WO1995012315A1 - Stabilisation of iodine compounds using inorganic supporting materials for use in material protection - Google Patents

Abstract

The application describes known iodine-containing microbicides stabilised against the action of light by inorganic supporting materials, and the use of these support/active agent combinations to protect technical materials.

Description

Stabilization of iodine compounds with the aid of inorganic carrier materials for ner endune in material protection

The application relates to iodine compounds of the formulas (I) to (XV) which are stabilized and / or fixed in the material to be protected by inorganic carrier materials against the action of light, heat or against washing out by water.

Iodine-containing microbicides and their use in protecting materials are known (US 3,923,870, US 4,865,892, DE 3,216,895, EP 490,566).

However, their use is limited since these Nerbindungen generally disintegrate under the influence of light and heat.

For use in paint films in particular, their use is generally limited to non-white paint films, since the iodine-containing compounds lead to yellow discoloration when exposed to UN light or daylight.

Even in plastics, these compounds cannot be used without restriction due to their thermolability, their tendency to discolour and other material-changing properties.

To solve this problem, JP 5 117 105 proposed to include the compounds in cyclodextrins. These organic molecules are themselves only thermally stable to a limited extent, and due to their high molecular weight, the proportion of active ingredient in the formulation is low. In addition, these complex / inclusion compounds with cyclodextrins and the above-mentioned active substances are more water-soluble than the active substances themselves, which leads to leaching out of materials which are in contact with water and thus to a loss of activity. It has now been found that these disadvantages do not occur when the iodine compounds are applied to zeolites or similar inorganic support materials.

The application therefore relates to iodine compounds applied to inorganic carrier materials and their use for protecting industrial materials.

Suitable carrier materials are preferably: nat. and synthetic zeolites, layered silicates, clays, precipitated silicas, kieselguhrs, silicas, aerosils, bentonites, kaolins, activated carbons, natural and synthetic clay minerals, TiO ₂ , ZnO, calcium carbonate, dolomites, pumice stones, attapulgites, sepiolites, ball clays, clays , including alumophosphates, silicoaluminophosphates, metal aluminophosphates and crystalline silicas with pore structure.

The zeolites or molecular sieves, which come under the following formula, have proven to be particularly suitable carrier materials:

M _{m / z} [mE ¹ O _z nE ² O _z ] qH ₂ O

in the

M is an exchangeable cation,

E ^{1 represents} a trivalent element,

E ^{2 represents} a tetravalent element, E ¹ and E ^{2 representing} the anionic skeleton,

n / m is the ratio of the elements E ¹ and E ² and can assume values from 1 to 3,000, preferably 1 to 2,000,

z stands for the value of the exchangeable cation and q means the amount of water sorbed,

and the zeolites preferably have pore sizes of at least 4 Å, in particular pore sizes in the range from 4 to 8 Å, preferably in the range from 5 to 8 Å.

The basic structure of zeolites consists of a network of SiO ₄ and AlO ₄ tetrahedra, whereby the individual tetrahedra are linked with each other by oxygen bridges via their corners and form a spatial network that is evenly interspersed with channels and cavities. The aluminum as a representative of the element E ^{1 can be} partially replaced by other trivalent or also divalent elements such as B, Ga, In, r ^' e, Cr, V, As, Sb or Be, Cu or Co. Furthermore, the silicon as a representative of the element E can be replaced by other tetravalent elements such as Ge. Interchangeable cations are stored to compensate for the negative charge of the lattice caused by the trivalent elements. The individual zeolite structures (types) also differ in the arrangement and size of the channels and cavities. Zeolites always contain q H ₂ O as a sorbed water phase, which can be removed reversibly without the structure losing its structure. A detailed description of the zeolites can be found, for example, in the monograph "Introduction to Zeolite Science and Practice" Ed. H. van Bekkum, zH Flanigen, JC Jansen in the series Studies in Surface Science and Catalysis Vol. 58, Elsevier, Amsterdam, Oxford, New York - Tokyo, 1991.

Zeolites of the following structure types and corresponding analogs are preferred:

Zeolite A, chabasite, cancrinite, gmelinite, zeolite L, heulandite, mazzite, mordenite, offretite, EU-1, faujasite, ferrierite, gismondin, ZK-5, ZSM 5, ZSM 11, ZSM 23, ZSM 22, ZSM 12, zeolite ß, PSH-3, zeolite Rho.

