EP1986500A2

EP1986500A2 - Biocidal composition

Info

Publication number: EP1986500A2
Application number: EP07704602A
Authority: EP
Inventors: Djamschid Amirzadeh-Asl
Original assignee: Sachtleben Chemie GmbH
Current assignee: Venator Germany GmbH
Priority date: 2006-02-16
Filing date: 2007-02-15
Publication date: 2008-11-05
Also published as: JP2009526822A; WO2007093627A3; KR20080102204A; WO2007093627A2; US20080317800A1; CN101511193A

Abstract

The present invention relates to a biocidal composition, a method for its production and the use of the biocidal composition.

Description

Biocide composition

The present invention is a biocidal composition, a process for their preparation and the use of the biocidal composition.

In particular, the present invention relates to a biocidal composition based on zinc sulfide, zinc oxide, barium sulfate, lithopones, titania, alumina, silica, calcium carbonate, calcium sulfate, and / or zeolites, preferably based on zinc sulfide, zinc oxide, barium sulfate, and / or lithopones ,

Biocides (from Greek / Latenian: life-killers) are agents used in a variety of products to kill, as the case may be, a wide range of organisms from viruses, bacteria, algae, fungi, insects to mollusks and rodents. There are around 8,000 biocidal products on the market that eliminate, deter or decimate small and microorganisms that are undesirable for humans in certain situations. These include above all agents against bacteria, algae and fungi, but also against spiders, mice, rats, flies or mosquitoes. Typical biocidal products include wood preservatives, insect repellents for domestic use, mold-resistant wall paints for bathrooms or kitchens, antibacterial household cleaners, disinfectant sprays and attractants against clothes moths. Biocidal products are widely available as ready-to-use articles to the consumer. Thus, textiles with the quality label "wool seal" are always equipped with moth protection.

According to their action against various groups of organisms one speaks of microbicides (against microorganisms), insecticides (against insects), molluscicides (against molluscs), rodenticides (against rodents) and so on. The microbicides include the algicides, bactericides, fungicides and virucides. Algicides are compounds that kill algae or inhibit their growth or multiplication. Paint-based paints are homogeneously distributed in paints so that paints made from them are permanently protected against algae growth, even under unfavorable conditions, such as the effects of rain and light. It follows that paint acidicides are practically insoluble in water and light stable. It is also expected that paint acidicides will not discolor the paint, are non-volatile, low in toxicity and compatible with other paint components. Examples of paint gallicides are chlorothalonil, diuron and dichlofluanid.

Fungicides are microbicides that kill fungi and their spores. They are used, inter alia, in wood protection against blue stain (wood decaying fungi) and wood-destroying fungi, but also to prevent the growth of harmful fungi on food, textiles, walls, paper, wood, glue, paints, lubricants and even fuels etc. ,

Antifouling paints are paints which are applied in the underwater area of ships, derricks, etc., where they inhibit growth. Characteristic of antifouling paints is the content of algicidal and fungicidal compounds, usually copper oxide and organotin compounds, in particular, the tin organics are environmentally questionable.

In applications such as paints, coatings, plastics, medical products, etc., metal ions are used as biocides, in particular as microbicides, in particular in the form of compositions based on metal salts. The metal ions are, in particular, heavy metal ions, for example copper, silver, tin and nickel ions.

For the treatment of water, for example, water-soluble inorganic metal salts such as copper sulfate, copper nitrate and copper chloride are proposed in the prior art for use as algicides or bactericides for the treatment. However, the use of copper or copper ion sources, inter alia, has the disadvantage that copper ions in alkaline or near alkaline React media with naturally occurring anions and fail as insoluble salts, such as carbonates, oxides or hydroxides. This pH-dependent precipitation leads to losses of biocidal activity, since then copper ions are no longer available.

In addition, copper salt biocides are more effective against algae than against bacteria and other pathogens. Therefore, to achieve significant biocidal activity of copper salts against bacteria, higher concentrations of copper are needed, which is undesirable. If bacteria or other pathogens are to be active with copper salt-containing algicides, this generally requires the use of additional biocides.

Also known from the prior art is the preparation and use of microbicidal compositions in inorganic carriers such as, for example, the oxides of titanium, magnesium, aluminum, silicon, barium sulfate and zeolites, in particular for use in polymers (US Pat. No. 4,525,410, US Pat. US-A-4,775,585, US-A-4,906,466).

