NZ623963B2 - Stabilization of compounds containing iodine having polymers comprising nitrogen - Google Patents

Abstract

Disclosed is a method of producing polymers of formula (I) containing nitrogen made of aziridines (e.g., trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate), and the use of the polymers for stabilizing biocides comprising iodine compounds (e.g., iodoalkynyl compounds) against chemical and light induced degradation. ight induced degradation.

Description

Stabilization of compounds containing iodine having polymers comprising nitrogen The invention relates to the production of nitrogen containing polymers from azin'dines, to the use of these nitrogen containing rs for stabilizing iodine containing compounds, to itions comprising at least the nitrogen containing polymers and also iodine containing nds, and to the use of these compositions as biocides and/or for controlling microorganisms.

Iodine containing biocides are used for protecting industrial materials such as coating materials, for example, fi‘om infestation, decomposition, destruction and visual tion by fungi, bacteria and algae. Furthermore, iodine containing biocides, both alone and in ation with biocides from other classes of active ingredient, are used as components of biocidally active materials protection compositions such as wood preservatives, for example. Besides iodoalkynyl compounds, active ients are also used here in which one or more iodine atoms are bonded to spz-hybridized carbon atoms of olefinic double bonds, or else to spa-hybridized carbon atoms.

A behaviour common to many iodine containing biocides is that on exposure to light, even as they are or as a ent of an industrial material, they undergo decomposition accompanied by yellowing, and this massively impairs both the biocidal y and the tactile ies of the material to be protected.

Many iodine containing biocides, especially kynyl compounds, are destroyed with ular rapidity by transition metal compounds. This fact prevents the use of iodine containing biocides, such as more particularly iodoalkynyl compounds, in solvent—based coating materials, such as paints, varnishes and stains, or in biocidal vatives, such as wood preservative s, wood preservative impregnation systems and wood preservative stains, since these alkyd resin-based coating and preservation systems typically comprise tion metal compounds. The transition metal compounds such as octoates of cobalt, of lead, of manganese and of vanadium, for example, function here as dryers (siccatives) of the alkyd resin-containing binder system. rmore, transition metal compounds are also used as colour-imparting pigments, and have destructive properties comparable with those of the siccatives.

Besides the siccatives there are a range of further constituents in the aforementioned solvent-based systems that lead in different ities to the degradation of iodine ning biocides. Whereas with the solvents commonly used the destabilizing effect is still relatively weakly nced, the other customary components of a paint formulation, such as in-process additives, plasticizers, colour pigments, anti-steeling agents, thixotropic agents, corrosion inhibitors, anti-skinning agents and binders, for example, exhibit a more or less strongly pronounced destabilizing effect.

As well as in the above-described solvent-based systems, the use of iodine containing biocides in certain based industrial materials also presents problems. Where, for example, the filming and film curing of a water-based coating material is based on oxidative crosslinking of water-soluble or emulsified alkyd resins, tion metal compounds are employed as siccatives in these systems as well, with a consequent accompanying destruction of the iodine containing biocides.

The prior art has disclosed techniques for ting the breakdown of iodopropargyl compounds in transition metal-containing, solvent-based paints comprising alkyd resin, and thereby stabilizing them.

Thus, for example, the addition of chelating ts (WO 98/22543 A), organic epoxides (W0 00/16628 A, US 4,276,211, US 258) optionally in conjunction with UV absorbers (WO 99/29176 A) or benzylidene-camphor derivatives (US 6,472,424), tetraalkylpiperidine compounds and/or UV absorbers (EP 0 083 308 A), 2-(2-hydroxypheny1)benzotriazoles (W0 2007/028527 A) or azole compounds (W0 2007/101549 A) is known.

The action of the abovementioned stabilizers, r, is not always adequate and is hampered by performance disadvantages. For instance, in particular, drying times of paints are significantly prolonged, this being in many cases unacceptable to the user. Moreover, the inhibition of ouration is not always sufficient.

EP 2 236 033 A bes stabilization by means of stabilizers containing aziridine groups. In this way, r, it is not possible to produce e-stable concentrates of iodine containing biocides.

