EP1926367A1 - Stabilization of iodine biocides - Google Patents

Abstract

2-(2-Hydroxyphenyl)benzotriazoles are excellent at stabilizing iodine-containing biocides in industrial materials, particularly in paints based on alkyd resin.

Description

Stabilization of iodine-containing biocides

The invention relates to the use of known 2- (2-hydroxyphenyl) benzotriazoles as stabilizers of iodine-containing biocides, as well as active ingredient formulations, concentrates and technical products containing iodine-containing biocide and 2- (2-hydroxyphenyl) benzotriazoles.

Iodine-containing biocides are generally used to protect engineering materials from decomposition / destruction and optical change by fungi, bacteria and algae, preferably fungi. In addition to iodoalkynyl compounds, active substances are also used here in which one or more iodine atoms are bonded to double bond systems, but also to singly bonded carbon atoms.

All iodine-containing biocides have in common that on the one hand under the action of light to a yellowing, with simultaneous loss of active ingredient and effect and on the other in many applications, but especially in solvent-based formulations, paints, glazes or paints even without the action of light chemically are unstable, which manifests itself in a degradation of the active ingredient with the result of a reduced biological effect.

Particularly strong is the chemical degradation in the presence of transition metal compounds, which are preferably used as driers (siccatives) in alkyd resin-containing paints. Cobalt-containing dryers should be mentioned here in particular, but lead and manganese and vanadium dryers, which are used alternatively and in part, lead to a considerable reduction in active ingredient.

In addition to the dryers, there are a number of other constituents in paints, lacquers, primers, impregnations, glazes and active ingredient formulations which lead to a degradation of iodine-containing biocides in varying degrees of intensity. While among the commonly used

Solvents the destabilizing effect is still relatively weak, the other common components of a color formulation, e.g. Process additives, plasticizers,

Color pigments, anti-settling agents, thixotropic agents, corrosion inhibitors, skin inhibitors and binders more or less pronounced destabilizing effects.

Surprisingly, it has now been found that iodine-containing biocides can be stabilized by the use of certain 2- (2-hydroxyphenyl) benzotriazoles, so that the disadvantages described above, such as color changes and chemical degradation, can be prevented.

The 2- (2-hydroxyphenyl) benzotriazoles to be used according to the invention are known and are widely used as UV absorbers, for example for the protection of plastics (see JF Rabek, Photostabilization of polymers: principles and applications Elsevier Science Publisher Ltd., London 1990, pp. 229-241).

While 2- (2-hydroxyphenyl) benzotriazoles have hitherto been used only as UV absorbers, other methods are already known for preventing the degradation of halopropargyl compounds in transition metal-containing alkyd resin paints. Thus, for example, WO 98/22543 describes the addition of chelating reagents.

Furthermore, transition metal-containing alkyd paints are known in which Halogenpropargylverbindungen are stabilized by organic epoxides (see WO 00/16628).

The stabilizing effect of the o.g. Stabilizers, however, are not always adequate and are subject to application-related disadvantages. Thus, when using o.g. Stabilizers especially the drying times of the colors significantly extended, which is unacceptable to the user in many cases.

The present invention therefore provides active substance mixtures comprising at least one iodine-containing biocide and at least one 2- (2-hydroxyphenyl) benzotriazole of the general formula (I),

in which

R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen, sulfo, sulfato or halogen

and

R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, halogen, hydroxyl, sulfo,

Sulfato or are each optionally substituted alkyl, cycloalkyl, alkoxy or aryl.

Preference is given to mixtures comprising at least one iodine-containing biocide and at least one 2- (2-hydroxyphenyl) benzotriazole of the formula (I), in which

R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydrogen, sulfo, sodium sulfonate,

Potassium sulfonate, lithium sulfonate, chlorine, bromine or fluorine,

and

R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, bromine, chlorine, fluorine, hydroxyl,

Sulfo, sodium sulfonate, potassium sulfonate, lithium sulfonate, straight-chain or branched, unsubstituted or mono- or polysubstituted or differently substituted Ci-C ₂₀ alkyl, straight-chain or branched, unsubstituted or mono- or polysubstituted or differently substituted Ci-C ₂ o alkoxy, unsubstituted or mono- or polysubstituted C ₃ -C ₂ are cycloalkyl,

wherein the substituents for the mono- or polysubstituted or differently substituted or differently substituted alkyl radicals, alkoxy radicals and cycloalkyl radicals are selected from the group: halogen; nitro; cyano; hydroxy; C 1 -C ₁₀ -alkoxy; C ₂ -C ₂ o-Polyethylenglycoloxy, C ₁ -C ₆ -Acyl, C _r C ₂₀ acyloxy, C ₁ - Cao alkoxycarbonyl, C ₁ -C ₂₀ - Polyethylenglycoloxycarbonyl, carboxyl and its lithium, sodium and potassium salts.

Very particular preference is given to mixtures of active substances containing at least one iodine-containing biocide and at least one 2- (2-hydroxyphenyl) benzotriazole of the formula (I),

in which

R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydrogen, sulfo, sodium sulfonate,

Potassium sulfonate, chlorine or fluorine

and

R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, chlorine, fluorine, hydroxyl, sulfo,

Sodium sulfonate, potassium sulfonate, is straight-chain or branched, unsubstituted or monosubstituted to trisubstituted by identical or different substituents represent straight-chain or branched, unsubstituted or mono- to trisubstituted by identical or different substituents C ₁ -C ₁₅ -alkoxy, unsubstituted or monosubstituted to trisubstituted C ₃ -C ₈ -cycloalkyl, wherein the substituents for the mono- to trisubstituted by identical or different substituted CVC ₁₅ .

Alkyl radicals, C _r Ci ₅ .Alkoxy and C ₃ -C ₈ -cycloalkyl radicals are selected from the series chlorine; Fluorine; nitro; cyano; hydroxy; unbranched or branched Q-Cg alkoxy; C ₂ -C ₆ - Polyethylenglycoloxy, straight or branched displayed QC ₄ -acyl, non-displayed or branched C _r C ₁₈ acyloxy, straight or branched C _r displayed Ci ₈ alkoxycarbonyl, C _r C ₁₆ - Polyethylenglycoloxycarbonyl, carboxy, sodium carboxylate and potassium carboxylate.

The radicals given in the respective definitions or preferred and particularly preferred definitions can be replaced, irrespective of the particular combination given, optionally also by radical definitions of other combinations. In addition, remainder definitions from any preferred area can be omitted.