EP-B-146341 1 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.

However, the prior art does not disclose a technical teaching which makes it possible to provide a biocidal composition which acts as an algicide and / or fungicide and / or antibacterial by the combination of inorganic solids and biocidal substances in various applications as required.

Also, no technical teaching is disclosed in the prior art which overcomes the problem that certain inorganic solids, such as the pigments such as zinc oxide, zinc sulfide, titanium dioxide, and lithopone, are only a very slower - A -

Have activity against algae as well as bacteria and / or other pathogens. In addition, zinc oxide, zinc sulfide, titanium dioxide and lithopone are generally more effective against algae than against bacteria and other pathogens. To achieve significant biocidal activity, it is necessary in the prior art to use high concentrations, which is undesirable. Barium sulfate is even completely inert, that is, it shows no biocidal activity even in high concentrations.

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

In particular, the object of the invention is to provide a biocidal composition which, depending on the application and need, acts as algicide and / or fungicide and / or antibacterial.

Another object of the present invention is to provide a biocidal composition which is effective against algae as well as against fungi as well as against bacteria.

According to a further object of the invention, this composition should be able to be used in various applications such as paints and inks, for example water-based or water-based paints, coatings, roughcast or plaster coatings, glazes, impregnations, semidicken coatings, plastics, medical articles.

According to a further object of the invention, the biocidal composition should consist of inorganic solids, preferably of pigments, fillers and / or nanoscale particles, nanoscale particles being understood to mean those whose average particle size is below 250 nm.

According to a further object of the invention, the inorganic solids used are preferably themselves biocidal properties. According to a further object of the invention, the pigment or filler properties of the inorganic solids are to be retained.

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

According to a further object of the invention, the novel coating composition is said to have a higher, immediate and long-lasting activity against algae, fungi and / or bacteria. In addition, this coating composition is said to be useful as an antifouling paint and to prevent the marine vegetation such as algae, bivalves, crabs, etc. in marine and other marine vehicles, equipment and devices.

Surprisingly, the objects have been solved by the features of the main claim. Preferred embodiments can be found in the subclaims.

In particular, it has surprisingly been found that the abovementioned objects are achieved by inorganic solids which have been surface-modified with one or more biocidal substances, in particular metal salt compounds.

As the inorganic solid, there may be used any of pigments or fillers such as 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 may be of both natural and synthetic origin.

For surface modification, metal salts having a biocidal property are preferably used. In this case, inorganic or organic substances, individually or in mixture, can be used as metal salts. When Starting material for the surface modification of the inorganic solids, the compounds or salts of metals, for example, zinc, copper, silver and / or tin, preferably of zinc, find application.

In principle, all soluble or sparingly soluble salts of biocidal metals can be used singly or in admixture for the surface modification of inorganic solids.

The amount of metal salts added is 0.01 to 50% by weight, preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, based on the weight of the inorganic solid.

The average particle size 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, very particularly preferably between 80 and 5 nm.

The mean particle size of the inorganic solids, as far as they are not nanoscale, is between 0.25 and 500 .mu.m, preferably between 0.3 and 200 .mu.m, particularly preferably between 0.3 and 30 .mu.m.

The particles may have different shapes, for example, platelet, needle, spherical or epitaxial form.

The inorganic solids used are preferably substances which themselves have a biocidal property, for example algicidal and / or microbicidal. In particular, zinc oxide, zinc sulfide, titanium dioxide and / or lithopone are used in the preparation of the biocidal composition according to the invention.

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

Zinc salts are preferably used as metal salts, for example zinc sulfate (hepta- and / or monohydrate), zinc chloride, zinc nitrate, zinc bromite, zinc iodide,

Zinc borate, zinc fluoride, zinc acetate, zinc acetate, zinc acetylacetonate, zinc formate, Zinc lactate, zinc oxalate, zinc salicylate, zinc laurate, zinc valerate, zinc stearate, zinc phosphate or mixtures of at least two of these substances.

Particular preference is given to using organic zinc salts, for example zinc acetate, zinc acetate, zinc acetylacetonate, zinc formate, zinc salicylate, zinc benzoate or mixtures of at least two of these substances. Zinc acetate, Zinkeitrat, zinc oxalate or mixtures of at least two of these substances are particularly preferably used.

