonium, dihexadecyldimethylammonium, Dioctadecyldimethylammonium, dioctadecylviologen, trioctadecylmethylammonium and tetrabutylammonium,
• - Mono-, di-, tri- or tetra- (C ₁ -C ₂₀ 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 having one or more protonated basic amino acid residues.

[See. US 6,020,369 , Column 3, line 6, to column 4, line 29)

Examples of suitable POM are shown in Table 1. Table 1: Sum formulas of suitable POMs ^a) No. Molecular formula family structure 1 [(NMP) ₂ H] ₃ PW ₁₂ O ₄₀ 2 [(DMA) ₂ H] ₃ PMo ₁₂ O ₄₀ 3 (NH ₄ ) ₁₇ Na [NaSb ₉ W ₂₁ O ₈₆ ] Inorganic crypt 4 a- and bH ₅ BW ₁₂ O ₄₀ " 5 a- and bH ₆ ZnW ₁₂ O ₄₀ " 6 a and bH ₆ P ₂ W ₁₈ O ₆₂ " 7 alpha- (NH ₄ ) ₆ P ₂ W ₁₈ O ₆₂ Wells-Dawson structure 8th K ₁₀ Cu ₄ (H ₂ O) ₂ (PW ₉ O ₃₄ ) ₂ · 20H ₂ O " 9 K ₁₀ Co ₄ (H ₂ O) ₂ (PW ₉ O ₃₄ ) ₂ .20H ₂ O " 10 Na ₇ PW ₁₁ O ₃₉ " Na ₇ PW ₁₁ O ₃₉ .20H ₂ O + 2C ₆ H ₅ P (O) (OH) ₂ " 11 [(n-butyl) ₄ N] ₄ H ₃ PW ₁₁ O ₃₉ " 12 b-Na ₈ HPW ₉ O ₃₄ " 13 [(n-butyl) ₄ N] ₃ PMoW ₁₁ O ₃₉ " 14 a - [(n-butyl) ₄ N] ₄ Mo8O26 " 15 [(n-butyl) ₄ N] ₂ W ₆ O ₁₉ " 16 [(n-butyl) ₄ N] ₂ Mo ₆ O ₁₉ " 17 a- (NH ₄ ) _n H _(4-n) SiW ₁₂ O ₄₀ " 18 a- (NH ₄ ) _n H _(5-n) BW ₁₂ O ₄₀ " 19 AK ₅ BW ₁₂ O ₄₀ " 20 K ₄ W ₄ O ₁₀ (O ₂ ) ₆ " 21 b-Na ₉ HSiW ₉ O ₃₄ " 22 Na ₆ H ₂ W ₁₂ O ₄₀ " 23 (NH ₄ ) ₁₄ [NaP ₅ W ₃₀ O ₁₁₀ ] Preyssler structure 24 a- (NH ₄ ) ₅ BW ₁₂ O ₄₀ " 25 a-Na ₅ BW ₁₂ O ₄₀ " 26 (NH ₄ ) ₄ W ₁₀ O ₃₂ " "27 (Me ₄ N) ₄ W ₁₀ O ₃₂ " 28 (HISH ⁺ ) _n H _(5-n) BW ₁₂ O ₄₀ " 29 (LYSH ⁺ ) _n H _(5-n) BW ₁₂ O ₄₀ " 30 (ARGH ⁺ ) _n H _(5-n) BW ₁₂ O ₄₀ " 31 (HISH ⁺ ) _n H _(4-n) SiW ₁₂ O ₄₀ " 32 (LYSH ⁺ ) _n H _(4-n) SiW ₁₂ O ₄₀ " 34 (ARGH ⁺ ) _n H _(4-n) SiW ₁₂ O ₄₀ " 35 K ₁₂ [EuP ₅ W ₃₀ O ₁₁₀ ] · 22H ₂ O ^b) " 36 AK ₈ SiW ₁₁ O ₃₉ " 37 K ₁₀ (H ₂ W ₁₂ O ₄₂ ) " 38 K ₁₂ Ni ₃ (II) (PW ₉ O ₃₄ ) ₂ · nH ₂ O " 39 (NH ₄ ) ₁₀ Co ₄ (II) (PW ₉ O ₃₄ ) ₂ · nH ₂ O " 40 K ₁₂ Pd ₃ (II) (PW ₉ O ₃₄ ) ₂ · nH ₂ O " 41 Na ₁₂ P ₂ W ₁₅ O ₅₆ .18H ₂ O Lacunare (defective) structure 42 Na ₁₆ Cu ₄ (H ₂ O) ₂ (P ₂ W ₁₅ O ₅₆ ) ₂ · nH ₂ O " 43 Na ₁₆ Zn ₄ (H ₂ O) ₂ (P ₂ W ₁₅ O ₅₆ ) ₂ · nH ₂ O " 44 Na ₁₆ Co ₄ (H ₂ O) ₂ (P ₂ W ₁₅ O ₅₆ ) ₂ .nH ₂ O " 45 Na ₁₆ N _i4 (H ₂ O) ₂ (P ₂ W ₁₅ O ₅₆ ) ₂ · nH ₂ O Wells-Dawson sandwich structure 46 Na ₁₆ Mn ₄ (H ₂ O) ₂ (P ₂ W ₁₅ O ₅₆ ) ₂ · nH ₂ O " 47 Na ₁₆ Fe ₄ (H ₂ O) ₂ (P ₂ W ₁₅ O ₅₆ ) ₂ .nH ₂ O " 48 K ₁₀ Zn ₄ (H ₂ O) ₂ (PW ₉ O ₃₄ ) ₂ · 20nH ₂ O Keggin sandwich structure 49 K ₁₀ Ni ₄ (H ₂ O) ₂ (PW ₉ O ₃₄ ) ₂ · nH ₂ O " 50 K ₁₀ Mn ₄ (H ₂ O) ₂ (PW ₉ O ₃₄ ) ₂ · nH ₂ O " 51 K ₁₀ Fe ₄ (H ₂ O) ₂ (PW ₉ O ₃₄ ) ₂ · nH ₂ O " 52 K ₁₂ Cu ₃ (PW ₉ O ₃₄ ) ₂ · nH ₂ O " 53 K ₁₂ (CoH ₂ O) ₃ (PW ₉ O ₃₄ ) ₂ .nH ₂ O " 54 K ₁₂ Zn ₃ (PW ₉ O ₃₄ ) ₂ · 15H ₂ O " 55 K ₁₂ Mn ₃ (PW ₉ O ₃₄ ) ₂ · 15H ₂ O " 56 K ₁₂ Fe ₃ (PW ₉ O ₃₄ ) ₂ .25H ₂ O " 57 (ARGH ⁺ ) ₁₀ (NH ₄ ) ₇ Na [NaSb ₉ W ₂₁ O ₈₆ ] " 58 (ARGH ⁺ ) ₅ HW ₁₁ O ₃₉ · 17H ₂ O " 59 K ₇ Ti ₂ W ₁₀ O ₄₀ " 60 [(CH ₃ ) ₄ N] ₇ Ti ₂ W ₁₀ O ₄₀ " 61 Cs ₇ Ti ₂ W ₁₀ O ₄₀ " 62 [HISH ⁺ ] ₇ Ti ₂ W ₁₀ O ₄₀ " 63 [LYSH ⁺ ] _n Na _7-n PTi ₂ W ₁₀ O ₄₀ " 