DE102007008026A1 - Biocidal composition especially for use e.g. on ships or in paints, plastics or medical materials or apparatus contains an inorganic solid as a pigment and/or filler - Google Patents

Abstract

A biocidal composition contains an inorganic solid as a pigment and/or filler. An independent claim is also included for production of the composition involving mixing the inorganic solid in known fashion and modifying its surface, especially during or after precipitation. ACTIVITY : Algicide; Fungicide; Microbiocide.

Description

object The present invention is a biocidal composition Process for their preparation and use of the biocidal composition.

Especially The present invention is concerned with a biocidal composition based on zinc sulfide, zinc oxide, barium sulfate, lithopones, Titanium dioxide, alumina, silica, calcium carbonate, calcium sulfate, and / or zeolites, preferably based on zinc sulfide, zinc oxide, Barium sulfate, and / or lithopones.

biocides (from Greek / Latenisch: Lebensstöter) are active substances in a variety of products are used to, depending on the individual case, a broad spectrum of organisms of viruses, bacteria, algae, To kill fungi, insects, mollusks and rodents. On There are around 8,000 biocidal products on the market, including small and microorganisms Eliminate, put off or decimate, that for the people in certain Situations undesirable are. These include especially agents against bacteria, algae and fungi, but also such against spiders, mice, Rats, flies or mosquitoes. Typical biocidal products are wood preservatives; Insect sprays for the household, moldy wall paints for Bathroom or kitchen, antibacterial household cleaners, disinfectant sprays and attractants against clothes moths. Biocide products are widely available as ready-to-use Article to the consumer. Thus, textiles with the quality label "Wool Seal" are always moth-proofed equipped.

Corresponding their effect against different groups of organisms one speaks of Microbicides (against microorganisms), insecticides (against insects), Molluscicides (against mollusks), rodenticides (against rodents) and immediately. The microbicides include the algicides, bactericides, fungicides and virucides.

algaecides are compounds that kill algae or inhibit their growth or reproduction. Are paint acidicides homogeneously distributed in paints, with the resulting paints are permanently protected against fouling by algae, even under unfavorable conditions Conditions, such as exposure to rain and light. It follows that Painting acidides practically insoluble in water and light stable. It is also expected that paint acidicides do not discolour the paint, nonvolatile, low in toxicity and compatible with other paint components. examples for Paleuricides include chlorothalonil, diuron and dichlofluanid.

fungicides are microbicides that kill fungi and their spores. They will be among others in wood protection against blue stain (Wood discoloring Mushrooms) and wood destroying Mushrooms used, as well as to increase the growth of harmful fungi Food, textiles, walls, Paper, wood, glue, paints, lubricants and even fuels etc. to prevent.

Antifouling paints are paints that are applied in the underwater area of ships, derricks, etc. become and inhibit growth there. Characteristic of antifouling paints is the content of algicidal and fungicidal compounds, usually Copper oxide and organotin compounds, in particular the Organotin organically are questionable.

In Applications such as paints, paints, plastics, medical Products etc. are used as biocides, especially as microbicides, metal ions used, in particular in the form of compositions based on of metal salts. The metal ions are in particular heavy metal ions, such as copper, silver, tin and Nickel ions.

For the treatment Water, for example, water-soluble inorganic in the art Metal salts such as copper sulfate, copper nitrate and copper chloride for use as algaecides or bactericides for the treatment proposed. The use of copper or copper ion sources However, it has the disadvantage, among other things, that copper ions in alkaline or near alkaline media with naturally occurring anions react and as insoluble Salts, for example as carbonates, oxides or hydroxides precipitate. These pH dependent precipitation leads to Losses of biocidal activity, since then no more copper ions are available.

Besides, they are Copper salt biocides are more effective against algae than against bacteria and other pathogens. Therefore, a significant biocidal activity of copper salts to achieve against bacteria are higher concentrations of copper necessary, which is not desired is. Should be with copper salt algicides and bacteria or other pathogens are effective, so this generally requires the use of additional Biocides.