The composition can be prepared by methods known per se, for example by mixing the constituents according to the invention. In this case, the surfaces of the inorganic solids may preferably be modified.

In the surface modification of the inorganic solids by the corresponding metal salts, all possible variants which are known in the art and known, can be used. For example, the surface modification may be carried out in the precipitation of the inorganic solids, in the treatment of the inorganic solids in suspension prior to drying, or also before or after the milling.

The finely divided, inorganic solids are preferably present as aqueous suspension or as filter cake (paste-like or as dough). It is advantageous to use a filter cake undried, for example, from ongoing production.

The drying of the suspension provided with the metal salts or of the filter cake provided with the metal salts can be effected by means of customary drying units. Preferably, spray dryers, grinding dryers or vacuum dryers are used.

In the case of surface treatment of the inorganic solids after drying, the addition of the biocidal compounds may be in liquid form or in powder form. To homogenize the mixture, the usual mixing units, such as plowshare mixers or drum mixers can be used. Depending on the compound used, before, during and after mixing a temperature treatment can be performed. If necessary, subsequent grinding can be carried out. In this case, the mixtures are preferably subjected to a steam jet, air jet or pin grinding.

Another way to modify metal salts on the surface of the inorganic solids is to directly treat the inorganic solids with the appropriate acid. In this case, for example, by the treatment of zinc sulfide, zinc oxide, zinc sulfide, titanium dioxide, barium sulfate and / or lithopones with appropriate acids such as 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 or a fatty acid formed the desired zinc salts. The acids can be used individually or in mixture.

For surface treatment of the inorganic solids with acids, any of the possible procedures known can be used. The treatment can be carried out during precipitation, before drying, after drying, before grinding or after grinding.

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

Depending on the field of use, the biocidal composition according to the invention can be in the form of a powder, paste, suspension or slurry.

The subject of the present invention is in detail:

> a biocidal composition containing inorganic solids, wherein the inorganic solids are pigments and / or fillers, wherein

o 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;

o the inorganic solids are in the form of nanoscale and / or non-nanoscale particles,

the average 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, very particularly preferably between 80 and 5 nm,

o the mean particle diameter of the inorganic solids, if they are not nanoscale, is between 0.25 and 500 μm, preferably between 0.3 and 200 μm, particularly preferably between 0.3 and 30 μm,

o the inorganic solids in platelet, needle, spherical and / or epitaxial form, are present

o 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 them

Metalsalts acts,

^■ the metal salt is a metal salt of sulfuric, nitric, hydrofluoric, hydrochloric, bromoic, iodic, boric, phosphoric, peroctanoic, glycolic, oxalic, lactic, citric, benzoic, salicylic, acetylacetone,

Fatty acid or a mixture of at least two of the salts of these acids, the preferred fatty acid being 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,

^"It is preferably the metal salt is a metal salt of

Acetic acid, which is oxalic acid or citric acid,

^■ it 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 organic zinc salts, zinc formate, zinc acetate, zinc valerate, Zinc laurate, zinc stearate, zinc phosphate, zinc oxalate, zinc lactate, Zinkeitrat, zinc salicylate, zinc benzoate, zinc acetylacetonate, or mixtures of at least two of these salts, more preferably selected from zinc acetate, zinc oxalate, Zinkeitrat or

Mixtures of at least two of these metal salts

^■ and / or the proportion of the metal salt, based on the mass of the inorganic solid, 0.01 to 50 wt, -%, preferably 0.1 to 30 wt, -%, particularly preferably 0.5 to 20 wt, -% is ;

> a biocidal composition as described above which, as a powder, paste,

Suspension or slurry is present;

> 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.

The invention further relates

> A process for the preparation of a biocide as described above

Composition in which ... and the surface of inorganic solids is modified at and / or after precipitation, wherein

o the surface of the inorganic solids is modified before, during and / or after drying,

o the surface of the inorganic solids is modified before, during and / or after the grinding

o and / or the surface of the inorganic solids is modified by 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 the fatty acid is a Ci to Ciβ 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

^■ and / or the acid is acetic, oxalic or citric acid.

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 preparation of and / or for use in paints, inks, preferably

Water-based and / or water-based paints, glazes, impregnations, coatings, plasters, plastics and / or medical materials and equipment.