64 [ARGH ⁺ ] _n Na _7-n PTi ₂ W ₁₀ O ₄₀ " 65 [n-butyl ₄ N ⁺ ] ₃ H ₃ V ₁₀ O ₂₈ " 66 K ₇ HNb ₆ O ₁₉ · 13H2O " 67 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O [SiCH ₂ CH ₂ C (O) OCH ₃ ] ₂ Organically modified structure 68 [(CH ₃ ) ₄ N ⁺ ] ₄ PW ₁₁ O ₃₉ - (SiCH ₂ CH ₂ CH ₂ CN) " 69 [(CH ₃ ) ₄ N ⁺ ] ₄ PW ₁₁ O ₃₉ - (SiCH ₂ CH ₂ CH ₂ Cl) " 70 [(CH ₃ ) ₄ N ⁺ ] ₄ PW ₁₁ O ₃₉ - (SiCH ₂ = CH ₂ ) " 71 Cs ₄ [SiW11O ₃₉ - (CH ₂ CH ₂ C (O) OCH _{3) 2] 4} " 72 Cs ₄ [SiW11O ₃₉ - (SiCH ₂ CH ₂ CH ₂ CN)] ₄ " 73 Cs ₄ [SiW11O ₃₉ - (CH ₂ CH ₂ CH ₂ Cl) _{2] 4} " 74 Cs ₄ [SiW11O ₃₉ - (SiCH ₂ = CH ₂ )] ₄ " 75 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O- (SiCH ₂ CH ₂ CH ₂ Cl) ₂ " 76 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O (SiCH ₂ CH ₂ CH ₂ CN) ₂ " 77 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O (SiCH ₂ = CH ₂ ) ₂ " 78 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O (SiC (CH ₃ ) ₂ " 79 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O (SiCH ₂ CH (CH ₃ )] ₂ " 80 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O [SiCH ₂ CH ₂ C (O) OCH ₃ )] ₂ " 81 K ₅ Mn (II) PW ₁₁ O ₃₉ · nH ₂ O Transition-metal-substituted structure 82 K ₈ Mn (II) P ₂ W ₁₁ O ₆₁ .nH ₂ O " 83 K ₆ Mn (II) SiW ₁₁ O ₃₉ · nH ₂ O " 84 K ₅ PW ₁₁ O ₃₉ [Si (CH ₃ ) ₂ ] .nH ₂ O " 85 K ₅ PW ₁₁ O ₄₁ [PC ₆ H ₅ ) ₂ * nH ₂ O " 86 Na ₃ PW ₁₁ O ₄₁ [PC ₆ H ₅ ) ₂ .nH ₂ O " 87 K ₅ PTiW ₁₁ O ₄₀ " 88 Cs ₅ PTiW ₁₁ O ₃₉ " 89 K ₆ SiW ₁₁ O ₃₉ [Si (CH ₃ ) ₂ ] .nH ₂ O " 90 KSiW ₁₁ O ₃₉ [Si (C ₆ H ₅ ) (tert-C ₄ H ₉ )] nH ₂ O. " 91 KSiW ₁₁ O ₃₉ [Si (C ₆ H ₅ ) ₂ ] nH ₂ O. " 92 K ₇ SiW ₉ Nb ₃ O ₄₀ · nH ₂ O " 93 Cs ₇ SiW ₉ Nb ₃ O ₄₀ · nH ₂ O " 94 Cs ₈ Si ₂ W ₁₈ Nb ₆ O ₇₇ · nH ₂ O " 95 [(CH ₃ ) ₃ NH ⁺ ] ₇ SiW ₉ Nb ₃ O ₄₀ · nH ₂ O Substituted Keggin structure 96 (CN ₃ H ₆ ) ₇ SiW ₉ Nb ₃ O ₄₀ · nH ₂ O " 97 (CN ₃ H _{6) 8} Si ₂ W ₁₈ Nb ₆ O ₇₇ · nH ₂ O " 98 Rb ₇ SiW ₉ Nb ₃ O ₄₀ · nH ₂ O " 99 Rb ₈ Si ₂ W ₁₈ Nb ₆ O ₇₇ · nH ₂ O " 100 K ₈ Si ₂ W ₁₈ Nb ₆ O ₇₇ · nH ₂ O " 101 K ₆ P ₂ Mo ₁₈ O ₆₂ · nH ₂ O " 102 (C ₅ H ₅ N) ₇ HSi ₂ W ₁₈ Nb ₆ O ₇₇ · nH ₂ O " 103 (C ₅ H ₅ N) ₇ SiW ₉ Nb ₃ O ₄₀ · nH ₂ O " 104 (ARGH ⁺ ) ₈ SiW ₁₈ Nb ₆ O ₇₇ · 18H ₂ O " 105 (LYSH +) ₇ KSiW ₁₈ Nb ₆ O ₇₇ · 18H ₂ O " 106 (HISH ⁺ ) ₆ K ₂ SiW ₁₈ Nb ₆ O ₇₇ · 18H ₂ O " 107 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O (SiCH ₂ CH ₃ ) ₂ " 108 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O (SiCH ₃ ) ₂ " 109 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ -O (SiC ₁₆ H ₃₃ ) ₂ " 110 Li ₉ P ₂ V ₃ (CH ₃ ) ₃ W ₁₂ O ₆₂ " 111 Li ₇ HSi ₂ W ₁₈ Nb ₆ O ₇₇ " 112 Cs ₉ P ₂ V ₃ CH ₃ W ₁₂ O ₆₂ " 113 Cs ₁₂ P ₂ V ₃ W ₁₂ O ₆₂ " 114 K ₄ H ₂ PV ₄ W ₈ O ₄₀ " 115 Na ₁₂ P ₄ W ₁₄ O ₅₈ " 116 Na ₁₄ H ₆ P ₆ W ₁₈ O ₇₉ " 117 aK ₅ (NbO ₂ ) SiW ₁₁ O ₃₉ " 118 aK ₅ (TaO ₂ ) SiW ₁₁ O ₃₉ " 119 [(CH ₃ ) ₃ NH ⁺ ) ₅ NbSiW ₁₁ O ₄₀ " 120 [(CH ₃ ) ₃ NH ⁺ ] ₅ TaSiW ₁₁ O ₄₀ " 121 K ₆ Nb ₃ PW ₉ O ₄₀ Peroxo Keggin structure 122 [(CH ₃ ) ₃ NH ⁺ ] ₅ (NbO ₂ ) SiW ₁₁ O ₃₉ " 123 [(CH ₃ ) ₃ NH ⁺ ] ₅ ((TaO ₂ ) SiW ₁₁ O ₃₉ " 124 K ₄ (NbO ₂ ) PW ₁₁ O ₃₉ " 125 K ₇ (NbO ₂ ) P ₂ W ₁₂ O ₆₁ " 126 [(CH ₃ ) ₃ NH ⁺ ] ₇ (NbO ₂ ) ₃ SiW ₉ O ₃₇ " 127 Cs ₇ (NbO ₂ ) ₃ SiW ₉ O ₃₇ " 128 K ₆ (NbO ₂ ) ₃ PW ₉ O ₃₇ " 129 Na ₁₀ (H ₂ W ₁₂ O ₄₂ ) " 130 K ₄ NbPW ₁₁ O ₄₀ " 131 [(CH ₃ ) ₃ NH ₊ ] ₄ NbPW ₁₁ O ₄₀ " 132 K ₅ NbSiW ₁₁ O ₄₀ " 133 K ₅ TaSiW ₁₁ O ₄₀ " 134 K ₇ NbP ₂ W ₁₇ O ₆₂ Wells-Dawson structure 135 K ₇ (TiO ₂ ) ₂ PW ₁₀ O ₃₈ " 136 K ₇ (TiO ₂ ) ₃ SiW ₉ O ₃₇ " 137 K ₇ Ta ₃ SiW ₉ O ₄₀ " 138 K ₆ (TaO ₂ ) ₃ PW ₉ O ₃₇ " 139 K ₆ Ta ₃ PW ₉ O ₄₀ " 140 K ₈ Co ₂ W ₁₁ O ₃₉ " 141 H ₂ [(CH ₃ ) ₄ N ⁺ ] 4 (C ₂ H ₅ Si) ₂ CoW ₁₁ O ₄₀ " 142 H ₂ [(CH ₃ ) ₄ N ⁺ ] ₄ (iso-C ₄ H ₉ Si) ₂ CoW ₁₁ O ₄₀ " 143 K ₉ Nb ₃ P ₂ W ₁₅ O ₆₂ " 144 K ₉ (NbO ₂ ) ₃ P ₂ W ₁₅ O ₅₉ " 145 K ₁₂ (NbO ₂ ) ₆ P ₂ W ₁₂ O ₅₆ Well-Dawson peroxo 146 K ₁₂ Nb ₆ P ₂ W ₁₂ O ₆₂ Wells-Dawson structure ff. 147 a ₂ -K ₁₀ P ₂ W ₁₇ O ₆₁ " 148 K ₆ Fe (III) Nb ₃ P ₂ W ₁₅ O ₆₂ " 149 K ₇ Zn (II) Nb ₃ P ₂ W ₁₅ O ₆₂ " 150 (NH ₄ ) ₆ (aP ₂ W ₁₈ O ₆₂ ) nH ₂ O " 151 K ₁₂ [H ₂ P ₂ W ₁₂ O ₄₈ ] · 24H ₂ O " 152 K ₂ Na ₁₅ H ₅ [PtMo ₆ O ₂₄ ] .8H ₂ O " 153 K ₆ [a ₂ -P ₂ W ₁₇ MoO ₆₂ ] · nH ₂ O " 154 KHP ₂ V ₃ W ₁₅ O ₆₂ · 34H ₂ O " 155 K ₆ [P ₂ W ₁₂ Nb ₆ O ₆₂ ] · 24H ₂ O " 156 Na ₆ [V ₁₀ O ₂₈ ] .H ₂ O " 157 (Guanidinium) ₈ H [PV ₁₄ O ₆₂ ] .3H ₂ O " 158 K ₈ H [PV14O62] " 159 Na ₇ [MnV ₁₃ O ₃₈ ] · 18H ₂ O " 160 K ₆ [BW ₁₁ O ₃₉ Ga (OH) ₂ ]. 13H ₂ O " 161 K ₇ H [Nb ₆ O ₁₉ ]. 13H ₂ O " 162 [(CH ₃ ) ₄ N ⁺ / Na ⁺ / K ⁺ ] ₄ [Nb ₂ W ₄ O ₁₉ ] " 163 [(CH ₃ ) ₄ N ⁺ ] ₉ [P ₂ W ₁₅ Nb ₃ O ₆₂ ] " 164 [(CH ₃ ) ₄ N ⁺ ] ₁₅ [HP ₄ W ₃₀ Nb ₆ O ₁₂₃ ] x 16H ₂ O " 165 [Na / K] ₆ [Nb ₄ W ₂ O ₁₉ ] " 166 [(CH _{3) 4} N ⁺ / Na ⁺ / K ^+] 5 _[Nb3W3O19] .6H ₂ O " 167 K ₅ [CpTiSiW ₁₁ O ₃₉ ] · 12H ₂ O " 169 b ₂ -K ₈ [SiW ₁₁ O ₃₉ ] x 14H ₂ O " 170 aK ₈ [SiW ₁₀ O ₃₆ ] · 12H ₂ O " 171 Cs ₇ Na ₂ [PW ₁₀ O ₃₇ ] x 8H ₂ O " 172 Cs ₆ [P ₂ W ₅ O ₂₃ ] · 7.5H ₂ O " 173 g-Cs ₇ [PW ₁₀ O ₃₆ ] · 7H ₂ O " 174 K ₅ [SiNbW ₁₁ O ₄₀ ] .7H ₂ O " 175 K ₄ [PNbW ₁₁ O ₄₀ ] · 12H ₂ O " 176 Na ₆ [Nb ₄ W ₂ O ₁₉ ]. 13H ₂ O " 177 K ₆ [Nb ₄ W ₂ O ₁₉ ] .7H ₂ O " 180 K ₄ [V ₂ W ₄ O ₁₉ ] · 3.5H ₂ O " 181 Na ₅ [V ₃ W ₃ O ₁₉ ] .12H ₂ O " 182 K ₆ [PV ₃ W ₉ O ₄₀ ] · 14H ₂ O " 183 Na ₉ [Ab-GeW ₉ O ₃₄ ] · 8H ₂ O " 184 Na ₁₀ [Aa-GeW ₉ O ₃₄ ] .9H ₂ O " 185 K ₇ [BV ₂ W ₁₀ O ₄₀ ] .6H ₂ O " 186 Na ₅ [CH ₃ Sn (Nb ₆ O ₁₉ )] x 10H ₂ O " 187 Na ₆ [Pt (P (m-SO ₃ C ₆ N ₅ ) ₃ ) ₃ Cl] .3H ₂ O " 188 [(CH ₃ ) ₃ NH ⁺ ] ₁₀ (H) [Si (H) ₃ W ₁₈ O ₆₈ ] · 10H ₂ O " 189 K ₇ [Aa-GeNb ₃ W ₉ O ₄₀ ] · 18H ₂ O " 190 K ₇ [Ab-SiNb ₃ W ₉ O ₄₀ ] · 20H ₂ O " 191 [(CH ₃ ) ₃ NH ⁺ ] ₉ [Aa-HGe ₂ Nb ₆ W ₁₈ O ₇₈ " 192 K ₇ (H) [Aa-Ge ₂ Nb ₆ W ₁₈ O ₇₇ ] · 18H ₂ O " 193 K ₈ [Ab-Si ₂ Nb ₆ W ₁₈ O ₇₇ ] " 194 [(CH ₃ ) ₃ NN ⁺ ] ₈ [AB-Si ₂ Nb ₆ W ₁₈ O ₇₇ ] " a) cf. US 6,020,369 , TABLE 1, columns 3 to 10;
b) Tierui Zhang, Shaoquin Liu, Dirk G. Kurth and Charl FJ Faul, Organized Nanostructured Complexes of Polyoxometalates and Surfactants that Exhibit Photoluminescence and Electrochromism, Advanced Functional Materials, 2009, 19, 642-652 ;
n number, in particular integer, from 1 to 50.