Particular preference is given to mixtures according to the invention which contain at least one of the following 2- (2-hydroxyphenyl) benzotriazoles:

2- (2-hydroxy-5-tert-octylphenyl) benzotriazoles, 2- (2-hydroxy-5-methylphenyl) benzotriazoles, 2- (2-hydroxy-5-hydroxyethylphenyl) benzotriazoles,

2- (3-Ally] -2-hydroxy-5-methylphenyl) benzotriazoles,

2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole,

2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorbenzotriazole,

2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazoles, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -benzotriazoles,

2- (3-tert-butyl-2-hydroxy-5- (2-octyloxycarbonylethyl) phenyl) benzotriazoles,

2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazoles,

2- [3- (2H-l, 2,3-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl,

2-methyl acrylates 2- (2-hydroxy-5-tert-octylphenyl) benzotriazoles, 2- (3-sec-butyl-5-tert-butyl-2-hydroxyphenyl) benzotriazoles,

2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol],

2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazoles, α-3- [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] -1 -oxopropyl-ω- [3- [3- (2H-benzotriazol-2-yl) -5-l, 1-dimethylethyl] -4-hydroxyphenyl] -1-oxopropylpoly (oxy-1,2-ethanediyl) (CAS No. 104810-47-1), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol,

2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole,

1,6-hexanediol bis (3-benzotriazol-2-yl-5-tert-butyl-4-hydroxybenzene propionate),

2- (2H-benzotriazole-2-yl) -4,6-bis (l-methyl-l-phenylethyl) phenol. The iodine-containing biocides contained in the mixtures according to the invention are preferably iodoalkynyl compounds. By this is meant compounds wherein one or more iodine atoms are attached to double bond systems or compounds wherein one or more iodine atoms are attached to singly bonded carbon atoms.

The iodine-containing active substances are particularly preferably the following compounds: 3-iodo-2-propynyl-propyl-carbamate, 3-iodo-2-propynyl-butyl-carbamate (IPBC), 3

Iodo-2-propynyl-m-chlorophenyl carbamate, 3-iodo-2-propynyl-phenyl-carbamate, 3-iodo-2-propynyl

2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenylformal (IPCF), di (3-iodo-2-propynyl) hexyl dicarbamate, 3-iodo-2-propynyl oxyethanol ethylcarbamate, 3 -Iodo-2-propynyl-oxyethanol-phenylcarbamate, 3-iodo-2-propynyl-thioxo-thioethylcarbamate, 3-iodo-2-propynylcarbamic acid ester (IPC), N-iodopropargyloxycarbonyl-alanine, N-iodopropargyloxycarbonyl-alanine ethyl ester, 3- (3-iodopropargyl) -benzoxazol-2-one, 3- (3-iodopropargyl) -6-chlorobenzoxazol-2-one,

Diiodomethyl-p-tolylsulfone, diiodomethyl-p-chlorophenylsulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3, 3-Triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynylcyclohexylcarbamate.

The mixtures according to the invention generally contain 0.01-70% by weight of at least one iodine-containing biocide and 0.001-50% by weight of at least one 2- (2-hydroxyphenyl) benzotriazole of the formula (I), preferably 0 , 05-60% by weight of at least one iodine-containing biocide and 0.005-40% by weight of at least one 2- (2-hydroxyphenyl) benzotriazole of the formula (I), and more preferably 0.1-50% by weight .-% of at least one iodine-containing biocide and 0.01 to 30 wt .-% of at least one 2- (2-hydroxyphenyl) benzotriazole of the formula (I).

The mixtures according to the invention can be prepared by mixing the individual components with one another depending on their respective physical and / or chemical properties without additives or converting them into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and finest encapsulations in polymeric substances.

The mixtures according to the invention are suitable for the protection of industrial materials. Among technical materials, non-living materials are in the present context too which have been prepared for use in the art. For example, the technical materials are adhesives, glues, paper and cardboard, textiles, leather, wood, wood-based materials, paints and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms.

Another object is the use of the mixtures according to the invention for the protection of industrial materials against attack and / or destruction by microorganisms.

As microorganisms that can cause degradation or a change in the technical materials, for example, bacteria, fungi, yeasts, algae and mucus organisms may be mentioned. The active compounds according to the invention preferably act against fungi, in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and bacteria.

For example, microorganisms of the following genus are mentioned:

Alternaria, such as Alternaria tenuis,

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

Coniophora, like Coniophora puetana,

Lentinus, like 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, like Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.

Furthermore, the mixtures according to the invention, depending on their respective physical and / or chemical properties, can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and ultrafine encapsulations in polymeric substances. These formulations can be prepared in a known manner, for example by mixing the

Single active substances with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. 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 and dimethyl sulfoxide, and water. By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifiers and / or foam-formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylarylpolyglycolether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may 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.

The formulations generally contain between 0.1 and 95 percent by weight of active compound mixture, preferably between 2 and 75 percent by weight. The present invention furthermore relates to microbicidal compositions based on the mixtures according to the invention, comprising at least one solvent or diluent and, if appropriate, processing auxiliaries and optionally further antimicrobial substances. Here, the active ingredients may be present either in dissolved form or as suspensions or emulsions. The solvents or diluents are either water or all common organic solvents.

The efficacy and spectrum of activity of the mixtures according to the invention or of the preparations obtainable therefrom can be increased if, if desired, further antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active substances are added to increase the spectrum of activity or to achieve particular effects. These mixtures can have an even broader spectrum of activity.

In many cases synergistic effects, i. E. the effectiveness of the mixture is greater than the effectiveness of the individual components. Particularly favorable mixing partners are e.g. the following connections:

Triazoles such as:

Azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, epoxyconazole, etaconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, isozofos, myclobutanil, metconazole, paclobutrazole, penconazole, Propioconazole, prothioconazole, simeoconazole, (+) - cis-1- (4-chlorophenyl) -2- (1H-l, 2,4-triazol-1-yl) -cycloheptanol, 2- (1-tert-butyl) - 1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) -propan-2-ol, tebuconazole, tetraconazole, triadimefon, triadimol, tri-pentenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts ;

Imidazoles like:

Clotrimazole, bifonazole, climbazole, econazole, fenapamil, imazalil, isoconazole, ketoconazole, lombazole, miconazole, pefurazoate, prochloraz, triflumizole, thiazol-1-l-imidazolyl-1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one and the like their metal salts and acid adducts;

Pyridines and pyrimidines such as:

Ancymidol, buthiobate, fenarimol, mepanipyrine, nuarimol, pyroxyfur, triamirole;

Succinate dehydrogenase inhibitors such as: Benodanil, Carboxime, Carboximsulfoxide, Cyclafluramid, Fenfuram, Flutanil, Furcarbanil,

Furmecyclox, Mebenil, Mepronil, Methfuroxam, Metsulfovax, Nicobifene, Pyrocarbolide, Oxycarboxin, Shirlan, Seedvax;

Naphthalene derivatives such as:

Terbinafϊn, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-yn); Sulphenamides like:

Dichlorofluidide, tolylfluanid, folpet, fluorfolpet; Captan, Captofol; Benzimidazoles such as:

Carbendazim, benomyl, fuberidazole, thiabendazole or their salts; Morpholine derivatives such as:

Aldimorph, dimethomorph, dodemorph, falimorph, fenpropidin, fenpropimorph, tridemorph, trimorphamide and their arylsulfonic acid salts, e.g. p-toluenesulfonic acid and p-dodecylphenylsulfonic acid;

Benzothiazoles such as: 2-mercaptobenzothiazole;

Benzothiophene dioxides such as:

BenzofbJthiophen-S ^ dioxide-carboxylic acid cyclohexylamide;

Benzamides like:

2,6-Dichloro-N- (4-trifluoromethylbenzyl) benzamide, Tecloftalam; Boron compounds such as:

Boric acid, boric acid ester, borax;

Formaldehyde and formaldehyde-releasing compounds such as:

Benzyl alcohol mono- (poly) -hemiformal, 1,3-bis (hydroxymethyl) -5,5-dimethylimidazolidine-2,4-diones (DMDMH), bisoxazolidines, n-butanol hemiformal, cis 1- (3-chloroallyl) -3 , 5,7-triaza-1-azoniaadamantane chloride, 1- [1,3-bis (hydroxymethyl-2,5-dioxoimidazolidin-4-yl] -l, 3-bis (hydroxymethyl) urea, dazomet, dimethylolurea, 4, 4-dimethyl-oxazolidines, ethylene glycol hemiformal, 7-ethylbicyclooxazolidines, hexa-hydro-S-triazines, hexamethylenetetramine, N-hydroxymethyl-N'-methylthiourea, methylenebismorpholine, sodium N- (hydroxymethyglycinate, N-methylolchloroacetamide, oxazolidines, paraformaldehyde , Tauroline, tetrahydro-1,3-oxazine, N- (2-hydroxypropyl) -amine-methanol, tetramethylol-acetylene-diurea (TMAD); Isothiazolinones such as:

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, 5-chloro-N-octylisothiazolinone, N-octylisothiazolin-3-one on, 4,5-trimethylene-isothiazolinone, 4,5-benzisothiazolinone;

Aldehydes such as:

Cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde, o-phthaldialdehyde;

Thiocyanates such as:

Thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate; quaternary ammonium compounds and guanidines such as: benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, dichlorobenzyldimethylalkylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, N-hexadecyltrimethylammonium chloride,

1-hexadecylpyridinium chloride, iminoctadine-txis (albesilat);

Iodine derivatives such as:

Diiodomethyl-p-tolylsulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoallylic alcohol, 3-bromo- 2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate, 3-iodo-2-propynylcyclohexylcarbamate, 3-iodo-2- propynyl phenylcarbamate;

Phenols like:

Tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, dichlorophen, 2-benzyl-4-chlorophenol, triclosan, diclosan, hexachlorophene, p-hydroxybenzoic acid methyl ester, p-hydroxybenzoic acid ethyl ester, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, octyl p-hydroxybenzoate, o-phenylphenol, m-phenylphenol, p-phenylphenol, 4- (2-tert-butyl-4-methyl-phenoxy) -phenol, 4- (2- Isopropyl 4-methylphenoxy) phenol, 4- (2,4-dimethylphenoxy) phenol and their alkali and alkaline earth metal salts; Microbicides with activated halogen group such as:

Bronopol, Bronidox, 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 1-bromo-3-chloro-4,4,5,5-tetramethyl-2-imidazoledione , β-bromo-β-nitrostyrene, chloroacetamide, chloramine T, l, 3-dibromo-4,4,5,5-tetramethyl-2-imidazoledione, dichloramine T, 3,4-dichloro (3H) -l, 2 dithiol-3-one, 2,2-dibio-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, halanes, halazones, mucochloric acid, phenyl (2-chloro-cyanovinyl) sulfone, Phenyl (1, 2-dichloro-2-cyanovinyl) sulfone, trichloroisocyanuric acid;

Pyridines like:

l-hydroxy-2-pyridinethione (and its Cu, Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrrithione, 1-hydroxy-4-methyl-6- ( 2,4,4-trimethylpentyl) -2 (1H) -pyridine;

Methoxyacrylates or similar such as:

Azoxystrobin, Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, 2,4-dihydro-5-methoxy-2-methyl-4- [2 - [[[[l- [3- (trifluoromethyl ) phenyl] ethylidenes] amino] oxy] methyl] phenyl] -3H-l, 2,4-triazol-3-ones (CAS No. 185336-79-2);

Metal soaps like:

Salts of the metals tin, copper and zinc with higher fatty, resinous, naphthenic and phosphoric acid e.g. Tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;

Metal salts like:

Salts of the metals tin, copper, zinc, as well as chromates and dichromates such. Copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;

Oxides like:

Oxides of the metals tin, copper and zinc, e.g. Tributyltin oxide, Q12O, CuO, ZnO;

Oxidizing agents such as:

Hydrogen peroxide, peracetic acid, potassium persulfate;

Dithiocarbamates such as: Cufraneb, Ferban, potassium N-hydroxymethyl-N'-methyl-dithiobarbamate, Na- or K-dimethyl-dithiocarbamate, Macozeb, Maneb, Metam, Metiram, Thiram, Zineb, Ziram;

Nitriles like:

2,4,5,6-tetrachloroisophthalodinitrile, disodium cyanodithioimidocarbamate; Chinolins like:

8-hydroxyquinoline and its Cu salts; other fungicides and bactericides such as:

Bethoxazine, 5-hydroxy-2 (5H) -furanone; 4,5-benzdithiazolinone, 4,5-trimethylenedithiazolinone, N- (2-p-chlorobenzoylethyl) hexaminium chloride, 2-oxo-2- (4-hydroxyphenyl) -aceto-hydroximic acid chloride, tris-N- (cyclohexyldiazeniumdioxy) -aluminum , N- (cyclohexyldiazeniumdioxy) -tributyltin or K-salts, bis-N- (cyclohexyldiazeniumdioxy) -copper, iprovalicarb, fenhexamide, spiroxamine, carpropamide, diflumetorin, quinoxyfen, famoxadone, polyoxorim, acibenzolar-S-methyl, Furametpyr, thifluzamide, methalaxyl-M, benthiavalicarb, metrafenone, cyflufenamid, tiadinil, tea tree oil, phenoxyethanol,

Ag, Zn or Cu-containing zeolites alone or included in polymeric materials.

Very particular preference is given to mixtures with

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, diuron, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet, methfuroxam, carboxin, benzotbjthiophene-S-dioxide-carboxylic acid cyclohexylamide, fenpiclonil, 4- (2,2- Difluoro-1, 3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile, butenafine, imazalil, N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazoline 3-one, dichloro-N-octylisozhiazolinone, mercaptobenzothiazole, thiocyanatomethylthiobenzothiazole, thiabendazole, benzisothiazolinone, N- (2-hydroxypropyl) amino methanol, benzyl alcohol (hemi) formal, N-methylolchloroacetamide, N- (2-hydroxypropyl) -aminomethanol, glutaraldehyde, Omadine, Zn-Omadine, dimethyldicarbonate, 2-bromo-2-nitro-1,3-propanediol, 3-iodo-2-propynyl-n-butylcarbamate, Bethoxazine, o-phthaldialdehyde, 2 , 2-DibiOm-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, 1,3-bis (hydroxymethyl) -5,5-dimethylimidazolidine-2,4-dione (DMDMH), tetramethylol -ac ethenylene diurea (TMAD), ethylene glycol hemiformal, p-hydroxybenzoic acid, carbendazim, chlorophene, 3-methyl-4-chlorophenol, o-phenylphenol.