By applying aziridines or other nitrogen containing compounds to inorganic carrier materials, such as s (W02010/142790 A), for e, it is possible to obtain good stabilizers, but the requisite spray drying makes their production very energy-intensive.

It is also known that iodine containing biocides can be protected from attack by destabilizing influences in a polymer preparation (W0 2011/000794 A). At the same time, r, the activity is restricted to an extent such that the ary application rate becomes uneconomically high.

The object, therefore, was to provide compositions which allow effective stabilization of iodine ning compounds, are easy to produce, and cause as little disruption as possible in their application, for example, in coating materials.

It has now been found that nitrogen containing polymers are suitable for effectively protecting iodine containing compounds, especially in (organic) solvent-based and water—based systems, against both chemical and light induced degradation, and hence are able to prevent colour changes and loss of action.

The invention accordingly relates to the use of nitrogen containing polymers for stabilizing iodine containing compounds and also to a method for stabilizing iodine containing compounds by contacting them with nitrogen containing polymers.

Stabilization in the context of the invention means the protection of iodine containing compounds against chemical and/or light induced degradation.

Iodine containing compounds are, for example, kynyl nds and also compounds in which one or more iodine atoms are bonded to spz—hybridized carbon atoms of olefinic double bonds, or to sp3-hybridized carbon atoms. Such compounds preferably t biocidal action.

Examples of iodine containing compounds with biocidal activity are N—(C,-Cn)-alkyl-iodotetrazoles, N-(C5-C1,)-aryl-iodotetrazoles, N-(Cé-ClQ-arylallcyl-iodotetrazoles , diiodomethyl p-tolyl ne, diiodomethyl rophenyl sulphone, 3-bromo-2,3-diiodopropenyl alcohol, triiodoallyl alcohol, 4-chloro(2-chloromethylpropyl)[(6-iodopyridinyl)methoxy]-3(2H)-pyridazinone (CAS RN: 1209553), iodofenfos, 3-iodopropynyl 2,4,5-trichlorophenyl ether, - 2-propynyl 4-chlorophenyl formal (IPCF), N-iodopropargyloxycarbonyl-alanine, N-iodopropar- carbonyl-alanine ethyl ester, 3-(3-iodopropargyl)benzoxazol-Z-one, 3-(3—iodopropargyl) chlorobenzoxazolone, 3-iodopropynyl alcohol, 4-chloropheny1 3-iodopropargyl formal, 3-iodo- 2-propynyl propylcarbamate, 3-iodopropynyl butylcar’oamate ([PBC), 3-iodopropynyl m-chlorophenylcarbamate, 3-iodopropynyl phenylcarbamate, di-(3-iodopropynyl)hexyl dicarbarnate, 3-iodopropynyloxyethanol ethylcarbamate, 3-iodopropynyloxyethanol phenylcarbamate, 3-iodopropynyl thioethylcarbamate, propynyl-carbamic ester (IPC), 3-bromo-2,3-diiodo-Z-propenyl ethylcarbamate, propynyl n-hexylcarbamate and 3-iodopr0pynyl cyclohexylcarbamate.

Preferred iodine containing compounds with biocidal activity are propynyl 2,4,5- trichlorophenyl ether, 3-iodopropynyl 4»chlorophenyl formal (IPCF), propargy]oxycarbonyl- alanine, N-iodopropargyloxycarbonyl-a1anine ethyl ester, 3-(3-iodopropargyl)benzoxazolone, 3-(3-iodopropargyl)chlorobenzoxazolone, 3-iodopropynyl alcohol, 4-chlorophenyl 3-iodo- propargyl formal, 3-iodopropynyl propylcarbamate, 3-iodopropynyl arbarnate (IPBC), 3-iodopropynyl m-chlorophenylcarbamate, 3~iodopropynyl phenylcarbamate, di-(3-iodo- 2-propynyl)hexyl dicarbarnate, 3-iodopropynyloxyethanol ethylcarbamate, 3-iodo- 2-propynyloxyethanol phenylcarbamate, 3-iodopropynyl thioxothioethylcarbamate, 3-iodo- ynyl-carbamic ester (IPC), 3-bromo-2,3-diiodopropenyl ethylcarbamate, 3-iodopropynyl n-hexylcarbamate and 3-iodo—2-propynyl cyclohexylcarbamate. ‐ 4 (followed by 4A) ‐ In a particular ment, the present invention provides a use of nitrogen containing polymers for stabilizing iodine containing compounds, characterized in that the nitrogen containing polymers are polymers obtained by reaction of aziridines in the presence of water and have a fraction of 5 % or less of aziridine nitrogen, based on the total nitrogen content.