Further examples of suitable POM are from the American patent US Pat. No. 7,097,858 B2 , Column 14, line 56, to column 17, line 19, and from TABLE 8a, column 22, line 41, to column 23, line 28, compounds number 1-53, and TABLE 8b, column 23, line 30, to column 25, line 34, compounds number 1 to 150, known.

Very particularly preferred are H ₄ [Si (W ₃ O ₁₀ ) ₄ ] .xH ₂ O (CAS No. 12027-43-9) and H ₃ [P (W ₃ O ₁₀ ) ₄ ] .xH ₂ O (CAS No. 12501-23-4) and / or their salts.

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.

The POM micro- and / or nanoparticles described above are functionalized, non-functionalized, aggregated, unaggregated, agglomerated, non-agglomerated, supported, and / or unsupported. For example, they may be functionalized, agglomerated and supported. But they can also not be functionalized and aggregated.

The POM micro- and / or nanoparticles to be used according to the invention can be present "naked". That is, their surface is not surrounded by a shell and / or is not functionalized.

In addition, the POM micro- and / or nanoparticles to be used according to the invention may be surrounded by a shell and / or carry at least one functional group. In this case, 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 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 material of the shell and / or the functional groups are selected such that the POM micro- and / or nanoparticles to be used according to the invention are distributed particularly rapidly and homogeneously in an organic and / or inorganic phase and / or the physical and / or modify or mask chemical properties of the POM micro- and / or nanoparticles in a particular 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, i. H. be solvable 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.