Also suitable are aluminophosphates such as A1PO-5, A1PO-11, A1PO-8, A1PO-17 and silicoaluminophosphates such as SAPO-5, SAPO-11, SAPO-34, SAPO 17 and others. In addition to zeolites, layered silicates such as magadiite or SKS-6 can also be used as carriers.

Preferred among the zeolites are the easily accessible zeolite structures such as zeolite A and faujasite with the types zeolite X and zeolite Y and the following formulas:

Type A Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] -27 H ₂ O

Type X Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] 264 H ₂ O

Type Y Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] 250 H ₂ O

In addition to the synthetic forms of the zeolites, the various ion-exchanged forms can also be used as carriers.

Preferred iodine compounds are compounds of the formulas (I) to (NU)

IC≡C-CH ₂ -OR (I)

I-CsC- (COO) _n -R (π)

(Sumplas)

(Triiodoalkyl alcohol) (IN)

IC≡C-CH ₂ -OH (iodopropyl alcohol) (N)

Me (Amical) (VI)

(Periodethylene) (VII)

in which

R represents phenyl, naphthyl, heterocyclyl or cyclohexyl optionally substituted by Cl, Me, Et, mono- to pentasubstituted, or

R represents the groups -CH ₂ CH ₂ -O-CO-NHR or -CO-NHR, where R represents linear, cyclic or branched

preferably C ₂ -C ₆ alkyl, or has the meaning of R, or

R stands for the group -CO-NR'R ", in which R 'and R" are identical or different and stand for hydrogen or have the meanings given for R, or together form a heterocycle,

n stands for the number zero or one.

The compounds of the formulas (I) to (VI) have a good microbicidal action against material-relevant microorganisms.

The iodine compounds of the formulas (VIII) to (XV) are particularly preferred

)

The carriers can be loaded with the iodine compounds in different ways, adapted to the respective carrier material. A description of such techniques can be found in DE 1 219 008.

According to this, molecular sieves or zeolites can be loaded by first removing water from the molecular sieve by heating, which can be done, for example, by heating at 400 to 450 ° C. for several hours, and then bringing it into contact with the active substance. The loading can take place in any manner, for example by passing it into the vapor form brought active ingredient by the Zecüth or by immersing the zeolite in the liquid or melted active ingredient or a solution of the active ingredient in a non-polar volatile solvent with subsequent evaporation of the solvent.

The amount of the active ingredient to be applied can be varied within wide limits. It depends on the active ingredient used and the conditions under which the carrier / active ingredient mixture is to be used.

In general, the carrier is loaded with amounts of 0.1 to about 40% by weight, preferably 0.5 to 30% by weight, in particular 1 to 20% by weight, of active compound, based on the carrier. The maximum loading is preferably selected in order to achieve a high active ingredient concentration per mass of carrier.

Further active substances and / or auxiliary substances can also be added to the mixture of carrier material and iodine compound, e.g. reduce dusting of the mixture or sensitivity to water.

The carrier A active substance combinations have a particularly high, microbicidal, in particular fungicidal activity, combined with a broad spectrum of activity against microorganisms relevant to material protection; they are particularly effective against mold, wood-staining and wood-destroying fungi. The groups of microorganisms listed below may be mentioned as examples - but without limitation.

The carrier / active substance combinations according to the invention can be used practically to combat unwanted microorganisms. The carrier / active substance combinations according to the invention are suitable for protecting industrial materials against attack and destruction by undesired microorganisms.

In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials made by Active substances according to the invention are to be protected against microbial change or destruction, adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be attacked or decomposed by microorganisms. In the context of the materials to be protected, parts of production systems, for example cooling water circuits, which may be impaired by the multiplication of microorganisms, may also be mentioned. In the context of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, coolants, lubricants and heat transfer liquids, particularly preferably paints.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The carrier / active ingredient combination which can be used according to the invention preferably acts against fungi, in particular molds, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against mucus organisms and algae.

For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, like Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus. The carrier / active substance combinations according to the invention can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances.