Claims

claims

1 . Biocidal composition, characterized in that it contains inorganic solids, wherein the inorganic solids are pigments and / or fillers.

2. Composition according to claim 1, characterized in that the inorganic solids are zinc sulfide, zinc oxide, barium sulfate, barite, mica, talc, kaolin, lithopone, titanium dioxide, aluminum oxide, silicon dioxide, calcium carbonate, calcium sulfate, zeolites, iron oxide, magnesium hydroxide, Aluminum hydroxide, carbon, in particular graphite, or mixtures of at least two of these substances.

3. Composition according to claim 1 or 2, characterized in that the inorganic solids are present in the form of nanoscale and / or non-nanoscale particles.

4. The composition according to at least one of claims 1 to 3, characterized in that the average particle diameter of the inorganic

Solids, insofar as they are nanoscale, are between 200 and 1 nm, preferably between 120 and 2 nm, particularly preferably between 100 and 4 nm, very particularly preferably between 80 and 5 nm.

5. The composition according to at least one of claims 1 to 4, characterized in that the average particle diameter of the inorganic

Solids, unless they are nanoscale, are between 0.25 and 500 μm, preferably between 0.3 and 200 μm, particularly preferably between 0.3 and 30 μm;

6. The composition according to at least one of claims 1 to 5, characterized in that the inorganic solids in platelet, needle, spherical and / or epitaxial form, are present.

7. The composition according to at least one of claims 1 to 6, characterized in that the surface of the inorganic solids is modified, preferably with a metal salt.

8. The composition according to at least one of claims 1 to 7, characterized in that it is the metal salt is a salt of zinc, the

Copper, silver, tin or mixtures of at least two of these metal salts.

9. The composition according to at least one of claims 1 to 8, characterized in that it is the metal salt is a metal salt of sulfuric acid, nitric acid, hydrofluoric acid, hydrochloric acid, bromic acid, iodic acid,

Boronic 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 Cr to Cis 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 the metal salt is preferably a metal salt of acetic acid, oxalic acid or citric acid.

1 1. 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, Zinkeitrat, zinc salicylate, zinc benzoate, zinc acetylacetonate, or mixtures of at least two of these Salts, particularly preferably selected from zinc acetate, zinc oxalate, Zinkeitrat or mixtures of at least two of these metal salts.

^. A composition according to any one of claims 1 to 1 1, characterized in that, based on the mass of the inorganic solid, the proportion of the metal salt from 0.01 to 50 wt .-%, preferably 0.1 to 30 wt .-%, especially preferably 0.5 to 20 wt .-% is.

^. A composition according to any one of claims 1 to 12, characterized in that it is present as a powder, paste, suspension or slurry.

A composition according to at least one of claims 1 to 13, characterized in that the inorganic solids have algicidal, fungicidal and / or antibacterial properties.

^. A composition according to any one of claims 1 to 14, characterized in that the metal salt has algicidal, fungicidal and / or microbicidal properties.

^. Composition according to at least one of claims 1 to 15, characterized in that it has a high, immediate and long-lasting activity against algae, fungi and / or bacteria.

17. A process for preparing a composition according to any one of claims 1 to 16, characterized in that the inorganic solids are mixed by known methods and the surface of the inorganic solids is modified, preferably at and / or after their precipitation.

18. The method according to claim 17, characterized in that the surface of the inorganic solids before, during and / or after drying is modified.

19. The method according to claim 17 or 18, characterized in that the surface of the inorganic solids before, during and / or after the grinding is modified.

20. The method according to at least one of claims 16 to 19, characterized in that the surface of the inorganic solids through the

Treatment with an acid is modified.

21. 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 ₈ 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.

22. The 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

23. Use of a composition according to at least one of claims 1 to 16 as algicide, fungicide and / or microbiocide.

24. Use of a composition according to any one of claims 1 to 16 for inhibiting the growth of marine organisms such as algae, shells and crabs on ships and other marine vehicles, equipment and devices.

25. Use of a composition according to any one of claims 1 to 16 as a pigment and / or filler.

26. Use of a composition according to at least one of claims 1 to 16 for the preparation of and / or for use in paints, inks, preferably water-based paints and / or water-based paints, glazes,

Impregnations, coatings, plasters, plastics and / or medical materials and equipment.