The following are 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. 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.

Common and known functional groups:

• Fluorine, chlorine, bromine and iodine atoms; Hydroxyl, thiol, ether, thioether, amino, peroxide, aldehyde, acetal, carboxyl, peroxycarboxyl, ester, amide, hydrazide and urethane groups; Imide, hydrazone and hydroxime, amide and hydroxamic acid groups; Groups derived from formamidine, formamidoxime, formamidrazone, formhydrazidine, formhydrazidoxime, formamidrazone, formoxamidine, formhydroxamoxime and formoxamidrazone; Nitrile, isocyanate, thiocyanate, isothiocyanate, isonitrile, lactide, lactone, lactam, oxime, nitroso, nitro, azo, azoxy, hydrazine, hydrazone, azine, carbodiimide , Azide, azane, sulfen, sulfenamide, sulfonamide, thioaldehyde, thioketone, thioacetal, thiocarboxylic acid, sulfonium, sulfur halide, sulfoxide, sulfone, sulfimine, sulfoximine, sultone, sultam, , Sulfonic, silane, siloxane, phosphine, phosphine, phosphonium, phosphoric, phosphorous, phosphonic, phosphate, phosphinate and phosphonate groups.

Common and known functional additives:

Examples of suitable additives are low-boiling organic solvents and high-boiling organic solvents ("long solvents"), UV absorbers, light stabilizers, free-radical scavengers, defoamers, emulsifiers, wetting and dispersing agents and surfactants, leveling agents, film-forming auxiliaries, rheology control additives (thickeners), flame retardants , Siccatives, drying agents, skin preventatives, corrosion inhibitors, waxes or matting agents.

Examples of suitable low-boiling organic solvents and high-boiling organic solvents ("long 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 ^® .

Examples of suitable emulsifiers, wetting and dispersing agents or surfactants are the customary and known anionic, cationic, nonionic and zwitterionic wetting agents, as described, for example, in US Pat Römpp Online, April 2014, Georg Thieme Verlag, »Wetting Agents« will be described in detail.

An example of a suitable coupling agent is tricyclodecanedimethanol.

Examples of suitable film-forming auxiliaries are cellulose derivatives such as cellulose acetobutyrate (CAB).

Examples of suitable transparent fillers and carriers are those based on silica, alumina or zirconium oxide; In addition, it is still on the Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house, Stuttgart, 1998, pages 250 to 252 , referenced.

Examples of suitable rheology-controlling additives are those from the patents WO 94/22968 . EP 0 276 501 A1 . EP 0 249 201 A1 or WO 97/12945 known; crosslinked polymeric microparticles, as described for example in the EP 0 008 127 A1 are disclosed; inorganic phyllosilicates such as aluminum-magnesium silicates, sodium magnesium and sodium magnesium fluorine lithium phyllosilicates of the montmorillonite type; 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 copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates.

An example of a suitable matting agent is magnesium stearate.

Further examples of additives are dyes, colored pigments, white pigments, fluorescent pigments and phosphorescent pigments (phosphors) and the materials described below.

Carbohydrates:

• 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.

Monoalcohols:

• Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol isoamyl alcohol, cyclopentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and their stereoisomers.

polyols:

• 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-, undeca- and dodecaglycerol, -trimethylolpropane, -erythritol, -threitol and -pentaerythritol, 1,2,3,4-tetrahydroxycyclohexanes, 1,2,3,4,5-pentahydroxycyclohexanes, myo-, scyllo-, muco- , chiro-, neo-, allo-, epi- and cis-inositol.

polyhydroxycarboxylic:

• Glycerol, citric, tartaric, threonine, erythron, xylon, ascorbic, glucone, galacturon, iduron, mannuron, glucuron, guluron, glycuron, glucar, uluson, diketogulone, and lactobionic.

Polyhydroxyphenols and -benzenecarboxylic acids:

• Pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-trishydroxybenzene, phloroglucinol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dihydroxybenzoic and 2,4,6-, 2,4,5-, 2,3,4- and 3,4,5-trihydroxybenzoic acid (bile acid).

amines:

• Ammonia, ammonium, mono-, di- and trialkyl-, -aryl-, cycloalkyl-, -alkylaryl-, -alkylcycloakyl-, -cycloalkylaryl- and -alkylcycloalkylarylamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert. Butylamine, benzylamine, cyclohexylamine, dodecylamine, cocoamine, tallowamine, adamantylamine, aniline, ethylenediamine, propylenediamine, butylenediamine, piperidine, piperazine, pyrazolidine, pyrazine, quinuclidine and morpholine.

fatty acids:

• Lauric, myristic, oleic, palmitic, linoleic, stearic, arachinic and behenic acid.

Polymers and oligomers with functional groups:

• Poly (trimethylammoniumethylacrlylat), polyacrylamide, poly (D, L-lactide-co-ethylene glycol), Pluronic ^®, Tetronic ^®, Polyvinyl alcohol (PVA), polyvinyl pyrrolidone (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) (MATAC), 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 Arginylglycylasparginsäure (RGD), AGKGTPSLETTP peptide (A54), HSYHSHSLLRMF peptide (C10) and Gluthathion, enzymes such as glucose oxidase, dendrimers such Polypropyleneimine tetrahexacontaamine dendrimer generation 5 (PPI G5), poly (amidoamine) (PAMAM) and guanidine dendrimers, phosphonic acid and dithiopyridine functionalized polystyrenes, functionalized polyethylene glycols (PEG: degree of polymerization 4-10, especially 5) such as PEG (5) -nitroDOPA, -nitrodopamine, -mimosine, -hydroxydopamine, -hydroxypyridine, -hydroxypyrone and -carboxyl.

complexing agents:

• Complexones such as nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA), phosphonic acids such as [(2-aminoethyl) hydroxymethylene] - and [(5-aminopentyl) hyroxymethylene] diphosphonic acid and crown ethers.