In another particular embodiment, the present invention provides a method for stabilizing iodine containing compounds by contacting the iodine containing compounds with nitrogen ning polymers, characterized in that the nitrogen containing polymers are polymers obtained by reaction of ines in the presence of water and have a fraction of 5 % or less of aziridine nitrogen, based on the total en t.

In another particular ment, the present invention provides biocidal compositions comprising at least a) at least one iodine containing nd having a biocidal action b) at least one nitrogen containing polymer, ‐ 4A (followed by 5) ‐ terized in that the nitrogen containing polymers are polymers ed by reaction of aziridines in the presence of water and have a fraction of 5 % or less of aziridine nitrogen, based on the total nitrogen content.

In another particular embodiment, the present invention provides a binder formulation comprising a) at least one binder, b) at least one iodine containing compound with biocidal action and c) at least one nitrogen containing polymer, terized in that the nitrogen containing polymers are polymers obtained by reaction of aziridines in the presence of water and have a fraction of 5 % or less of aziridine en, based on the total nitrogen content. where R1 is en, alkyl or cycloalkyl, each of which is unsubstituted or substituted and/or mono- or polyethylenically unsaturated, or in each case substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl, arylcarbonyl or alkanoyl, R2, R3, R4 and R5 independently of one another have the same definition as R1 and additionally independently are n, hydroxyl, carboxyl, alkylsulphonyl, arylsulphonyl, nitrile, isonitrile, R2 and R‘ or R3 and R5, together with the carbon atoms to which they are attached, form a 5- to 10- membered carbocyclic ring which is unsubstituted or substituted and/or mono- or polyethylenically unsaturated.

Monofunctional ines of the formula (I) that are contemplated are, for e, those in which R2 and R4 or R3 and R5, together with the carbon atoms to which they are attached, form a 5- to 10- ed carbocyclic ring which is unsubstituted or substituted and/or mono- or polyethylenically unsaturated.

These are, more particularly, those of the formula (II) N—R (II) where the carbocyclic ring is unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, hydroxyl, oxo, carboxyl, alkylsulphonyl, arylsulphonyl, nitrile, isonitrile, alkyl or cycloalkyl, each of which is unsubstituted or substituted and/or mono- or hylenically unsaturated, or substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl or alkanoyl, and n is a number from 0 to 6, preferably from 0 to 1.

Likewise preferred are those nctional aziridine compounds of the a (I) in which R] is a radical of the formula R24—L o/\/]g/O\n/ CH20H2_ or in which R24 is —H or alkyl, preferably -H, -CH3, .csz, more preferably -CH3, -C2H5, g is a number from 1 to 4, preferably 1 to 3, more preferably 1 to 2, h is a number from 1 to 11, preferably 1 to 5 and more preferably 1 to 3, and the remaining radicals have the above definition.

More particular preference is given to those compounds of the formula (I) which m to the compound ofthe formula (III) or (IV) YVNKR” (III) goMNHWW/Nkfi ('V) where R23 is —H or alkyl, preferably —H or —CH;, more preferably —CH3, R25 is —H or alkyl, preferably —H or —CH3, more preferably —CH3, and the remaining radicals have the above definition.

Particularly preferred aziridines are those having two or more aziridine functions. Examples include compounds ofthe formula (V) in which A is an m-valent aliphatic, cycloaliphatic or aromatic radical, which is optionally substituted, m is a number from 2 to 5, more ularly 2 to 3, and R30 for each m unit is in each case independently hydrogen or C1-C4 alkyl, more particularly CH; 01' CH2CH3.