Furthermore, in addition to the above-mentioned fungicides and bactericides, well-effective mixtures with other active ingredients are also prepared: Insecticides / acaricides / nematicides:

Abamectin, Acephate, Acetamiprid, Acetoprole, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Aldrin, Allethrin, Alpha-Cypermethrin, Amidoflumet, Amitraz, Avermectin, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, barthrin, 4-bromo-2 (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, bioresmethrin, bioallethrin, Bistrifluron, Bromophos A, Bromophos M, Bufencarb, Buprofezin, Butathiophos, Butocarboxine, Butoxycarboxime,

Cadusafos, carbaryl, carbofuran, carbophenothione, carbosulfan, cartap, quinomethionate, cocoethocarb, 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone

(CAS-RN: 120955-77-3), chlorodanes, chloroethoxyfos, chlorfenapyr, chlorfenvinphos,

Chlorofluorazuron, chlormephos, N - [(6-chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethanimidide amide, chloφicrin, chlorpyrifos A, chlorpyrifos M, cis-resmethrin, clocythrin, clothiazoben,

Cypophenothrin Clofentezine, Coumaphos, Cyanophos, Cycloprothrin, Cyfluthxin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazine,

Decamethrin, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, dialiphos, diazinon, 1,2-dibenzoyl-l (1,1-dimethyl) -hydrazine, DNOC, dichlorofenthione, dichlorvos, dicliphos, dicrotophos, difethialone , Diflubenzuron, dimethoate, 3,5-dimethylphenyl-methylcarbamate, dimethyl (phenyl) -silyl-methyl-3-phenoxybenzyl ether, dimethyl (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzyl ether, dimethylvinphos, dioxathione, disulfone,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethioπ, Ethofenprox, Etrimphos, Etoxazole, Etobenzanide,

Fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fensulfothion, fenthione, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flupyrazofos, fluffine, flumethrin flufenprox , Fluvalinate, Fonophos, Formethanates, Formothion, Fosmethilan Fosthiazat, Fubfenprox, Furathiocarb,

Halofenocide, HCH (CAS RN: 58-89-9), heptenophos, hexaflumuron, hexythiazox, hydramethylnone, hydroprene,

Imidacloprid, imiprothrin, indoxycarb, iodoffen, iprinomectin, Iprobenfos, isazophos, isoamidophos, isofenphos, isoprocarb, isoprothiolanes, isoxathion, ivermectin, Kadedrin

Lambda-Cyhalothrin, Lufenuron,

Malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathione, methiocarb, methomyl, metalcarb, milbemectin, monocrotophos, moxiectin,

Naled, NI 125, nicotine, nitenpyram, noviflumuron,

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, parathion M, penfluron, permethrin, 2- (4-phenoxyphenoxy) ethyl-ethylcarbamate, phenthoate, phorate, phosalone, phosmet, phosphamidone, phoxim, pirimicarb, pirimiphos M, pirimiphos A, prallethrin, profenophos, promecarb, propaphos, Propoxur, Prothiophos, Prothoate, Pymetrozine, Pyrachlophos, Pyridaphenthione, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyrimidifen, Pyriproxifen, Pyrithiobac Sodium

quinalphos,

Resmethrin, Rotenone,

Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfotep, Sulprofos,

Tau fluvalinate, Taroils, Tebufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Tetramethrin, Tetramethacarb, Thiacloprid, Thiafenox, Thiamethoxam, Thiapronil, Thiodicarb, Thiofanox, Thiazophos, Thiocyclam, Thiomethone, Thionazine, Thuringiensin, Tralomethrin, transfluthrin, triarathene, triazophos, triazamates, triazuron, trichlorfon, triflumuron, trimethacarb,

Vamidothione, xylylcarb, zetamethrin;

molluscicides:

Fentin acetate, metaldehyde, methiocarb, niclosamide;

Herbicides and algicides:

Acetochlor, Acifluorfen, Aclonifen, Acrolein, Alachlor, Alloxydim, Ametryn, Amidosulfuron, Amitrole, Ammonium sulfamate, Anilofos, Asulam, Atrazine, Azafenidine, Aziptrotryn, Azimsulfuron, Benazoline, Benfluralin, Benfuresat, Bensulfuron, Bensulfide, Bentazone, Benzofencap,

Benzothiazuron, Bifenox, Bispyribac, B ispyribac sodium, Borax, Bromacil, Bromobutide, Bromofenoxime, Bromoxynil, Butachlor, Butamifos, Butraline, Butylate, Bialaphos, Benzoyl-prop, Bromobutide, Butroxydim,

Carbetamido, carfentrazone-ethyl, carfenstrol, chlomethoxyfen, chloramphene, chlorobromuron, chloroflorene, chloridazon, chlorimuron, chloronitrofen, chloroacetic acid, chloransulam-methyl, cinidon-ethyl, chlorotoluron, chloroxuron, chlorpropham, chlorosulfuron, chlorothal, chlorthiamide, cinmethylin, cinofulsuron, clefoxydim, Clethodaz, clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, cycloate, cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron, clometoxyfen, cyhalofop, cyhalofop-butyl, clopyrasuluron, cyclosulfamuron,

Diclosulam, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, difluufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethipine, dinitramine, dinoseb, dinoseb acetates, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, DSMA , 2,4-D, daimurone, dalapon, dazomet, 2,4-DB, desmedipham, desmetryne, dicamba, dichlobenil, dimethamide, dithiopyr, dimethametryn,

Eglinazine, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethidimuron, Ethofumesate, Ethobenzanide, Ethoxyfen, Ethametsulfuron, Ethoxysulfuron,

Fenoxaprop, Fenoxaprop-P, Fenuron, Flamprop, Flamprop-M, Flazasulfuron, Fluazifop, Fluazifop-P, Fuenachlor, Fluchloralin, Flufenacet Flumeturon, Fluorocglycofen, Fluoronitrofen, Flupropanate, Flurenol, Fluridone, Flurochloridone, Fluroxypyr, Fomesafen, Fosamine, Fosametine, Flamprop -isopropyl, flamprop-isopropyl-L, flufenpyr, flumiclorac-pentyl, flumipropyne, flumioxzim, flurtamone, flumioxime, flupyrsulfuron-methyl, fluthiacet-methyl,

Glyphosate, glufosinate-ammonium

Haloxyfop, hexazinone,

Imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, imazosulfuron, imazomox, isoxaflutole, imazapic,

ketospiradox,

Lactofen, Lenacil, Linuron,

MCPA, MCPA hydrazide, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron, metam, metamifop, metamitron, metazachlor, methabenzthiazuron, Methazole, methopyrone, methyldyrarone, methylisothiocyanate, metobromuron, metoxuron,

Metribuzin, metsulfuron, molinate, monalid, monolinuron, MSMA, metolachlor, metosulam, metobenzuron,

Naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, sodium chlorate,

Oxadiazon, oxyfluorfen, oxysulfuron, orbencarb, oryzalin, oxadiargyl,

Propyzamide, Prosulfocarb, Pyrazolates, Pyrazolesulfuron, Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Paraquat, Pebulate, Pendimethalin, Pentachlorophenol, Pentoxazone, Pentanochlor, Petroleum Oils, Phenmedipham, Picloram, Piperophos, Pretilachlor, Primisulfuron, Prodiamine, Profoxydim, Prometryn, Propachlor, Propanil, Propaquizafob, propazine, prophyne, propisochlor, pyriminobac-methyl, pelargonic acid, pyrithiobac, pyraflufen-ethyl,

Quinmerac, quinocloamine, quizalofop, quizalofop-P, quinchlorac,

rimsulfuron

Sethoxydim, sifuron, simazine, simetryn, sulfosulfuron, sulfometuron, sulfentrazone, sulcotrione, sulfosate,

Tar oils, TCA, TCA sodium, tebutam, tebuthiuron, terbacil, terbumetone, terbutylazine, terbutryn, thiazafluorone, thifensulfuron, thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimine, thiazopyr, triflusulfuron,

Vernolate.