Out Also known in the art is the manufacture and Use of microbicidal compositions in inorganic carriers such as For example, the oxides of titanium, magnesium, aluminum, silicon, of barium sulfate and zeolites, especially for use in polymers (US-A-4,525,410, US-A-4,775,585, US-A-4,906,466).

EP-B-1463411 discloses the use of zinc sulfide as an anti-mite agent. Zinc sulfide is used in formulations for sizing threads, fibers, and filaments and in a liquid or solid composition for the cleaning or treatment of textile surfaces.

in the However, the prior art does not disclose a technical teaching which allows, to provide a biocidal composition by the combination inorganic solids and biocidal substances in various Applications as required as algaecide and / or fungicide and / or antibacterial effect.

Also In the prior art, no technical teaching is disclosed which fixes the problem that certain inorganic solids, such as the Pigments such as zinc oxide, zinc sulfide, titanium dioxide, and lithopone, only a very slower activity against algae as well as bacteria and / or have other pathogens. Furthermore For example, zinc oxide, zinc sulfide, titanium dioxide and lithopone are generally more effective against algae as against bacteria and other pathogens. To reach a significant biocidal activity, it is according to the state the technique required to use high concentrations, what not wished is. Barium sulfate is even completely inert, that is, it shows even in high concentrations no biocidal activity.

task The object of the present invention is to overcome the disadvantages of the prior art Technology to overcome.

Especially The object of the invention is to provide a biocidal composition depending on the application and need as algaecide and / or fungicide and / or antibacterial effect.

A Another object of the present invention is to provide a biocidal To provide a composition that works against algae as well works against fungi as well as against bacteria.

According to one Another object of the invention is this composition in various applications such as paints and paints, such as water colors or on water based inks, coatings, rough plaster or plaster layers, Glazes, impregnations, semidicken coatings, plastics, medical items used can be.

According to one Another object of the invention is the biocidal composition consist of inorganic solids, preferably pigments, fillers and / or nanoscale particles, wherein among nanoscale particles those are understood whose average particle size is below of 250 nm.

According to one Another object of the invention is the inorganic used Preferably solids themselves have biocidal properties.

According to one Another object of the invention is the pigment or filler properties of inorganic solids are retained.

A Another object of the invention is to provide a novel coating composition to provide a biocidal effect in the end use having.

According to one Another object of the invention is the new coating composition a higher, immediate and long-lasting efficacy against algae, fungi and / or bacteria exhibit. About that In addition, this coating composition should be used as an antifouling paint be used and in ships and other marine vehicles, devices and devices fouling marine creatures such as algae, shells, Prevent cancers etc.

Surprisingly the tasks were solved by the features of the main claim. Preferably Embodiments can be found in the subclaims.

Especially it was surprisingly found that the above-mentioned objects are achieved by inorganic solids, those with one or more biocidal substances, in particular Metal salt compounds, surface-modified.

When inorganic solid can all as pigment or fillers usable compounds, for example zinc sulfide, zinc oxide, Barium sulfate, barite, mica, talc, kaolin, lithopone, titanium dioxide, Alumina, silica, calcium carbonate, calcium sulfate, zeolites, Iron oxide, magnesium hydroxide, aluminum hydride, carbon, in particular Graphite, are used. The solid can be both natural as well as of synthetic origin.

to surface modification are preferably metal salts which have a biocidal property, used. It can as metal salts, inorganic or organic substances, individually or in mixture, to be used. As starting material for the surface modification of inorganic solids the compounds or salts of metals, for example zinc, Copper, silver and / or tin, preferably of zinc, find application.

Basically, all soluble or sparingly soluble salts of biocidal metals may be used singly or in admixture for surface modification of inorganic solids.

The Addition amount of the metal salts is based on the mass of the inorganic Solid at 0.01 to 50% by weight, preferably at 0.1 to 30% by weight, particularly preferably at 0.5 to 20% by weight.

The mean particle size of the inorganic Solids, as far as they are nanoscale, are between 200 and 1 nm, preferably between 120 and 2 nm, more preferably between 100 and 4 nm, most preferably between 80 and 5 nm.