These formulations are prepared in a known manner, for example by mixing the components with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or Glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; the following are suitable as solid carriers: e.g. natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble , Pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; emulsifiers and / or foaming agents are suitable: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acids ureester, polyoxyethylene fatty alcohol ether, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolyzates; Possible dispersants are: lignin sulfite leaching and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The microbicidal agents or concentrates used to protect the industrial materials contain the carrier / active ingredient combination in a concentration of 0.01 to 99% by weight, in particular 0.1 to 60% by weight.

The application concentrations of the carrier / active substance combinations to be used according to the invention depend on the type and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, of the active ingredient, based on the material to be protected.

The carrier / active substance combinations are particularly preferably used in paints or antifouling agents or films.

In the present context, painting is to be understood as meaning a coating made of paints on a substrate. The paint may have penetrated more or less into the surface. It can consist of one or more layers and can be produced by processes such as brushing, spraying, dipping, flooding or similar processes. The carrier / active ingredient combinations to be used according to the invention are incorporated into the paints or into precursors for producing the paints by customary methods, for example by mixing the carrier / active ingredient combinations with the other components.

The paints according to the invention therefore contain, in addition to at least one carrier / active ingredient combination, generally customary paint components in e.g. liquid, pasty or powdery form such as

Colorants, such as pigments or dyes, preferably pigments. Examples include titanium dioxide, zinc oxide and iron oxide.

- Binders, such as, for example, oxidatively drying alkyd resins, vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers, plastic powder, novolacs, amino resins, polyester resins, epoxy resins, silicone resins, isocyanate resins, vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers are preferred other binders which can be used in water-dilutable paints.

In addition, the paints may contain the following additives

Fillers, such as, for example, heavy spar, calcite, dolomite and talc (possibly partially substituted by the inorganic carrier used).

Solvents, such as, for example, alcohols, ketones, esters, glycol ethers and aliphatic and aromatic hydrocarbons, as well as thickening and thixotropic agents, dispersing and wetting agents, drying agents, skin inhibitors, leveling agents, anti-foaming agents, corrosion inhibitors, UV absorbers, fragrances, antistatic agents and antifreezes.

The following may preferably be mentioned as paints or precursors for the production of paints: Glues and adhesives based on the well-known animal, vegetable or synthetic raw materials.

Plastic dispersions such as latex dispersions or dispersions based on other polymers. - Starch solutions, dispersions or slurries or others based on

Starch products such as Pressure thickener.

Slurries of other raw materials such as color pigments (e.g. iron oxide pigments,

Carbon black pigments, titanium dioxide pigments) or slurries of fillers such as

Kaolin or calcium carbonate. - coats and finishes.

Bitumen emulsions.

Preliminary and intermediate products of the chemical industry, e.g. in the

Dye production and storage.

Inks or inks. - emulsion paints for the painting industry.

It is also of particular importance that the carrier / active substance combinations according to the invention e.g. not only equip aqueous paints with fungicide and algicide (film protection), but also preserve them reliably and permanently during storage in tanks or containers.

The effectiveness and the spectrum of activity of the carrier / active substance combinations according to the invention or the agents, precursors or very generally formulations which can be prepared therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active substances are used to enlarge the spectrum of activity or Achieving special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components. Particularly favorable mixture partners are, for example, one or more of the following compounds: N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylene isothiazolinone, 4,5-benzisothiazolinone, benzyl alcohol mono (poly) hemiformal, N-methylolchloroacetamide;

Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, bromcinnamaldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate;

quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride;

Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;

Bromine derivatives such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane , -Bromo-nitrostyrene;

Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione;

Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;

Oxides such as tributyltin oxide, Cu ₂ O, CuO, ZnO;

Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;

Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;

Quinolines such as 8-hydroxyquinoline and their Cu salts; Mucochloric acid, 5-hydroxy-2 (5H) furanone;

4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dichloro- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l, 3, 5-thiadiazin-2-thione, N- (2-p-chlorobenzoylethyl) hexaminium chloride, potassium N-hydroxymethyl-N'-methyl-dithiocarbamate,

2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride,

Phenyl- (2-chloro-cyano-vinyl) sulfone,

Pheny l- (1,2-dichloro-2-cy an-vinyl) sulfone;

Compounds which are formed by reacting N-substituted propylenediamines with glutamic acid esters in accordance with EP-A-156 275.