Another object of the present invention is the use of 2- (2-hydroxyphenyl) - benzotriazole of the formula (I) for the stabilization of iodine-containing biocides against chemical degradation reactions. The substances to be protected from degradation may in principle be all iodine-containing active substances. The use according to the invention is preferred for stabilizing the iodine-containing biocides listed above as being preferred and particularly preferred.

In addition to the known effect as UV absorber, the 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) to be used according to the invention also have a strongly stabilizing effect on iodine-containing biocides in formulations and industrial products in which the instability does not affect the Presence of UV light is due. Another object of the present invention is the use of 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) as Stabilizers in iodine-containing formulations and technical products against chemical

Degradation reactions and color changes.

In particular, the 2- (2-hydroxyphenyl) benzotriazoles of formula (I) can be used to suppress the chemical degradation of iodine-containing biocides in drug formulations, especially paints such as paints, varnishes, primers, Impregnierungen, glazes and other engineering materials or at least to slow down. The 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) which can be used according to the invention for stabilizing iodine-containing biocides have a very good stabilizing effect, especially in alkyd resin-based systems such as paints containing transition metal dryers.

The present invention furthermore relates to the use of 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) for stabilizing iodine-containing biocides in alkyd resin-based paints containing transition-metal dryers.

The paints used according to the invention are in particular paints, lacquers, primers, impregnations and glazes which contain binders based on alkyd resins.

The alkyd resins contained in the paints are generally polycondensation resins of polyols, polybasic carboxylic acids or their anhydrides and fatty oils or free natural and / or synthetic fatty acids. The alkyd resins may optionally be chemically modified.

The polyols mentioned are preferably glycerol, pentaerythritol, trimethylolethane, trimethylolpropane and various diols, such as ethane / propane diol, diethylene glycol, neopentyl glycol.

The polybasic carboxylic acids or their anhydrides mentioned are preferably phthalic acid, phthalic anhydride, maleic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, adipic acid, azelaic acid or sebacic acid.

The oils or fatty acids mentioned are generally linseed oil, oiticia oil, wood oil, soybean oil, sunflower oil, safflower oil, ricinole oil, tall oil, castor oil, coconut oil, peanut oil, their fatty acids and synthetic monocarboxylic acids.

Optionally, the alkyd resins may optionally be modified with natural resins, phenolic resins, acrylic resins, styrene, epoxy resins, silicone resins, isocyanates, polyamides or aluminum alcoholates. The alkyd resins generally have a molecular weight of 500 to 100,000. Preferably, the

Molar mass 1000 to 50,000 and more preferably 1500 to 20,000.

The alkyd resins are generally present at from 1 to 80% by weight, preferably from 2 to 70% by weight and more preferably from 3 to 60% by weight, in the paints, preferably paints, lacquers, primers, impregnations or glazes ,

The transition metal dryers are used to accelerate the drying and curing of oxidatively drying alkyd paints. The salts of transition metals of the groups Vb, VIb, VIIb, VIH and Ib of the chemical periodic table are preferably used according to the invention. It is preferably the salts of cobalt, manganese, vanadium, nickel, copper and iron, in particular cobalt, manganese, iron and vanadium .. They are not necessarily used alone, but sometimes also in combination with non-transition metal salts, such as For example, lead, calcium or zirconium.

The transition metal salts generally consist of the organic solvent-soluble salts of said transition metals. In principle, it may be the salts of all carboxylic acids which have a good compatibility with the alkyd resin binders and ensure sufficient solubility of the metal salt. The transition metal salts of fatty acids such as oleates or linoleates, resin acids such as resinates or salts of 2-ethylhexanoic acid (octoates) are preferably used. Preferred transition metal dryers are cobalt octoate and cobalt naphthenate.

The amounts of dryers in the alkyd resin based paints can be varied over a wide range and are e.g. the nature and concentration of the alkyd resin binder and the other color components and the desired dry behavior of the color. The necessary amount of dryers can be determined by routine experimentation. In general, from 0.001 to 1 wt .-%, preferably 0.005 to 0.5 wt .-% and very particularly preferably 0.01 to 0.1 wt .-% dryer used, each based on the amount of binder.

In the use according to the invention, in general 1 to 150% by weight of at least one compound of the formula (I), preferably 2 to 100% by weight, in particular 5 to 80% by weight, based on the iodine-containing biocide, are added.

The iodine-containing biocides to be stabilized in the use according to the invention are the compounds generally and specifically listed above. In particular, the use according to the invention of 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) is for the stabilization of IPBC in alkyd resin-based paints containing transition metal dryers. In the use according to the invention, it is preferred to use paints of the following composition:

Color pigments: generally 0 to 50 wt .-%, preferably 0 to 45 wt .-%, particularly preferably 0 to 40 wt .-%.

Alkyd resin binder: generally 1 to 80 wt .-%, preferably 2 to 70 wt .-%, particularly preferably 3 to 60 wt .-%.

Iodinated biocide: generally 0.01 to 5% by weight, preferably 0.05 to 3% by weight, particularly preferably 0.1 to 2% by weight

Compound of formula (I): generally 0.001 to 5 wt .-%, preferably 0.005 to 3 wt .-%, particularly preferably 0.01 to 2 wt .-%.

The paints may also contain fillers, anti-skinning agents, rheology additives such as anti-settling agents and thixotropic agents, other biocides such as fungicides, bactericides, antifouling agents and algicides, solvents, process additives, plasticizers, UV and heat stabilizers, corrosion inhibitors in customary amounts known to those skilled in the art.

Iodine-containing biocides are degraded, especially in the presence of the dryer described in more detail above. Although the strongest effects are observed in the presence of these dryers, a number of other color components also have a destabilizing effect on iodine-containing biocides. Mention may be made of inorganic and organic pigments, fillers, anti-skinning agents, rheology additives such as anti-settling agents and thixotropic agents, other biocides such as fungicides, bactericides, antifouling and algicides, solvents, process additives, plasticizers, UV and heat stabilizers, corrosion inhibitors, etc. The 2- (2 Hydroxyphenyl) benzotriazoles of the formula (I) also show a strong stabilizing effect here.

However, the stabilizing effect of 2- (2-hydroxyphenyl) -benzotriazoles of formula (I) is not limited to drug formulations, paints, varnishes and glazes, but also includes the stabilization of iodine-containing biocides in other media, e.g. Plastics, sealants, adhesives, glues, coolants, active substance concentrates and formulations.

The stabilizing effect of the 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) is independent of the type of addition. Thus, for example, the stabilizer may be added directly or as a solution, suspension or emulsion to the medium containing the iodine-containing biocide. you However, the stabilizer can also be added to the biocide formulation or the biocide concentrate, which moreover has the advantage that the iodine-containing biocide is not only protected from degradation in the final medium, but also already in the active ingredient formulation.

In addition, other stabilizers may also be added, such as, for example, the chelating reagents mentioned in WO 98/22543 or the organic epoxides mentioned in WO 00/16628. In many cases, synergistic effects are observed here.

In addition, one or more antioxidants, free-radical scavengers, UV absorbers and other stabilizers can be added, some of which have synergistic effects.