The mean particle size of the inorganic Solids, unless they are nanoscale, are between 0.25 and 500 μm, preferably between 0.3 and 200 μm, more preferably between 0.3 and 30 microns.

there can the particles have different shapes, for example platelets, Needle, sphere or epitaxial shape.

When Inorganic solids are preferably used substances which itself a biocidal property, for example algicide and / or have microbicide. In particular, in the manufacture of the biocides according to the invention Composition zinc oxide, zinc sulfide, titanium dioxide and / or lithopone used.

In addition, can According to the invention also barium sulfate be used.

When Metal salts are preferably used zinc salts, for example Zinc sulfate (hepta- and / or monohydrate), zinc chloride, zinc nitrate, Zinc bromoite, zinc iodide, zinc borate, zinc fluoride, zinc acetate, zinc citrate, Zinc acetylacetonate, zinc formate, zinc lactate, zinc oxalate, zinc salicylate, Zinc laurate, zinc valerate, zinc stearate, zinc phosphate or mixtures at least two of these substances.

Especially Preferably, organic zinc salts are used, for example Zinc acetate, zinc citrate, zinc acetylacetonate, zinc formate, zinc salicylate, Zinc benzoate or mixtures of at least two of these substances. Especially Zinc acetate, zinc citrate, zinc oxalate or mixtures are preferred used from at least two of these substances.

The Composition can be prepared by methods known per se, be, for example by mixing the ingredients of the invention. It can the surfaces the inorganic solids are preferably modified.

at the surface modification of inorganic solids by the corresponding metal salts can all possible Variants that correspond to the prior art and are known used become. For example, the surface modification in the precipitation of the inorganic solids, in the treatment of inorganic solids in suspension before drying or before or after grinding carried out become.

The finely divided, inorganic solids are preferably in the form of an aqueous suspension or as a filter cake (paste-shaped or as dough). It is advantageous to leave a filter cake undried, for example, from ongoing production use.

The Drying of the provided with the metal salts suspension or the provided with the metal salts filter cake can by means of conventional drying units respectively. Preference is given to spray dryers, Grinder or vacuum dryer used.

in the Trap of surface treatment The inorganic solids after drying can be added the biocidal compounds in liquid form or in powder form respectively. To homogenize the mixture, the usual mixing units, for example Plowshare mixer or drum mixer. Depending on used compound before, during and after the mixture one Temperature treatment can be performed. If necessary, subsequent grinding can be carried out. In In this case, preferably the mixtures of a steam jet, Subjected to air jet or pin grinding.

A different possibility, Metal salts on the surface to modify the inorganic solids is the direct treatment of inorganic solids with the appropriate acid. there For example, by the treatment of zinc sulfide, zinc oxide, Zinc sulfide, titanium dioxide, barium sulfate and / or lithopones with corresponding acids like sulfuric acid, Nitric acid, Hydrofluoric acid, Hydrochloric acid, bromic, iodic acid, boric acid, Phosphoric acid, peroctanoic acid, glycolic acid, oxalic acid, lactic acid, citric acid, benzoic acid, salicylic acid, Acetylacetone or a fatty acid the desired zinc salts educated. It can the acids used singly or in mixture.

to surface treatment The inorganic solids with acids can be all kinds of procedures that are known to be used. The treatment during the Precipitation, before drying, after drying, before grinding or else after grinding done.

The Addition of acids is controlled so that the amount of metal salts formed based on the mass of inorganic solids at 0.01 to 50% by weight, preferably at 0.1 to 30% by weight, more preferably at 0.5 to 20% by weight.

The Biocide according to the invention acting composition can, depending on the field of use as a powder, Paste, suspension or slurry are present.