Where m is 2, A is preferably C2-Cm alkylene, more particularly -(CH2)6)-, )2 CH2 C(CH3)2 CH2- or - C(CH3)2 CH2 CH(CH3) CH2 — or is a ene, more particularly the divalent radical of the formula If m is 3, A is preferably the trivalent radical ofthe formula Preferred compounds of the formula (V) are those conforming to the formulae (Va) — (Vd).

R30 N/>\R30 (Vb) R30 />\ 30 \</Nk©wN/>_ R30 (Vd) Likewise preferred as polyfunctional azin'dine compounds are Michael adducts of optionally substituted ethylenimine with esters of polyhydric alcohols with a,[3-unsaturated carboxylic acids and the adducts of optionally substituted ethylem'mine with ocyanate.

Suitable alcohol components are, for example, trimethylolpropane, neopentyl glycol, glycerol, pentaerythritol, 4,4'-isopropylidenediphenol and 4,4'-methylenediphenol. Examples of suitable call-unsaturated carboxylic acids include acrylic acid and methacrylic acid, crotonic acid and cinnamic acid.

With particular preference the composition of the ion comprises c esters.

The corresponding polyhydric alcohols of the 0t,[3-unsat11rated carboxylic esters may optionally be alcohols which have been ed on some all of their OH functions in some cases completely with alkylene oxides, singly or multiply. These may be, for example, the aforementioned alcohols ed singly or multiply with alkylene oxides. In this respect, nce is also made to US 4,605,698, the P001 0065 A oxides which disclosure content of which is included by reference in the present invention. Alkylene are ethylene oxide and ene oxide. are particularly suitable in accordance with the invention those Examples of polyisocyanates suitable for reaction with optionally substituted ethylenimine are specified at page 4 lines 33 — 35 of A. those specified at page 3 es of aziridines that are suitable in accordance with the ion are lines 29 — 34 of A. in US 3,225,013 Preference is likewise given to those aziridines of the kind described, for example, (Fram), US 4,490,505 (Pendergrass) and US 5,534,391 (Wang). least three aziridine groups, Likewise preferred are those aziridines of the formula (I) which possess at such as, for example, trimethylolpropane tris[3-(1-aziridinyl)propionate], trimethylolpropane tris[3-(2- -l dinyl)propionate], trimethylolpropane tris[2-aziridinylbutyrate], tris(l-aziridinyl)- phosphine oxide, tris(2-methyl-l -aziridinyl)phosphine oxide, rythritol tris[3-(1-aziridinyl)- propionate] and pentaerythritol tetrakis[3-(1-aziridiny1)propionate].

Of these, ence is given ularly to trimethylolpropane tris[3—(l-aziridiny1)propionate], trimethylolpropane tris[3-(2-methy1aziridiny1)propionate], trimethylolpropane tris[2-aziridinyl- pentaerythritol tris-[3-(1-aziridinyl)propionate] and pentaerythritol tetrakis[3—(l- te], aziridinyl)propionate].

Particularly preferred are trimethylolpropane tris[3-(l-aziiidinyl)propionate], trimethylolpropane tris[3-(2-methyl-1—aziridinyl)propionate] and pentaerythritol tetrakis-[3-(l -aziridinyl)propionate].

Likewise preferred are polyfunctional aziridines of the formula (VI) R38 R40 R (VI) B OWNgI in which P001 00659A B is the radical of an aliphatic polyol which contains at least xOH functions, where xOH functions are substituted by the radical of the above brackets, f is a number from 0 to 6, more particularly from 1 to 3, x is a number r than or equal to 2, and more particularly is 2 to 100 000, and R38 and R39 or R40 and R“, together with the carbon atoms to which they are attached, form a 5- to 10- membered yclic ring which is unsubstituted or substituted and/or mono- or hylenically unsaturated.

With particular preference B is the radical of a polyvinyl alcohol. Particularly preferred azin'dines of the formula (VI) are those in which x is 3 or 4 and B is a trebly or quadruply OH-functional polyol.