To call here are:

hindered phenols, such as

2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) - 4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol or 2,6-di-tert-butyl-4-methoxymethylphenol, diethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonates, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, 2-methyl-4,6-bis [(octylthio) methyl] phenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,2'-thio-bis (6-tert. -butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio-bis (6-tert-butyl-3-methylphenol), 4,4'- Thio-bis (6-tert-butyl-2-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (4 -methyl-6-cyclohexylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol ), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), l, l bis (5-tert-butyl-4-hydrox y-2-methylphenyl) -butane, 1,1,3-tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 1,3,5-tri- (3,5-di tert -butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester, 1,3,5-tris- (3 , 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1, 3.5 -Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) -propionyloxyethyl] isocyanurate, 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester, 3,5-di-tert. butyl-4-hydroxybenzylphosphonic acid monoethyl ester calcination salt, N, N'-di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-di- (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine,

N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) -hydrazine, 3,9-bis [1,1-dimethyl-2 - [(3-tert-butyl-4 -hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, bis [3,3-bis (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] ethylene glycol ester, 2,6-bis [[3- (1,1-dimethylethyl) -2-hydroxy-5-methylphenyl] octahydro-4,7-methano-1H-indenyl] -4-methylphenol (= Wingstay L), 2,4-bis (n-octylthio) -6- (3,5-di-tert-butyl-4-hydroxyphenylamino) -s-triazines, N- (4-)

Hydroxypheny octadecanamides, 2,4-di-tert-butylphenyl 3 ', 5'-di-tert-butyl-4'-hydroxybenzoates, (benzoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy-, hexadecyl ester), 3-hydroxyphenyl benzoate, 2,2'-methylenebis (6-tert-butyl-4-methylphenol) monoacrylate, 2- (1, 1-dimethylethyl) -6- [1 - [3- (1, 1 -dimethylethyl) -5- (1, 1-dimethylpropyl) -2-hydroxyphenyl] ethyl] -4- (1,1-dimethylpropyl) phenyl ester,

Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate or di-hydroxyethyl-oxalic acid diamide,

Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with monohydric or polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate or di-hydroxyethyl-oxalsäurediamid. Hindered amines like,

Bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butyl malonate, bis (2,2,6,6 tetramethyl-4-piperidyl) decanedioate, dimethyl succinate 1 - (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine copolymer, poly [[6 - [(1, l, 3,3- tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl- 4-piperidyl) imino]] (CAS No. 71878-19-8), l, 5,8,12-tetrakis [4,6-bis (N-butyl-Nl, 2,2,6,6-pentamethyl- 4-piperidylamino) -l, 3,5-triazin-2-yl] -l, 5, 8, 12-tetraazadodecane (CAS No. 106990-43-6), bis (l, 2,2,6,6 pentamethyl-4-piperidyl) decanedioate, bis (l, 2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butyl malonate, Decanedioic acid, bis (2,2,6,6-tetramethyl-4-piperidinyl) ester, reaction products with tert-Bu hydroperoxide and octane (CAS No. 129757-67-1), Chimasorb 2020 (CAS No. 192268-64 -7), poly [[6-methylphenyl-l, 3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -l, 6-hexanediole l [(2,2,6,6-tetramethyl-4-piperidinyl) imino]], poly [[6- (4-morpholinyl) -l, 3,5-triazine-2,4-diyl] [l, 2,2,6,6-pentamethyl-4-piperidinyl) imino] -l, 6-hexanediyl [(1, 2,2,6,6-pentamethyl-4-piperidinyl) imino]] (9CI), 3-dodecyl -l- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-diones, 3-dodecyl-1 - (1, 2,2,6,6-pentamethylpiperidin-4-yl) pyrrolidines 2,5-dione "4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, poly [[6- (cyclohexylamino) -l, 3,5-triazine-2,4-diyl] [(2,2, 6,6-tetramethyl-4-piperidinyl) imino] -l, 6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino]], 1H, 4H, 5H, 8H-2,3a, 4a, 6,7a, 8a-hexaazacyclopenta [def] fluorenene-4,8-diones, hexahydro-2,6-bis (2,2,6,6-tetramethyl-4-piperidinyl) - (CAS No. 109423-00 -9), N, N'-bis (formyl) -N, N ¹ -bis (2,2,6,6-tetramethyl-4-piperidyl) -l, 6-hexanediamine, N- (tetramethyl-4-) piperidinyl) maleimide-C20-24-α-olefin copolymer (CAS No. 199237-39-3), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate , Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,6,6-pentamethyl-4-piperidinyl tridecyl 1,2,3,4 - butanetetracarboxylate, (1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester), (2,4,8,10-tetraoxaspiro [5.5] undecane-3.9 diethanol, β, β, β ', β'-tetramethyl, polymer with 1,2,3,4-butanetetracarboxylic acid) (CAS No. 115055-30-6), 2,2,4,4-tetramethyl- 21-oxo-7-oxa-3,20-diazadispiro [5.1.11.2] heneicosane, (7-oxa-3,20-diazadispiro [5.1.11.2] heneicosane-20-propanoic acid, 2,2,4,4- tetramethyl-21-oxo, tetradecyl ester), (7-oxa-3,20-diazadispiro [5.1.11.2] - heneicosan-21-one, 2,2,4,4-tetramethyl-20- (oxiranylmethyl) -), (Propanamides, N- (2,2,6,6-tetramethyl-4-piperidinyl) -3 - [(2,2,6,6-tetramethyl-4-piperidinyl) amino] -), (1,3-Propanediamine , N, N "-l, 2-ethanediylbis, polymer with 2,4,6-trichloro ro-I, 3,5-triazines, reaction products with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine) (CAS No. 136504-96-6), I, I'-ethylene-bis (3 , 3,5,5-tetramethyl-2-piperazinone), (piperazinone, 1, 1 ', 1 "- [l, 3,5-triazine-2,4,6-triyltris [(cyclohexylimino) -2, l- ethanediyl]] tris [3,3,5,5-tetramethyl-], (7-oxa-3,20-diazadispiro [5.1.11.2] heneicosane-20-propanoic acid, 2,2,4,4-tetramethyl-21 oxo, dodecyl ester), 1,1-bis (l, 2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, (2-propenoic acid, 2-methyl- , methyl ester, polymer with 2,2,6,6-tetramethyl-4-piperidinyl 2-propenoate) (CAS No. 154636-12-1), (propanamides, 2-methyl-N- (2,2,6, 6-tetramethyl-4-piperidinyl) -2 - [(2,2,6,6-tetramethyl-4-piperidinyl) amino] -), (D-glucitol, 1,3: 2,4-bis-O- ( 2,2,6,6-tetramethyl-4-piperidinylidenes) -) (CA No. 99473-08-2), N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) isophthalamides, 4-hydroxy2,2,6,6-tetramethylpiperidines, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpip eridines, 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidines, 4-stearoyloxy-2,2,6,6-tetramethylpiperidines, 1-ethyl-4 -salicyloyloxy-2,2,6,6-tetramethylpiperidines, 4-methacryloyloxy-l, 2,2,6,6-pentamethylpiperidines, 1,2,6,6-pentamethylpiperidin-4-yl-β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionates, 1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl maleinates,

(Di-2,2,6,6-tetramethylpiperidin-4-yl) adipate, (di-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (Di-1, 2,3,3 , 6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate, (di-1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, l-propargyl4-β- cyanoethyl-oxy-2,2,6,6-tetramethylpiperidine, 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, (trimellitic acid-tri- (2,2,6,6-tetramethylpiperidine -4-yl) ester),