Preferred mixing partners are also:

Triazoles:

Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imiben-conazole, Isozofos, Myclobutanil, Opus, Paclobutrazol, Penconazole, 1 4-chlorophenyl) -2- (1H-1, 2,4-triazol-1-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, uniconazole;

Imidazole:

Imazalil, pefurazoate, prochloraz, triflumizole, 2- (l-tert-butyl) -l- (2-chlorophenyl) -3- (l, 2,4-triazol-l-yl) -propan-2-ol, thiazolecarboxanilides such as 2 ', 6'-Dibromo-2-methyl ^ -trifluoromethoxy ^' - trifluoromethyl-l ^ -thiazole-S-carboxanilide.

Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylates, methyl (E) -2- [2- [6- (2-thioamidophenoxy) pyrimidine- 4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy-acrylate, methyl (E) -2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-meth-oxyacrylates, methyl (E) -2- [2- [3- (pyrimidin-2-yloxy ) phenoxy] phenyl] -3-methoxy- acrylates, methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-meth-oxyacrylates, methyl (E) -2- [2- [3- ( phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylates, methyl (E) -2 - [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dimethylbenzoyl) pyrrol-l-yl] -3-methoxyacrylate, methyl (E) -2- [2- ( 3-methoxyphenoxy) phenyl] -. 3 methoxy acrylates, methyl (E) -2- [2- (2-phenylethen-l-yl) phenyl] -3- methoxyacrylates, methyl (E) -2- [ 2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (E) -2- (2- (3- (l, l, 2,2-tetrafluoroethoxy) phenoxy) phenyl) -3-methoxy-acrylates, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxy-acrylates, methyl (E) -2- (2- (4th -phenoxypyridin-2-yloxy) phenyl) -3-methoxy acrylate, methyl (E) -2- [2- (3-n-propyloxyphenoxy) phenyl] 3-methoxyacrylate, methyl (E) -2- [2- (3rd -isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) - 2- [2- (3-ethoxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (4-tert-butylpyridin-2-yloxy) phenyl] -3-methoxyacrylate, methyl (E ) -2- [2- [3 - (3 -cyanophenoxy) phenoxy] phenyl] -3-methoxy oxyacrylates, methyl (E) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3- meth-oxyacrylates, methyl (E) -2- [2- [6- (2-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3- methoxyacrylates, methyl (E) -2- [2- (5-bromopyridine- 2-yloxymethyl) phenyl] -3-methoxy acrylates, methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylates, methyl (E ) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, (E), (E) methyl-2- [2- (5th , 6-dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] -3-methoxyacrylate, (E) -methyl-2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl } -3-methoxyacrylate, (Ei, (E) methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl-2- {2- (6- (2nd azidophenoxy) pyrimidin-4-yloxy] phenyl} 3-methoxyacrylates, (E), (E) methyl-2- {2- [6-phenylpyrimidin-4-yl) -met hyloximinomethyl] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2 - [(4-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl-2- {2 - [6- (2-n-propylphenoxy) -1, 3,5-triazin-4-yloxy] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2 - [(3-nitrophenyl ) methyloximinomethyl] - phenyl} -3-methoxyacryiate;

Succinate dehydrogenase inhibitors such as: Fenfuram, furcarbanil, cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut);

Naphthalene derivatives such as:

Terbinafme, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-in);

Sulfenamides such as dichlorfluanide, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;

Benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazole or their salts;

Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; Aldimorph, fenpropidine and their arylsulfonic acid salts, e.g. p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;

Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram:

Benzothiazoles such as 2-mercaptobenzothiazole;

Quinolines such as 8-hydroxyquinoline and their Cu salts;

Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide;

Boron compounds such as boric acid, boric acid ester, borax;

Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poly) -hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;

Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) - tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper.

Mixtures with are very particularly preferred Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl- (E) -methoximino [- (o-tolyloxy) -o-tolyl)] acetate, methyl- (E) -2 {2- [6- (2-cyanophenoxy) pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fen piclonil, 4- (2,2-difluoro-l, 3- benzodioxol-4-yl) -lH-pyrrole-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinones , N- (2-hydroxypropyl) amino-methanol, benzyl alcohol (hemi) formal, glutaraldehyde, omadine, dimethyl dicarbonate, and / or 3-iodo-2-propynyl-n-butyl carbamate.