• – eine biozide Zusammensetzung, die anorganische Feststoffe enthält, wobei es sich bei den anorganischen Feststoffen um Pigmente und/oder Füllstoffe handelt, wobei – es sich bei den anorganischen Feststoffen um Zinksulfid, Zinkoxid, Bariumsulfat, Schwerspat, Glimmer, Talkum, Kaolin, Lithopone, Titandioxid, Aluminiumoxid, Siliciumdioxid, Calciumcarbonat, Calciumsulfat, Zeolithe, Eisenoxid, Magnesiumhydroxid, Aluminiumhydroxid, Kohlenstoff, insbesondere Graphit, oder Mischungen aus mindestens zwei dieser Stoffe handelt; – die anorganischen Feststoffe in Form von nanoskaligen und/oder nicht nanoskaligen Partikeln vorliegen, – der mittlere Teilchendurchmesser der anorganischen Feststoffe, soweit sie nanoskalig sind, zwischen 200 und 1 nm, bevorzugt zwischen 120 und 2 nm, besonders bevorzugt zwischen 100 und 4 nm, ganz besonders bevorzugt zwischen 80 und 5 nm beträgt, – der mittlere Teilchendurchmesser der anorganischen Feststoffe, soweit sie nicht nanoskalig sind, zwischen 0,25 und 500 µm, bevorzugt zwischen 0,3 und 200 µm, besonders bevorzugt zwischen 0,3 und 30 µm beträgt, – die anorganischen Feststoffe in Plättchen-, Nadel-, Kugel- und/oder epitaktischer Form, vorliegen – und / oder die Oberfläche der anorganischen Feststoffe modifiziert ist, bevorzugt mit einem Metallsalz, wobei • es sich bei dem Metallsalz um ein Salz des Zinks, des Kupfers, des Silbers, des Zinns oder um Mischungen aus mindestens zwei dieser Metallsalze handelt, • es sich bei dem Metallsalz um ein Metallsalz der Schwefelsäure, Salpetersäure, Flusssäure, Salzsäure, Bromsäure, Iodsäure, Borsäure, Phosphorsäure, Peroctansäure, Glykolsäure, Oxasäure, Milchsäure, Zitronensäure, Benzoesäure, Salicylsäure, des Acetylacetons, einer Fettsäure oder um eine Mischung aus mindestens zwei der Salze dieser Säuren handelt, wobei als Fettsäure eine C₁- bis C₁₈-Fettsäure, vorzugsweise Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Valeriansäure, Caprinsäure, Laurinsäure, Stearinsäure oder eine Mischung aus mindestens zwei dieser Säuren bevorzugt ist, • es sich bei dem Metallsalz vorzugsweise um ein Metallsalz der Essigsäure, der Oxalsäure oder der Zitronensäure handelt, • es sich es sich bei dem Metallsalz um ein Zinksalz handelt, bevorzugt ausgewählt aus den anorganischen Zinksalzen Zinksulfat, vorzugsweise Zinksulfatheptahydrat oder Zinksulfatmonohydrat, Zinknitrat, Zinkfuorid, Zinkchlorid, Zinkbromid, Zinkiodid, Zinkborat, und/oder den organischen Zinksalzen Zinkformiat, Zinkacetat, Zinkvalerat, Zinklaurat, Zinkstearat, Zinkphosphat, Zinkoxalat, Zinklactat, Zinkcitrat, Zinksalicylat, Zinkbenzoat, Zinkacetylacetonat, oder Mischungen aus mindestens zwei dieser Salze, besonders bevorzugt ausgewählt aus Zinkacetat, Zinkoxalat, Zinkcitrat oder Mischungen aus mindestens zwei dieser Metallsalze • und / oder der Anteil des Metallsalzes, bezogen auf die Masse des anorganischen Feststoffes, 0,01 bis 50 Gew;-%, bevorzugt 0,1 bis 30 Gew;-%, besonders bevorzugt 0,5 bis 20 Gew;-% beträgt;
• – eine wie oben beschriebene biozide Zusammensetzung, die als Pulver, Paste, Suspension oder Slurry vorliegt;
• – eine wie oben beschriebene biozide Zusammensetzung, wobei die anorganischen Feststoffe algizide, fungizide und/oder antibakterielle Eigenschaften aufweisen;
• – eine wie oben beschriebene biozide Zusammensetzung, wobei das Metallsalz algizide, fungizide und/oder mikrobizide Eigenschaften aufweist;
• – eine wie oben beschriebene biozide Zusammensetzung, wobei diese eine hohe, sofortige und lang anhaltende Wirksamkeit gegenüber Algen, Pilze und/oder Bakterien aufweist.