Metal Complexes:

Usual and known coordination, sandwich and chelate complexes of the abovementioned metals and their cations with organic and inorganic anions, in particular fluoride, chloride, bromide, iodide, ammonia, amines, phosphines, thiols, sulfides, cyanide, cyanate, isocyanate, thiocyanate, Isothiocyanate, boranes, carbon monoxide, aromatics or heteroaromatics.

In particular, wetting agents or surfactants are used as additives, since - if necessary - prevents aggregation and / or agglomeration of the POM micro- and / or nanoparticles and a homogeneous distribution in an organic and / or inorganic phase 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 list is therefore intended to illustrate the variety of possibilities, and the expert can readily specify other options due to his general expertise.

The POM micro- and / or nanoparticles to be used according to the invention can be present "naked". That is, their surface is not surrounded by a shell and / or is not functionalized.

Preferably, the POM micro- and / or nanoparticles to be used according to the invention are surrounded by a shell and / or carry at least one functional group. In this case, 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 phase, in particular an organic and / or inorganic polymer Phase or inorganic ceramic phase, which acts as a carrier material and / or binder, distribute 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 nanoparticles and the shell and / or the functional groups may be permanent or reversible, i. H. be solvable 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.

The following are 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. 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.

Common and known functional groups:

• Fluorine, chlorine, bromine and iodine atoms; Hydroxyl, thiol, ether, thioether, amino, peroxide, aldehyde, acetal, carboxyl, peroxycarboxyl, ester, amide, hydrazide and urethane groups; Imide, hydrazone and hydroxime, amide and hydroxamic acid groups; Groups derived from formamidine, formamidoxime, formamidrazone, formhydrazidine, formhydrazidoxime, formamidrazone, formoxamidine, formhydroxamoxime and formoxamidrazone; Nitrile, isocyanate, thiocyanate, isothiocyanate, isonitrile, lactide, lactone, lactam, oxime, nitroso, nitro, azo, azoxy, hydrazine, hydrazone, azine, carbodiimide , Azide, azane, sulfen, sulfenamide, sulfonamide, thioaldehyde, thioketone, thioacetal, thiocarboxylic acid, sulfonium, sulfur halide, sulfoxide, sulfone, sulfimine, sulfoximine, sultone, sultam, , Sulfonic, silane, siloxane, phosphine, phosphine, phosphonium, phosphoric, phosphorous, phosphonic, phosphate, phosphinate and phosphonate groups.

Common and known functional additives:

Examples of suitable additives are low-boiling organic solvents and high-boiling organic solvents ("long solvents"), water, UV absorbers, light stabilizers, free-radical scavengers, deaerating agents, slip additives, defoamers, emulsifiers, wetting and dispersing agents and surfactants, adhesion promoters, leveling agents, film-forming auxiliaries rheology control additives (thickeners), skin preventatives, corrosion inhibitors, waxes, matting agents, perfumes, perfumes, dyes, pigments, fillers, ureas and abrasives.

Examples of suitable low-boiling organic solvents and high-boiling organic solvents ("long 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 ^® .

Examples of suitable emulsifiers, wetting and dispersing agents or surfactants are the customary and known anionic, cationic, nonionic and zwitterionic wetting agents, as described, for example, in US Pat Römpp Online, April 2014, Georg Thieme Verlag, »Wetting Agents« will be described in detail.

An example of a suitable coupling agent is tricyclodecanedimethanol.

Examples of suitable film-forming auxiliaries are cellulose derivatives such as cellulose acetobutyrate (CAB).

Examples of suitable transparent fillers are those based on silica, alumina or zirconia; In addition, it is still on the Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house, Stuttgart, 1998, pages 250 to 252 , referenced.

Examples of suitable rheology-controlling additives are those from the patents WO 94/22968 . EP 0 276 501 A1 . EP 0 249 201 A1 or WO 97/12945 known; crosslinked polymeric microparticles, as described for example in the EP 0 008 127 A1 are disclosed; inorganic phyllosilicates such as aluminum-magnesium silicates, sodium magnesium and sodium magnesium fluorine lithium phyllosilicates of the montmorillonite type; 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 copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates.

An example of a suitable matting agent is magnesium stearate.

Further examples of additives are dyes, colored pigments, white pigments, fluorescent pigments and phosphorescent pigments (phosphors).

Carbohydrates:

• 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 and glycosaminoglycans.

Monoalcohols:

• Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol isoamyl alcohol, cyclopentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and their stereoisomers.

polyols:

• 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-, undeca- and dodecaglycerol, -trimethylolpropane, -erythritol, -threitol and -pentaerythritol, 1,2,3,4-tetrahydroxycyclohexanes, 1,2,3,4,5-pentahydroxycyclohexanes, myo-, scyllo-, muco- , chiro-, neo-, allo-, epi- and cis-inositol.

polyhydroxycarboxylic:

• Glycerol, citric, tartaric, threonine, erythron, xylon, ascorbic, glucone, galacturon, iduron, mannuron, glucuron, guluron, glycuron, glucar, uluson, diketogulone, and lactobionic.

Polyhydroxyphenols and -benzenecarboxylic acids:

• Pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-trishydroxybenzene, phloroglucinol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dihydroxybenzoic and 2,4,6-, 2,4,5-, 2,3,4- and 3,4,5-trihydroxybenzoic acid (bile acid).

fatty acids:

• Lauric, myristic, oleic, palmitic, linoleic, stearic, arachinic and behenic acid.