Surprisingly, the effect of these combinations of active substances is considerably higher than the sum of the effects of the individual active substances. So there is an unforeseeable real synergistic effect and not just an addition.

If the active compounds are present in the active compound combinations according to the invention in certain weight ratios, the synergistic effect is particularly evident. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied within a relatively wide range.

Furthermore, well-effective mixtures with the following active ingredients are also produced:

Fungicides:

Acypetacs, 2-aminobutane, Ampropylfos, anilazine, benalaxyl, Bupirimate, chinomethionat, chloroneb, chlozolinate, cymoxanil, dazomet, Diclomezine, Dichloram, diethofencarb, dimethirimol, Diocab, dithianon, dodine, Drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Ofuraceurolήήruronήήruronήήή, Nuarirήήuronήήήήήή Nu Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamide, Tricyclazole, Triforine, Vinclozolin.

Insecticides:

Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, -l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos, dimethoate , Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphone;

Carbamates such as aldicarb, bendiocarb, -2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;

Organosilicon compounds, preferably dimethyl (phenyl) silyl-methyl-3-phenoxybenzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzylether or

(Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethylether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) -silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl] dimethyl silane, silafluofen;

Pyrethroids such as ailethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trif -methylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;

Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-lH-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N ² - cyano-N ^ methylacetamide (NI-25); Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethriproxyphid, Pyrethridafid, Pyrethridafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafide, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl -phosphorothiate, thiocyclam, thiofanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothion, verticillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, bromophone, bromine, bromine, bromophosphate Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionate, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha- cypermethrin, Cy ophenothrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Ethionofencarbon , Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Kiospine, Iodophane, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinone Mecarbam, Mephosfolan, Mercurous, chloride, Metam, Metarthician, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer Omachophenol, Methylvethophenolate , Petroleum oils, phenothrin, phenthoates, phorates;

Molluscicide:

Fentin acetates, metaldehydes, methiocarb. Niclosamide, thiodicarb, trimethacarb;

Algicide:

Coppersulfate, dichlororphen, Endothal, Fentinacetate, Quinoclamine; Herbicide:

acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, bensulfide, benzafthoxane, benzafone, benzafone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzafone, benzazone, benzazone benzax dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromynoxoxiloxyloxomiloxilyl, bromomoxililoxyl bromoboxane butamifos, fuenachlor, butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chloro otoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron , clethodim, clomazone, clomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate, dinoterb, diphenamide, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop , flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluoroxypyr, cycloate, cycloxydim, 2,4-D, daimuron, dalapon, DB, desometham, 2.4 , desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metachiazole meth , methoproptryne, methyldymron, methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, pyyzamide, prosulfynol azoxyfen, pyributicarb, pyridate, quinclorac, quinmerac, quinocloamine, quizalofop, quzizalofop-P, S-23121, sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachloretriburonuron , molinate, monalide, monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodi amines proglinazine, propmeton, Prometryne, propachlor, tebutam, tebuthiuron ^ terbacil, terbumeton, Terbuthylazine, terbutryn, thiazafiuoron, thifensulfuron, thiobencarb, tiocarbazil , tioclorim, tralkoxydim, tri-allate, triasulfuron, tribenzuron, triclopyr, tridiphane, trietazine, trifluralin, IBI-C4874 vemolate, propanil, propaquizafop, propazine, propham.

The weight ratios of the active ingredients or the carrier / active ingredient combination in these active ingredient combinations can be varied within relatively large ranges.

The active substance combinations preferably contain the carrier / active substance combination in an amount of 0.1 to 99.9%, in particular 1 to 75%, particularly preferably 5 to 50%, the rest being filled 100% by one or more of the above-mentioned mixing partners.

Carrier / active ingredient combinations with zeolites as the carrier material and with active ingredients such as iodopropyl carbamates such as iodopropargyl butyl carbamate, chlorophenyl formal, phenyl carbamate, hexyl carbamate, cyclohexyl carbamate, iodopropargyloxyethylenyl carbamate compounds and iodopropargyloxyamate carbamate compounds and binders thereof with iodopropargyloxyamate carbamate Diuron.