1-Acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, dibutyl-malonic acid-di-

(l, 2,2,6,6-pentamethylpiperidin-4-yl) ester, butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid di (l, 2.2 , 6,6-pentamethylpiperidin-4-yl) ester, dibenzyl malonic acid di (l, 2,2,6,6-pentamethylpiperidin-4-yl) ester, dibenzyl malonic acid di (l, 2 , 3,6-tetramethyl- 2,6-diethyl-piperidin-4-yl) ester, hexane-1 ', 6'-bis-

(4-carbamoyloxy-in-butyl-2,2,6,6-tetramethylpiperidines), toluene-2 ', 4'-bis (4-carbamoyloxy-ln-propyl-2,2,6,6-tetramethylpiperidines), Dimethylbis (2,2,6,6-tetramethylpiperidines-4-oxy) silanes, phenyltris (2,2,6,6-tetramethylpiperidines-4-oxy) silanes, tris (1-propyl -2,2,6,6-tetramethylpiperidin-4-yl) phosphites, tris

(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosphates, phenyl [bis- (1,2,2,6,6-pentamethylpiperidin-4-yl) -phosphonates, di (1,2 , 2,6,6-pentamethylpiperidin-4-yl) sebacate, N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine, N, N'-bis (2 , 2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diacetamide, 1-acetyl-4- (N-cyclohexylacetamido) -2,2,6,6-tetramethylpiperidine,

4-Benzylamino-2,2,6,6-tetramethylpiperidines, N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dibutyladipamide, N, N ' -B is- (2,2,6,6-tetramethylpiperidin-4-yl) - N, N'-dicyclohexyl- (2-hydroxypropylene), N, N'-bis- (2,2,6,6-tetramethylpiperidine-4 -yl) -p-xylylenediamine, 4- (bis-2-hydroxyethyl) amino-1, 2,2,6,6-pentamethylpiperidine, 4- (3-methyl-4-hydroxy-5-tert.-butyl) benzoicacidamido) -2,2,6,6-tetramethylpiperidines, 4-methacrylamino-1, 2,2,6,6-pentamethylpiperidines, 9-aza-8,8,10,10-tetramethyl-l, 5-dioxaspiro [5.5 ] undecane, 9-aza-8,8,10,10-tetramethyl-3-ethyl-l, 5-dioxaspiro [5.51 undecane, 8-aza-2,7,7,8,9,9-hexamethyl-1, 4-dioxaspiro [4.5] decane, P-aza-S-hydroxymethyl-S-ethyl-S ^^ JO.lO-pentamethyl-1S-dioxaspiroCS.S-jundecane, 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl -8,8,10,10-tetramethyl-l, 5-dioxaspiro [5.5] undecane, 2,2,6,6-tetramethyl-piperidine-4-spiro-2 '- (l ¹ , 3'-dioxane) 5 ¹ -spiro-5 "- (l ', 3" -dioxane) -2 "-spiro4" - (2'',2'", 6 '", 6 ^I "-tetrameth ylpiperidine), 3-benzyl-l, 3,8-triaza-7,7,9,9-tetramethyl methyl spiro [4.5] decane-2,4-diones, 3-n-octyl-l, 3,8-triaza-7,7,9,9-tetramethyl-spiro [4.5] decane-2,4-diones, 3-allyl-l, 3,8-triazala, 7,7,9,9-pentamethyl-spiro [4.5] decane-2,4-dione, 3-glycidyl-1,3,8-triaza-7, 7,8,9,9-pentamethyl-spiro (4.5) decane-2,4-dione, 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4- oxyspiro [4.5] decane, 2-butyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxyspiro [4.5] decane, 2-isopropyl-7,7,9,9- tetramethyl-l-oxa-4,8-diaza-oxyspiro [4.5] decane, 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxyspiro [4.5] decane, Bis [β- (2,2,6,6-tetramethylpiperidino) -ethyl] -sebacate, α- (2,2,6,6-tetramethylpiperidino) -acetic acid-n-octyl ester, 1,4-bis- (2,2,6,6-tetramethylpiperidino) -2-butenes, N-hydroxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea, N-methoxymethyl-N'-2, 2,6,6-tetramethylpiperidin-4-yl-urea, N-methoxymethyl-N'-n-dodecyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea, O- (2 , 2,6,6-tetramethylpiperidin-4-yl) -N-methoxymethylurethanes.

Phosphites and phosphonates like, Tri (nonylphenyl) phosphites, tris (2,4-di-tert-butylphenyl) phosphites, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphites, bis (2,6-di-tert-butyl-4-methylphenyl ) pentaerythritol diphosphites, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphites, tetrakis (2,4-di-tert-butylphenyl) [l, 1'-biphenyl] -4,4'- diyl bisphosphonites, 2,2'-ethylidene bis (4,6-di-tert-butylphenyl) fluorophosphites, dioctadecyl pentaerythritol diphosphonites, 2 - [[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f ] - [1,2,2] dioxaphosphepin-6-yl] oxy] -N, N-bis [2 - [[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f ] [l, 3,2] dioxaphosphepin-6-yl] oxy] ethyl] ethanamines (CAS No. 80410-33-9), bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphites, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite,

Hydroxylamines like,

Amines bis (hydrogenated tallow alkyl), oxidized,

Secondary arylamines like,

N- (2-naphthyl) -N-phenylamines, 2,2,4-trimethyl-1,2-dihydroquinoline polymer (CAS No: 26780-96-1), N-2-propyl-N'-phenyl-p phenylenediamines, N- (1-naphthyl) -N-phenylamines, (Benzeneamines, N-phenyl-, reaction products with 2,4,4-trimethylpentenes) (CAS No. 68411-46-1), 4- (1 -Methyl-1-phenylethyl) -N- [4- (1-methyl-1-phenylethyl) phenyl] aniline.

Lactones and benzofuranones like,

Irganox HP 136 (CAS No. 181314-48-7)

Thioethers and thioesters like,

Distearyl-3,3-thiodipropionate, dilauryl 3,3'-thiodipropionate, ditetradecyl thiodipropionate, di-n-octadecyl disulfide.

UV absorbers like,

(Methanones, [methylene bis (hydroxymethoxyphenylenes)] to [phenyl], (methanones, [1,6-hexanediylbis [oxy (2-hydroxy-4, 1-phenylene)]] to [phenyl], 2-benzoyl-5 methoxyphenol, 2,4-dihydroxybenzophenones, 2,2'-dihydroxy-4-methoxybenzophenones, 2-hydroxy-4-octyloxybenzophenones, 2-hydroxy-4-dodecyloxybenzophenones, 2- (2-hydroxy-4-hexyloxyphenyl) - 4,6-diphenyl-l, 3,5-triazines, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazines, 2-ethoxy -2'-ethyloxalic acid bisanilides, N- (5-tert-Butyl-2-ethoxyphenyl) -N '- (2-ethylphenyl) oxamides, dimethyl (p-methoxybenzylidene) malonates, 2,2' - (l, 4- Phenylenes) to [3,1-benzoxazin-4-one], N '- (4-ethoxycarbonylphenyl) -N-methyl-N- phenylformamidine, 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid isoamyl ester, 2-phenylbenzimidazole-5-sulfonic acid, 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester, 2-ethylhexyl salicylate, 3- (e.g. 4-Methylbenzylidene) bornan-2-one,