The subject of the present invention is in detail:

• A biocidal composition containing inorganic solids, the inorganic solids being pigments and / or fillers, the inorganic solids being zinc sulphide, zinc oxide, barium sulphate, barite, mica, talc, kaolin, lithopone, Titanium dioxide, alumina, silica, calcium carbonate, calcium sulfate, zeolites, iron oxide, magnesium hydroxide, aluminum hydroxide, carbon, in particular graphite, or mixtures of at least two of these substances; The inorganic solids are in the form of nanoscale and / or non-nanoscale particles, the mean particle diameter of the inorganic solids, insofar as they are nanoscale, is between 200 and 1 nm, preferably between 120 and 2 nm, particularly preferably between 100 and 4 nm, most preferably between 80 and 5 nm, - the average particle diameter of the inorganic solids, unless they are nanoscale, between 0.25 and 500 microns, preferably between 0.3 and 200 .mu.m, more preferably between 0.3 and 30 microns is, - the inorganic solids in platelet, needle, spherical and / or epitaxial form, are present - and / or the surface of the inorganic solids is modified, preferably with a metal salt, wherein • the metal salt is a salt of Zinc, copper, silver, tin or mixtures of at least two of these metal salts, • the metal salt is a metal salt d it is sulfuric acid, nitric acid, hydrofluoric acid, hydrochloric acid, bromic acid, iodic acid, boric acid, phosphoric acid, peroctanoic acid, glycolic acid, oxalic acid, lactic acid, citric acid, benzoic acid, salicylic acid, acetylacetone, a fatty acid or a mixture of at least two of the salts of these acids, wherein as fatty acid a C ₁ to C ₁₈ fatty acid, preferably formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capric acid, lauric acid, stearic acid or a mixture of at least two of these acids is preferred, the metal salt is preferably a metal salt of Acetic acid, oxalic acid or citric acid, • the metal salt is a zinc salt, preferably zinc sulfate zinc sulfate, preferably zinc sulfate heptahydrate or zinc sulfate monohydrate, zinc nitrate, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc borate, and / or the organic zinc salts Z zinc formate, zinc valerate, zinc laurate, zinc stearate, zinc phosphate, zinc oxalate, zinc lactate, zinc citrate, zinc salicylate, zinc benzoate, zinc acetylacetonate, or mixtures of at least two of these salts, more preferably selected from zinc acetate, zinc oxalate, zinc citrate or mixtures of at least two of these metal salts or the proportion of the metal salt, based on the mass of the inorganic solid, is from 0.01 to 50% by weight, preferably from 0.1 to 30% by weight, particularly preferably from 0.5 to 20% by weight;
• A biocidal composition as described above which is in the form of a powder, paste, suspension or slurry;
• A biocidal composition as described above, wherein the inorganic solids have algicidal, fungicidal and / or antibacterial properties;
• A biocidal composition as described above, wherein the metal salt has algicidal, fungicidal and / or microbicidal properties;
• A biocidal composition as described above, which has a high, immediate and long-lasting activity against algae, fungi and / or bacteria.

• – ein Verfahren zur Herstellung einer wie oebn beschriebenen bioziden Zusammensetzung, bei dem ... und die Oberfläche der anorganischen Feststoffe bei und/oder nach deren Fällung modifiziert wird, wobei – die Oberfläche der anorganischen Feststoffe vor, während und/oder nach der Trocknung modifiziert wird, – die Oberfläche der anorganischen Feststoffe vor, während und/oder nach der Mahlung modifiziert wird – und / oder die Oberfläche der anorganischen Feststoffe durch die Behandlung mit einer Säure modifiziert wird, wobei • es sich bei der Säure um Schwefelsäure, Salpetersäure, Flusssäure, Salzsäure, Bromsäure, Iodsäure, Borsäure, Phosphorsäure, Peroctansäure, Glykolsäure, Oxasäure, Milchsäure, Zitronensäure, Benzoesäure, Salicylsäure, Acetylaceton, eine Fettsäure oder um eine Mischung aus mindestens zwei dieser Säuren handelt, wobei als Fettsäure eine C₁- bis C₁₈-Fettsäure, vorzugsweise Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Valeriansäure, Caprinsäure, Laurinsäure, Stearinsäure oder eine Mischung aus mindestens zwei dieser Säuren bevorzugt ist • und / oder es sich bei bei der Säure um Essigsäure, Oxalsäure oder Zitronensäure handelt.