Other particularly preferred mixing partners of the iodine compounds bound to a carrier are: tetrachloroisophthalonitrile, benzisothiazolinones, n-octylisothiazolinones, 2,3,5 ₃ 6-tetrachloro-4-methylsulfonylpyridine, 4,5-dichloro-2-n-octyl 4-isothiazolin-3-one and / or propi conazole.

The following examples serve to illustrate the invention. The invention is not limited to the examples. Example 1 (not according to the invention, comparative example)

A sample of recrystallized white 3-iodo-2-propynyl-n-butyl carbamate (IPBC) was exposed to bright sunlight in a glass vial for 6 hours. The sample turned clearly yellow. After 15 min. When irradiated with a high pressure mercury lamp, the sample was deep yellow.

Example 2 (not according to the invention, comparative example)

A sample of IPBC (as above) was treated in a fine aqueous suspension as in Example 1. The suspension turned yellowish gray. After 15 min. When irradiated with a high pressure mercury lamp, the sample was deep yellow.

Example 3

A 10 g sample of IPBC (as above) was taken up in anhydrous hexane and 90 g of Na zeolite-X were added. After stirring for 20 minutes, the solvent was evaporated in a water jet vacuum. 105.9 g of white powder were obtained.

Example 4

A sample of the white powder from Example 3 was irradiated as described in Example 1. No discoloration, even superficial, was observed after the same period. After 75 min. No discoloration was observed when irradiated with a high pressure mercury lamp.

Example 5

A sample of the white powder as from Example 3 was suspended in water as described in Example 2 and also irradiated. No discoloration was observed, neither of the solution nor of the crystals. After 15 minutes of exposure to a high pressure mercury lamp, no discoloration was observed.

Claims

claims

1. carrier / active ingredient combination characterized by an inorganic carrier and an iodine-containing microbicidal compound as the active ingredient.

2. carrier / active ingredient combination according to claim 1, characterized in that the carrier materials nat. and synthetic zeolites, layered silicates,

Alumina, precipitated silica, diatomaceous earth, silica gels, aerosils, bentonites, kaolins, activated carbons, natural and synthetic clay minerals, TiO ₂ , ZnO, calcium carbonate, dolomites, pumice stones, attapulgites, seprolites, bell clays, clays, among others alumophosphates, silicoaluminophosphates, me- , crystalline silicas with pore structure or

Are mixtures of these.

3. carrier / active ingredient combination according to claim 1, characterized in that the iodine-containing compounds of formula (I) or (VI)

IC≡C-CH ₂ -OR (I)

IC≡C- (COO) _n -R '(II)

(Triiodoalkyl alcohol) (IN)

IC≡C-CH ₂ -OH (iodopropyl alcohol) (V)

SO-: // w • Me (Amical) (VI) (Periodethylene) (VII)

in which

R represents phenyl, naphthyl, heterocyclyl or cyclohexyl which is mono- to pentasubstituted or substituted by Cl, Me, Et, or

R stands for the groups -CH ₂ CH ₂ -O-CO-NHR ^' or -CO-NHR, in which R stands for linear or branched CT-C _jg alkyl, preferably C ₂ -C ₆ alkyl, or the meaning of R has, or

R stands for the group -CO-NR'R ", in which R and R" are identical or different and stand for hydrogen, have the meaning given for R or together form a heterocycle,

n stands for the number zero or one.

4. carrier / active ingredient combinations according to claim 1, characterized gekennzeich¬ net that the iodine-containing microbicides iodopropargylcarbamate such as iodopropargyl-butyl carbamate, chlorophenyl formal, phenyl carbamate, hexyl carbamate, cyclohexyl carbamate and oxyethylphenyl carbamate and iodoproparamyl carbamate and mixtures thereof.

5. Carrier / active ingredient combination of zeolites and IPBC.

6. Microbicidal compositions containing at least one carrier / active ingredient combination according to claim 1 and other customary additives.

7. A method for protecting industrial materials, characterized gekenn¬ characterized in that carrier / active substance combinations according to claim 1 mixed with the materials to be protected or applied to them.

8. The method of carrier / active ingredient combinations according to claim 1 for the protection of industrial materials.

9. A process for the preparation of carrier / active compound combinations according to claim 1, characterized in that the inorganic carrier is loaded with the iodine compounds.