Particularly preferred aziridines of the formula (VI) are those conforming to the formulae (VIa) — (VIc) CH30H2(C)‘[\/O\n/\/N& ]3 (VIa) HOCHzCH2(C)\[\/O\n/VN£ l3 (Vlb) (cflVom/VNA l4 (Vic) in which R38 is hydrogen or CH3. -1]- A particularly preferred product is the ine compound of the formula (VIa), with R38 = methyl, also known as Crosslinker CX-100 from DSM, and the hardener product l Hfirter AN” from BASF, which comprises the aziridine of the formula (VIa) with R38 = hydrogen.

In one embodiment the nitrogen containing polymers are obtained by reaction of aziridines, such as more particularly those specified above, in the presence of water and optionally in the presence of cosolvents.

The invention ingly also encompasses a method for producing nitrogen containing polymers that is characterized in that aziridines are reacted in the presence of water and optionally cosolvents.

The amount ofwater used here may be varied within a wide range. Generally speaking at least 10% by weight of water is used, based on the aziridines ed. The water amount is preferably 20% to There 1000% by weight, more preferably 30% to 300% by , based on the aziridines employed. is in principle no upper limit on the amount of water that can be used, gh high water amounts naturally make it more costly and inconvenient to isolate the nitrogen containing polymers.

The reaction temperature is for example 30 to 100°C, preferably 40 to 90°C and very preferably 50 to 80°C.

The reaction is preferably conducted until 95% or more, preferably 98% or more, more preferably 99% or more of the aziridine employed has been reacted, based on the fraction of aziridine rings. With until aziridine rings are no longer detectable. very particular preference the reaction is conducted Accordingly, the en containing polymers employed in accordance with the invention have a fraction of 5% or less, preferably 2% or less, more preferably 1% or less, and very preferably no detectable amounts of aziridine rings, based on the ines employed.

In another embodiment the nitrogen containing polymers employed in accordance with the invention have a fraction of 5% or less, preferably 2% or less, more preferably 1% or less, and very ably content. no detectable amounts of aziridine nitrogen, based on the total nitrogen NMR The fraction of ted aziridine rings can be determined by means, for example, of 13C a in ison to the aziridine employed.

The reaction time is generally 2 to 48 h, very preferably 3 to 24 h.

While the use of cosolvents is not absolutely necessary for achieving the desired stabilizers, it may nevertheless be useful, particularly when ing high concentrations of aziridine, since it allows gelling within the reaction batch to be effectively prevented.

Cosolvents which can be used are in general all compounds which are miscible with water and which under the on ions do not themselves react, or else react only to a minor , with the aziridines employed.

Preferred cosolvents are oligo- or polyalkylene glycols or triols, or ethers of the aforementioned compounds, having more particularly a molecular weight of less than 1000 g/mol. Particularly preferred are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, ylene glycol, polypropylene glcol, glycerol and also mono-, di-methyl, -ethyl, l or -butyl ethers of the aforementioned compounds, and also any desired mixtures of the aforementioned cosolvents.

Especially red for use as cosolvent is diethylene glycol butyl ether.

The amount of cosolvents used can be varied within a wide range. Generally speaking, for example, at least 20% by weight of cosolvents are used, based on the amount of water employed, ably 30% to 1000% by weight, more preferably 50% to 300% by weight.

The nitrogen containing polymers produced by the method of the invention can be used directly in the form of the resulting solution to ize iodine containing compounds, or optionally in isolated form following removal of cosolvents and/or water.

On the basis of their stabilizing action, the en containing polymers such as, more ularly, the nitrogen containing polymers obtainable in accordance with the invention and/or produced by the method of the invention are suitable for joint application with iodine containing compounds in biocidal compositions.

The invention therefore also embraces biocidal compositions comprising at least a) at least one iodine containing compound having a biocidal action b) at least one nitrogen containing polymer, the individual components being t to the abovementioned ranges and preference ranges in the same way.

Preferred biocidal compositions comprise a) IPBC and b) nitrogen containing polymers obtainable by reaction of at least one, preferably precisely one, aziridine of the formula (VI) in the presence of water.

The biocidal compositions of the invention comprise in general a) 0.01% to 70% by weight, preferably 0.05% to 60% by weight, more preferably 0.1% to 50% by weight of iodine containing compounds having a biocidal action and b) 0.001% to 50% by weight, preferably 0.005 to 40% by weight, more preferably 0.01% to 30% by weight of nitrogen containing rs.