The invention further relates

• A process for producing a biocidal composition as described above, in which ... and the surface of the inorganic solids is modified at and / or after precipitation, wherein - the surface of the inorganic solids is modified before, during and / or after drying is, - the surface of the inorganic solids before, during and / or after the grinding is modified - and / or the surface of the inorganic solids is modified by the treatment with an acid, wherein • the acid is sulfuric acid, nitric acid, hydrofluoric acid , Hydrochloric acid, bromic acid, iodic acid, boric acid, phosphoric acid, peroctanoic acid, glycolic acid, oxalic acid, lactic acid, citric acid, benzoic acid, salicylic acid, acetylacetone, a Fatty acid or a mixture of at least two of these acids, wherein as fatty acid, a C ₁ - to C ₁₈ fatty acid, preferably formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capric acid, lauric acid, stearic acid or a mixture of at least two of these acids is • and / or the acid is acetic acid, oxalic acid or citric acid.

• – die Verwendung einer wie oben beschriebenen bioziden Zusammensetzung als Algizid, Fungizid und/oder Mikrobiozid;
• – die Verwendung einer wie oben beschriebenen bioziden Zusammensetzung zur Hemmung des Bewuchses von marinen Lebewesen wie Algen, Muscheln und Krebsen an Schiffen und anderen marinen Fahrzeugen, Geräten und Vorrichtungen;
• – die Verwendung einer einer wie oben beschriebenen bioziden Zusammensetzung als Pigment und/oder Füllstoff;
• – die Verwendung einer wie oben beschriebenen bioziden Zusammensetzung zur Herstellung von und/oder zum Einsatz in Lacken, Farben, vorzugsweise Wasserfarben und/oder auf Wasser basierenden Farben, Lasuren, Imprägnierungen, Beschichtungen, Putzen, Kunststoffen und/oder medizinischen Materialien und Geräten.

The invention further relates

• The use of a biocidal composition as described above as algicide, fungicide and / or microbiocide;
• The use of a biocidal composition as described above for inhibiting the growth of marine organisms such as algae, shells and crabs on ships and other marine vehicles, equipment and devices;
• The use of a biocidal composition as described above as pigment and / or filler;
• The use of a biocidal composition as described above for the production of and / or for use in paints, inks, preferably water-based and / or water-based paints, varnishes, impregnations, coatings, plasters, plastics and / or medical materials and equipment.

Claims (26)