Complexing agents like,

Ethylenediamine tetraacetate (EDTA), ethylenediamine, acetylacetone, nitrilotriacetic acid, ethylene glycol bis (beta-aminoethyl ether) -N, N-tetraacetic acid, 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 2, 2 ', 6', 2 "-terpyridine, 4,4'-diphenyl-2,2'-bipyridine, 2,2'-bipyridine-3,3'-diol, 1,10-phenanthroline, 4-methyl-1 , 10-phenanthrolines, 5-methyl-l, 10-phenanthrolines, 4,7-dimethyl-l, 10-phenanthrolines, 5,6-dimethyl-l, 10-phenanthrolines, 3,4,7,8-tetramethyl-l , 10-phenanthrolines, 4,7-diphenyl-l, 10-phenanthrolines, 2,4,7,9-tetramethyl-l, 10-phenanthrolines, N, N, N ', N'-

Tetramethylethylenediamine, 2-hydroxyquinoline, 8-hydroxyquinoline, 2-hydroxy-4-methylchinaldine, 5-chloro-8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline, 2,4-quinolinediol, 2-quinolethiol, 8- Quinolethiol, 8-aminoquinoline, 2,2'-biquinoline, 2-quinoxalinol, 3-methyl-2-quinoxalinol, 2,3-dihydroxyquinoxaline, 2-mercaptopyridine, 2-dimethylaminopyridine, 1,2-bis (dimethylphosphino) ethane , l, 2-bis (diphenylphosphino) ethane, l, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, polyaspartic acid, iminodisuccinate,

or also other 2- (2-hydroxyphenyl) benzotriazoles of the formula (1).

The 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) and optionally mixtures protect the iodine-containing biocides not only from decomposition in the liquid color, but also have a stabilizing effect on the iodine-containing biocides in the dried paint film and against decomposing effects caused by light.

The amount of 2- (2-hydroxyphenyl) benzotriazole of the formula (I) which is necessary in order to stabilize the iodine-containing biocide in a technical medium can be determined by routine experimentation and depends both on the type and concentration of iodine. containing biocide, as well as the type and amount of additives in the technical medium, eg the color or formulation.

In the case of alkyd resin-based systems such as paints, the amount of 2- (2-hydroxyphenyl) benzotriazole of the formula (I) necessary for the stabilization depends on the type and amount of the drier used, the alkyd resins and other constituents in the color formulation.

In the case of alkyd resin paints, the amount must be adjusted so that the iodine-containing biocides do not degrade, but the actual effect of the dryer is not suppressed. In other media, the application amount must be adjusted so that although a stabilization is observed, but the properties of the medium are not changed.

In the technical media, the 2- (2-hydroxyphenyl) benzotriazoles of formula (I) are generally used in concentrations of from 0.001% to 5% by weight, based on the total amount of color. The 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) are preferably used in concentrations of 0.005% by weight to 3% by weight and more preferably between 0.01% by weight and 2% by weight. ,

In active ingredient formulations and concentrates, the 2- (2-hydroxyphenyl) benzotriazoles of the formula (I) are used in higher amounts. In general, from 0.5% by weight to 50% by weight, preferably from 1% by weight to 40% by weight and particularly preferably from 2% by weight to 30% by weight of 2- (2 Hydroxyphenyl) benzotriazoles of formula (I) based on the amount of formulation or concentrate.

Examples:

A solution is prepared in Dowanol TPM (tripropylene glycol methyl ether) containing 10% by weight of iodopropargyl butylcarbamate, 5% by weight of octasoligen cobalt 8 (from Borchers, Langenfeld, Germany) and 5% by weight of that indicated in Table 1 stabilizer. One stored at 40 ⁰ C. At the start and after two weeks, the content of IPBC by HPLC was determined.

Claims

claims

1. active substance mixtures comprising at least one iodine-containing biocide and at least one 2- (2-hydroxyphenyl) benzotriazole compound of the general formula (I),

in which

R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen, sulfo, sulfato or halogen

and

R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, halogen, hydroxyl, sulfo, sulfato or in each case optionally substituted alkyl,

Cycloalkyl, alkoxy or aryl.

2. Mixtures according to claim 1, characterized in that they contain at least one compound of formula (I),

in which

R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydrogen, sulfo, sodium sulfonate,

Potassium sulfonate, lithium sulfonate, chlorine, bromine or fluorine,

and

R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, bromine, chlorine, fluorine,

Hydroxy, sulfo, sodium sulfonate, potassium sulfonate, lithium sulfonate, straight-chain or branched, unsubstituted or mono- or polysubstituted by identical or different substituents, Ci-C ₂ o-alkyl, straight-chain or branched, unsubstituted or mono- or polysubstituted by identical or different substituents Q-Cio-alkoxy, unsubstituted or mono- or polysubstituted C ₃ -C ₂ -cycloalkyl, where the substituents for the mono- or polysubstituted or differently substituted

Alkyl radicals, alkoxy radicals and cycloalkyl radicals are selected from the group: halogen; nitro; cyano; hydroxy; C 1 -C ₁₀ -alkoxy; C ₂ -C ₂ o-Polyethylenglycoloxy, C ₁ -Co-ACyI, Ci-C ₂₀ - acyloxy, C _r C ₂ o-alkoxycarbonyl, Ci-C ₂₀ -Polyethylenglycoloxycarbonyl, carboxyl and its lithium, sodium and potassium salts.

3. Mixtures according to at least one of claims 1 and 2, characterized in that they are bound as iodine-containing biocide at least one iodoalkynyl compounds in which one or more iodine atoms to double bond systems or a compounds in the one or more iodine atoms to a single-bonded carbon atom are bound.

4. Mixtures according to at least one of claims 1 to 3, characterized in that they contain 0.01-70% by weight of at least one iodine-containing biocide and 0.001-50% by weight of at least one 2- (2-hydroxyphenyl) -benzotriazole contain compound of formula (I).

5. A microbicidal composition containing an active ingredient mixture according to at least one of claims 1 to 4 and at least one solvent or diluent and optionally processing aids and optionally other antimicrobial substances.

6. Use of a mixture according to claim 1 or an agent according to claim 5 for the protection of industrial materials from attack and / or destruction by

Microorganisms.

7. Use of 2- (2-hydroxyphenyl) benzotriazole of the formula (I)

in which

R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen, sulfo, sulfato or halogen

and R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, halogen, hydroxyl, sulfo,

Sulfato or are each optionally substituted alkyl, cycloalkyl, alkoxy or aryl,

for the stabilization of iodine-containing biocides against chemical degradation reactions.

8. Use according to claim 7, characterized in that it is the stabilization of iodine-containing biocides in engineering materials.

9. Use according to claim 7, characterized in that it is the stabilization of iodine-containing biocides in paints based on alkyd resin binders containing transition metal drier is.

10. Technical materials containing at least one iodine-containing biocide and at least one 2- (2-hydroxyphenyl) benzotriazole compound of the formula (I),

in which

R ¹ , R ² , R ³ and R ^{4 are} independently hydrogen, sulfo, sulfato or

Halogen stand

and

R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, halogen, hydroxyl, sulfo, sulfato or in each case optionally substituted alkyl, cycloalkyl, alkoxy or aryl.