Polymers and oligomers with functional groups:

• Poly (trimethylammoniumethylacrlylat), polyacrylamide, poly (D, L-lactide-co-ethylene glycol), Pluronic ^®, Tetronic ^®, Polyvinyl alcohol (PVA), polyvinyl pyrrolidone (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) (MATAC), 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 Arginylglycylasparginsäure (RGD), AGKGTPSLETTP peptide (A54), HSYHSHSLLRMF peptide (C10) and glutathione, enzymes such as glucose oxidase, dendrimers such as polypropyleneimine Tetrahexacontaamin dendrimer generation 5 (PPI G5), poly (amidoamine ) (PA MAM) and guanidine dendrimers, phosphonic acid and dithiopyridine functionalized polystyrenes, functionalized polyethylene glycols (PEG: degree of polymerization 4-10, especially 5) such as PEG (5) -nitroDOPA, -nitrodopamine, -mimosine, -hydroxydopamine, -hydroxypyridine, -hydroxypyrone and carboxyl.

complexing agents:

• Complexones such as nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA), phosphonic acids such as [(2-aminoethyl) hydroxymethylene] - and [(5-aminopentyl) hyroxymethylene] diphosphonic acid and crown ethers.

Metal Complexes:

Usual and known coordination, sandwich and chelate complexes of the abovementioned metals and their cations with organic and inorganic anions, in particular fluoride, chloride, bromide, iodide, ammonia, amines, phosphines, thiols, sulfides, cyanide, cyanate, isocyanate, thiocyanate, Isothiocyanate, boranes, carbon monoxide, aromatics or heteroaromatics.

In particular, wetting agents or surfactants are used as additives, since - if necessary - prevents aggregation and / or agglomeration of the POM nanoparticles and a homogeneous distribution in an organic and / or inorganic phase is achieved.

The above-listed functional groups and materials for the shells of the POM nanoparticles are given only by way of example 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 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. Preferably, the content is 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 respective cleaning or personal care product.

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.

Otherwise, 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.

The term "cleaning" includes in particular the cleaning of laundry and textiles with detergents, in particular with heavy duty detergents, color detergents or fabric conditioners, and gallic 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.

The term "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).

The term "personal care products" includes skin and hair cleansers such as lotions, creams, ointments, shower gels, shampoos, fluid and solid soaps, hand washing pastes, moisturizers (moisterizers), bath water additives, dentifrices and mouthwashes such as toothpastes and mouthwashes, manicure care products 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 conditioners and depilatory agents. 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 according to the invention. For this purpose, 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. For mixing, customary and known mixing units such as stirred tanks, inline dissolvers, counterflow mixers, extruders or kneaders can be used. After homogenization, the resulting cleaning and personal care products according to the invention for use according to the invention are filled into containers.

It is understood that the features mentioned above and explained in more detail below can be used not only in the specified combinations and configurations, but also in other combinations and configurations or in isolation, without departing from the scope of the present invention.

Examples

Examples 1 and 2 and Comparative Experiment 1

Nano-liquid cleaner

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). 0.5 part by weight of a surfactant, 0.5 part by weight of a fragrance and 2 parts by weight of H ₄ [Si (W ₃ O ₁₀ ) ₄ ] .xH ₂ O (CAS No. 12027-43-9) (mixture 1, example 1 ) or H ₃ [P (W ₃ O ₁₀ ) ₄ ] .xH ₂ O (CAS No. 12501-23-4) (Mixture 2, Example 2) each having an average particle size of 100 nm.

For comparison, a liquid cleaner of 60 parts by weight of distilled water, 39 parts by weight of a mixture of ethanol and isopropanol (1: 1), 0.5 parts by weight of a surfactant, 0.5 and 0.5 parts by weight of a fragrance was prepared (mixture 3 Comparative Experiment 1).

The three liquid cleaners were filled into one spray bottle each.

For the cleaning effect and biocidal effect tests, three planar glass sheets 1 to 3 heavily soiled with oil, fat, microorganisms and loam were provided.

For Comparative Experiment 1, a soiled glass sheet 3 was sprayed with the mixture 3. Subsequently, 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.

For Examples 1 and 2, the two other soiled glass panes 1 and 2 were each sprayed with the mixture 1 or the mixture 2. Subsequently, 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.

After 14 days, 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.

Example 3

The biocidal effect of polyoxometalate in commercial cleaning and personal care products

The following commercially available cleansing and personal care products were each containing 2% by weight of H ₄ [Si (W ₃ O ₁₀ ) ₄ ] .xH ₂ O (CAS No. 12027-43-9) (based on the respective composition) ( Series 1, Example 3) or H ₃ [P (W ₃ O ₁₀ ) ₄ ] .xH ₂ O (CAS No. 12501-23-4) (Series 2, Example 3), after which the respective mixtures of the two series were homogenized:

Hand Gel:

• Biogard ^® - surgical hand gel with aloe vera;

Make-up remover:

• Nivea ^® 2 in 1 milk and honey,
• Neutrogena ^® - oil-free eye make-up remover;

Facial Cleanser:

• Neutrogena ^® - naturally cleansing facial cleanser,
• Kiehl's ^® ULTRA FACIAL CLEANER FOR ALL SKIN TYPES,
• Cetaphil ^® Daily Facial Cleanser;

After shave:

• Weleda ^® ,
• Ax ^® Dark Temptation,
• Neal's Yard Men Aftershave Balm;

Deodorant:

• ^Nivea® Black and White;

Sun protection:

• ^Nivea® Sun Protection and Bronze;

Lip Care:

• ^Nivea® Lip Butter;

Shower gel:

• Nivea ^® Creame Care;

Hand Cream:

• Nivea ^® .