The al compositions of the invention preferably comprise the iodine containing compounds with a biocidal action and the nitrogen containing polymers in a sum total of 0.011% to 100% by weight, ably 0.05% to 80% by weight, more preferably 0.1% to 60% by weight.

In one embodiment the biocidal compositions of the invention comprise from 1% to 280% by weight of nitrogen containing polymers, preferably 2% to 225% by weight, more particularly 5% to 110% by weight, based on the iodine containing compounds having a biocidal action.

The biocidal itions may further comprise solvents, or not.

The solvents optionally present may if used be solvents of the kind already described above as cosolvents for the reaction to give nitrogen containing polymers. The ranges and preference ranges apply here analogously.

The biocidal compositions may further comprise acids, such as organic and/or inorganic acids, for example, or not.

To the d person it is clear that in view of the possible ty of the nitrogen ning rs, especially if ed from aziridines, the acids are present at least not completely in free form in the biocidal ition. The ty figures given below therefore relate to levels and amounts in each case ated on the basis of the free acid.

The inorganic acids optionally present may in principle be any inorganic acids that are soluble in the biocidal composition. Preferred inorganic acids are hydrochloric acid or HCl, sulphuric acid and phosphoric acid.

The organic acids optionally present may in principle be any organic acids which are soluble in the biocidal composition. Preferred organic acids are formic acid, acetic acid, citric acid, propionic acid or benzoic acid. Formic acid is particularly preferred.

P001 00659A it is 0.01% to 2% by weight, The level of acids may be varied within a wide range. In general based on the overall preferably 0.03% to 1.5% by weight and very preferably 0.05% to 1% by , al composition. other active ingredients and The abovevdescribed biocidal compositions may additionally comprise auxiliaries as well. They may take the form, for example, of a solution, emulsion or suspension.

It is possible for example for organic solvents to be included, or not. contemplated e ics, such Examples of organic solvents as xylene, toluene or hydrocarbons, such as alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic such as cyclohexane chlorobenzenes, chloroethylenes or methylene chloride, aliphatic arbons, or paraffins, e.g. eum fractions (white spirit, Shellsol D60 from Shell Chemical), monohydric ls such as, for example, ethanol, isopropanol and l, polyhydric alcohols such ® from Kuraray), glycols such as, example, glycerol, pentaerythritol, polyvinyl l (e.g. example, ethylene glycol and propylene glycol, oligoglycols and for polyglycols, ethers of ether (e.g. Dowanol® TPM from oligoglycols such as, for example, dipropylene glycol thyl such as acetone, Dow), ethers and esters of alcohols such as (Texanol® from Eastman), ketones, solvents, such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar c example, etherified glycols, dimethylformamide and dimethyl sulphoxide, and also, for totally etherified polyols and oligoglycols and polyglycols such as, for example, ethylene glycol l ether, esterified polyols, esters of monobasic and polybasic carboxylic acids, e.g. diisobutyl adipate, diisobutyl e (e.g. solv DIBQ). invention that may be included or not Further possible ingredients of the biocidal compositions of the natural and synthetic polymers in powder, particle or are adhesives such as carboxymethylcellulose, and also natural phospholipids, latex form, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, mineral and vegetable oils. such as cephalins and lecithins, and synthetic olipids, and also further ingredients colourants Moreover, the biocidal compositions of the invention may comprise as and organic dyes, such as such as inorganic pigments, e.g. iron oxide, titanium oxide, Prussian Blue, alizan'n dyes, azo dyes and metal phthalocyanine dyes. also comprise further stabilizers, such as, Furthermore, the biocidal compositions of the invention may for example, chelating reagents or organic epoxides. In many cases here istic effects are observed.