Biocidal composition, characterized in that it contains inorganic solids, wherein the inorganic solids are pigments and / or fillers. Composition according to Claim 1, characterized that the inorganic solids are zinc sulfide, zinc oxide, Barium sulfate, barite, mica, talc, kaolin, lithopone, titanium dioxide, Alumina, silica, calcium carbonate, calcium sulfate, zeolites, Iron oxide, magnesium hydroxide, aluminum hydroxide, carbon, in particular Graphite, or mixtures of at least two of these substances. Composition according to Claim 1 or 2, characterized that the inorganic solids in the form of nanoscale and / or are not nanoscale particles. Composition according to at least one of claims 1 to 3, characterized in that the average particle diameter of inorganic solids, as far as they are nanoscale, between 200 and 1 nm, preferably between 120 and 2 nm, more preferably between 100 and 4 nm, most preferably between 80 and 5 nm. Composition according to at least one of claims 1 to 4, characterized in that the average particle diameter of inorganic solids, as far as they are not nanoscale, between 0.25 and 500 μm, preferably between 0.3 and 200 μm, more preferably between 0.3 and 30 microns; Composition according to at least one of claims 1 to 5, characterized in that the inorganic solids in Tile-, Needle, ball and / or epitaxial form. Composition according to at least one of claims 1 to 6, characterized in that the surface of the inorganic solids is modified is, preferably with a metal salt. Composition according to at least one of claims 1 to 7, characterized in that the metal salt is a Salt of zinc, copper, silver, tin or mixtures from at least two of these metal salts. Composition according to at least one of Claims 1 to 8, characterized in that the metal salt is a metal salt of sulfuric acid, nitric acid, hydrofluoric acid, hydrochloric acid, bromic acid, iodic acid, boric acid, phosphoric acid, peroctanoic acid, glycolic acid, oxalic acid, lactic acid, citric acid, benzoic acid , Salicylic acid, acetylacetone, a fatty acid or a mixture of at least two of the salts of these acids, wherein the fatty acid is a C ₁ to C ₁₈ fatty acid, preferably formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capric acid, lauric acid, stearic acid or a mixture of at least two of these acids is preferred. Composition according to at least one of claims 1 to 9, characterized in that it is preferably in the metal salt a metal salt of acetic acid, the oxa acid or the citric acid is. A composition according to any one of claims 1 to 10, characterized in that it is the metal salt is a zinc salt, preferably selected from the inorganic zinc salts zinc sulfate, preferably zinc sulfate heptahydrate or zinc sulfate monohydrate, zinc nitrate, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc borate and / or the organic zinc salts zinc formate, zinc acetate, zinc valerate, zinc laurate, zinc stearate, zinc phosphate, zinc oxalate, zinc lactate, zinc citrate, zinc salicylate, zinc benzoate, zinc acetylacetonate, or mixtures of at least two of these salts, more preferably selected from zinc acetate, zinc oxalate, zinc citrate or mixtures from at least two these metal salts. Composition according to at least one of claims 1 to 11, characterized in that, based on the mass of the inorganic solid, the proportion of the metal salt 0.01 to 50 wt .-%, preferably 0.1 to 30 wt .-%, particularly preferably 0.5 to 20 wt .-% is. Composition according to at least one of claims 1 to 12, characterized in that these as powder, paste, suspension or slurry is present. Composition according to at least one of claims 1 to 13, characterized in that the inorganic solids are algicides, have fungicidal and / or antibacterial properties. Composition according to at least one of claims 1 to 14, characterized in that the metal salt algicidal, fungicidal and / or having microbicidal properties. Composition according to at least one of claims 1 to 15, characterized in that this high, immediate and long-lasting activity against algae, fungi and / or bacteria having. Process for the preparation of a composition according to at least one of the claims 1 to 16, characterized in that the inorganic solids be mixed according to known methods and the surface of the inorganic solids is modified, preferably at and / or after their precipitation. Method according to claim 17, characterized in that that the surface the inorganic solids before, during and / or after drying is modified. Method according to claim 17 or 18, characterized that the surface the inorganic solids before, during and / or after milling is modified. Method according to at least one of claims 16 to 19, characterized in that the surface of the inorganic solids by the treatment with an acid is modified. Process according to at least one of Claims 16 to 20, characterized in that the acid is sulfuric acid, nitric acid, hydrofluoric acid, hydrochloric acid, bromic acid, iodic acid, boric acid, phosphoric acid, peroctanoic acid, glycolic acid, oxalic acid, lactic acid, citric acid, benzoic acid, salicylic acid, acetylacetone , a fatty acid or a mixture of at least two of these acids, wherein the fatty acid is a C ₁ to C ₁₈ fatty acid, preferably formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capric acid, lauric acid, stearic acid or a mixture of at least two of these Acids are preferred. Method according to at least one of claims 16 to 21, characterized in that it is in the acid to acetic acid, oxalic acid or citric acid Use of a composition after at least one of the claims 1 to 16 as algicide, fungicide and / or microbiocide. Use of a composition after at least one of the claims 1 to 16 for the inhibition of the growth of marine organisms such as algae, Shellfish and crabs on ships and other marine vehicles, devices and devices. Use of a composition after at least one of the claims 1 to 16 as a pigment and / or filler. Use of a composition after at least one of the claims 1 to 16 for the production of and / or for use in paints, inks, preferably water colors and / or water-based colors, Glazes, impregnations, coatings, Cleaning, plastics and / or medical materials and equipment.