When the cleansing and care products were used as intended, it was found that the 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.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US Pat. No. 6713076 B1 [0024]
• EP 1078121 B1 [0024]
• EP 1439261 A2 [0024]
• US 6911470 B1 [0025]
• US 5824706 [0026]
• US 6020369 [0026, 0055, 0056]
• US 6723349 B2 [0027]
• US 7097858 B2 [0027, 0057]
• WO 2006/036269 A2 [0028]
• RO 122728 [0029]
• MD 4014 B1 [0030]
• WO 94/22968 [0076, 0095]
• EP 0276501 A1 [0076, 0095]
• EP 0249201 A1 [0076, 0095]
• WO 97/12945 [0076, 0095]
• EP 0008127 A1 [0076, 0095]

Cited non-patent literature

• Römpp Online, Version 3.47 »Heteropolyacids« [0015]
• Article »Fabrication and Characterization of Antibacterial-active Multilayer Films Based on Keggin Polyoxometalates and Methylene Blue«, in Z. Naturforsch. 2010, 65b, pages 140-146, describe Dan Chen, Jun Peng, Haijun Pang, Pengpeng Zhang, Yuan Chen, Yan Shen, Chanyung Chen, and Huiyuan Ma. [0016]
• Antibiotic protection by [P2W18O62] 6-, [SiMo12O40] 4-, and [PTi2W10O40] 7- by methicillin-resistant and vacomycin-resistant Staphylococcus aureus «in Journal of Inorganic Biochemistry, 100 (2006 ), Pages 1225 to 1233, describe Miyauo Inue, Tokomo Suzuki, Yutaka Fujita, Mayumi Oda, Nobuhiro Matsumato, and Thoshihiro Yamase. [0017]
• "K27 [KAs4W40O140] and K18 [KSb9W21O86], and Keggin-structural polyoxotungstates agaist Helicobacter pylori", in Journal of Inorganic Biochemistry, 99 (2005), pp. 1023 to 1031, describe Miyao Inoue, "Antibacterial Activity of Highly Negatively Charged Polyoxotungstates. Keiko Segawa, Sae Matsunaga, Nobuhiro Matsumoto, Mayumi Oda, and Toshihiro Yamase. [0018]
• Yuhua Feng, Zhangan Han, Jun Pen, Jun Lu, Bo Xue, Li Li, Describe Yuhua Feng, Jun Li, Huiyuan Ma and Enbo Wang [0019]
• Shuiping Chen, Guozhong Wu, Dewu Long, and Yaodang Liu describe the preparation, characterization, and antibacterial activity of chitosan-Ca3V10O28 complex membrane, in Carbohydrate Polymers, 64 (2006), pages 92 to 97. [0020]
• Article "Studies of the first antibacterial agent of pipemidic acid modifying Keggin polyoxometalate" in Inorganic Chemical Communication, 14, pp. 1192-1195, 2011, C. Li et al. [0021]
• J.-Q., Polyhedron 31, pp. 422-430, 2012, describe J.-Q. "Study on the ligation of copper complexes of quinolone antibacterial drugs and octamolybdate". Sha et al. [0022]
• "Studies on the interactions of Ti-containing polyoxometalates (POMs) with SARS-CoV 3Clpro by molecular modeling" in Journal of Inorganic Biochemistry, 101, pages 89 to 94, 2007, describe D. Hu et al. [0023]
• Zui, Shaoquin Liu, Dirk G. Kurth, and Charl FJ Faul, Organized Nanostructured Complexes of Polyoxometalates and Surfactants that Exhibit Photoluminescence and Electrochromism, Advanced Functional Materials, 2009, 19, 642-652 [0056]
• Römpp Online, April 2014, Georg Thieme Verlag, »Wetting Agents« [0072]
• Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252 [0075]
• Römpp Online, April 2014, Georg Thieme Verlag, »Wetting Agents« [0091]
• Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252 [0094]

Claims (8)

Hydrous cleaning and personal care products having a biocidal effect, comprising functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate nanoparticles having an average particle size of 1 nm to <1000 nm. Hydrous cleaning and personal care compositions according to claim 1, characterized in that five functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate nanoparticles have an average particle size of 2 nm to 500 nm. Hydrous cleaning and personal care products according to claim 1 or 2, characterized in that they contain the functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported nanoparticles of polyoxometalate in an amount of 0.1 to 50 % By weight, based in each case on the cleaning or personal care product in question. Hydrous cleaning and personal care products according to one of claims 1 to 3, characterized in that they additionally functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate microparticles having an average particle size of 1 micron to <1000 microns included. Hydrous cleaning and personal care products according to one of claims 1 to 4, characterized in that they are H ₄ [Si (W ₃ O ₁₀ ) ₄ ] .xH ₂ O (CAS No. 12027-43-9) and / or H ₄ [P (W ₃ O ₁₀ ) ₄ ] .xH ₂ O (CAS No. 12501-23-4) and / or their salts. Hydrous cleaning and personal care products according to any one of claims 1 to 5, characterized in that it contains at least one constituent selected from the group consisting of surfactants, abrasives, acids, bases, bleaches, enzymes, fragrances, deodorants, fragrances, perfumes antiperspirants, Odor absorbers, enzyme inhibitors, antioxidants, dyes, whiteners or ingredients that help prevent or reduce re-contamination. Process for the preparation of hydrous cleansing and personal care products having a biocidal effect according to one of Claims 1 to 6, characterized in that their constituents are mixed simultaneously or successively, after which the resulting mixture is homogenised and filled into containers. Use of the water-containing cleaning and personal care products with biocidal effect according to one of claims 1 to 6 or the water-containing cleaning and personal care products with biocidal effect prepared for the process according to claim 7 for cleaning laundry and textiles, dishes, surfaces in living and working spaces, Kitchen and bath utensils, pipes, brakes and automobiles as well as for the cleaning of skin and hair, for the skin care, the hair care, the tooth and oral care, the cleaning and care of the fingernails (manicure) and the feet (pedicure), influencing the Body odor, the decorative cosmetics, lip care, shaving, beard care and hair removal (depilation).