P001 00§59A increased The activity and the spectrum of action of the biocidal compositions of the invention may be if they include optionally further active ingredients selected from the group of further antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients. is r than the In many cases, synergistic effects are obtained, i.e. the ty of the mixture activity of the individual components. The following compounds, for example, are particularly favourable co-components, and may each individually be included or not: triazoles such as: azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, epoxiconazole, azole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, zole, flutriafol, furconazole, hexaconazole, conazole, ipconazole, isozofos, myclobutanil, metconazole, paclobutrazole, penconazole, conazole, prothioconazole, simeconazole, (:)-cis-l-(4-chlorophenyl)(1H-1,2,4-triazol—l cloheptanol, 2-(1 -tert-butyl) (2-chlorophenyl)(1,2,4-triazol—1-yl)propanol, tcbuconazole, tetraconazole, triadimefon, their metal salts and acid triadimenol, triapenthenol, izole, triticonazole, uniconazole and adducts; imidazoles such as: clotrimazole, bifonazole, climbazole, ole, fenapamil, imazalil, isoconazole, ketoconazole, lombazole, miconazole, pefurazoate, prochloraz, triflumizole, thiazolcar, 1-imidazolyl(4'-chloro- phenoxy)-3,3-dimethylbutanone, and their metal salts and acid adducts; pyridines and pyrimidines such as: ancymidol, buthiobate, fenarimol, mepanipyrin, nuarimol, pyroxyfi1r,triamirol; succinate dehydrogenase inhibitors such as: nil, carboxim, carboxim sulphoxide, cyclafluramid, fenfuram, flutanil, furcarbanil, furmecyclox, mebenil, mepronil, methfuroxam, metsulfovax, nicobifen, pyracarbolid, oxycarboxin, Shirlan, Seedvax; naphthalene tives such as: terbinafine, nafiifine, butenafine, 3-chloro(2-aza-2,7,7-trimethyloctenyne); sulphenamides such as: fluanid,toly1fluanid, folpet, fluorofolpet, captan, captofol; benzimidazoles such as: carbendazim, benomyl, dazole, thiabendazole or their salts; morpholine derivatives such as: aldimorph, dimethomorph, rph, falimorph, fenpropidin, fenpropimorph, tridemorph, phamid and their arylsulphonate salts such as, for example, p-toluenesulphonic acid and p-dodecylphenylsulphonic acid; benzothiazoles such as: 2-mercaptobenzothiazole; benzothiophene es such as: N-cyclohexyl-benzo[b]thiophenecarboxamide S,S-dioxide; benzamides such as: chloro-N-(4-trifluoromethylbenzyl)benzamide, teclofialam; boron compounds such as: boric acid, boric esters, borax; formaldehyde and formaldehyde-releasing compounds such as: benzyl alcohol oly)hcmiformal, l,3-bis(hydroxymethyl)-5,5~dimethylimidazolidine—2,4-dione (DMDMH), bisoxazolidine, n-butanol hemiformal, cis-l -(3 -chloroallyl)-3 ,5,7-triazaazoniaadamantane chloride, 1 -[1 ,3-bis(hydroxymethyl-2,5-dioxoimidazolidinyl]-1 ,3-bis- (hydroxymethyl)urea,.dazomet, dimethylolurea, 4,4-dimethyloxazolidine, ethylene glycol hemiformal, 7-ethylbicyclooxazolidine, hexahydro-S-triazine, hexamethylenetetramine, N-hydroxymethyl- N’-methylthiourea, methylenebismorpholine, sodium N—(hydroxymcthyl)glycinate, N-methylolchloroacetamide, idine, paraformaldehyde, taurolin, tetrahydro—l,3-oxazine, N-(2- hydroxypropyl)aminemethanol, tetramethylolacetylenediurea (TMAD); isothiazolinones such as: N-mcthylisothiazolinone, 5-chloro-N-methylisothiazolm-B-one, 4,5-dichloro-N-octylisothiazolin one, S-chloro-N-octylisothiazolinone, N-octylisothiazolinone, 4,5-trimethyleneisothiazolinone, 4,5- benzisothiazolinone; P001 00659A aldehydes such as: cinnamaldehyde, dehyde, aldehyde, B-bromocinnamaldehyde, o-phthalaldehyde; thiocyanates such as: thiocyanatomethylthiobenzothiazo1e, methylenebisthiocyanate; such as: quatemary ammonium compounds and guanidines benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethyl- dodecylammonium chloride, dichlorobenzyldimethylalkylammonium chloride, didecyldimethyl- chloride, ammonium chloride, dioctyldimethylammonium chloride, N-hexadecyltrimethylammonium l-hexadecylpyridinium chloride, iminoctadine lbesilate); phenols such as: tribromophenol, tetrachlorophenol, ylchlorophenol, 3,5-dimethylchlorophenol, methyl p-hydroxy- dichlorophene, 2-benzylchlorophenol, triclosan, diclosan, hexachlorophene, benzoate, ethyl p-hydroxybenzoate, propyl p—hydroxybenzoate, butyl p-hydroxybenzoate, octyl oxybenzoate, o-phenylphenol, m-phenylphenol, p-phenylphenol, 4-(2-tcrt-butyl- 4-methylphenoxy)phenol, 4-(2-isopropylmethylphenoxy)phenol, 4-(2,4-dimethylphenoxy)phenol and their alkali metal salts and ne earth metal salts; microbicides with an activated halogen group such as: l-bromo bronopol, bronidox, 2-bromonitro-1,3-propanediol, 2-bromo-4'-hydroxyacetophenone, chloro-4,4,5,5-tetramethylimidazolidinone, B-bromo-B-nitrostyrene, chloracetamide, mine T, l,3-dibromo—4,4,5,S-tetramethylimidazolidinone, dichloramine T, 3,4-dichloro—(3H)-l,2-dithiol one, 2,2-dibromonitrilepropionamide, 1,2-dibromo—2,4-dicyanobutane, halane, halazone, mucochloric acid, phenyl 2-chlorocyanovinyl sulphone, phenyl 1,2-dichlorocyanoviny1 sulphone, oroisocyanuric acid; pyridines such as: 1-hydroxypyridinethjone (and the Cu, Na, Fe, Mn, Zn salts f), tetrachloro—4-methyl- sulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithion, 1-hydroxymethyl(2,4,4-trimethy1- pentyl)-2(1H)-pyridine; methoxyacrylates or similar such as: P001 00659A azoxystrobin, dimoxystrobin, fluoxastrobin, im-methyl, metominostrobin, orysastrobin, strobin, pyraclostrobin, trifloxystrobin, 2,4-dihydromethoxymethyl[2-[[[[l-[3- (trifluoromethyl)pheny1]ethylidene]amino]oxy]methyl]phenyl]~3H-1 ,2,4-triazolone (CAS No. 1853362); metal soaps such as: salts of the metals tin, copper and zinc with higher fatty acids, resin acids, naphthenic acids and phosphoric acid, such as, for example, tin naphthenate, tin octoate, tin lhexanoate, tin oleate, phosphate, tin benzoate, copper naphthenate, copper octoate, copper 2-ethylhexanoate, copper oleate, zinc octoate, zinc lhexanoate, zinc oleate, copper phosphate, copper benzoate, zinc naphthenate, zinc phosphate, zinc benzoate; metal salts such as: for example, copper salts of the metals tin, copper, zinc, and also chromates and dichromates, such as, hydroxycarbonate, sodium mate, potassium dichromate, potassium chromate, copper sulphate, fluorosilicate; copper chloride, copper , zinc fluorosilicate, copper oxides such as: oxides ofthe metals tin, copper and zinc, such as, for example, tributyltin oxide, Cu20, CuO, ZnO; oxidizing agents such as: hydrogen peroxide, peracetic acid, potassium persulphate; dithiocarbamates such as: cufraneb, ferban, ium N—hydroxymethyl-N’-methy1dithiocarbamate, sodium dimethyl- dithiocarbamate, potassium dimethyldithiocarbamate, mancozeb, maneb, metam, metiram, thiram, zineb, ziram; nitriles such as: 2,4,5,6—tetrachloroisophthalonitrile, disodium cyanodithioimidocarbamate; quinolines such as: 8-hydroxyquinoline and the copper salts thereof; other fungicides and bactericides such as: bethoxazin, oxy—2(5H)-furanone, 4,5-benzodithiazolinone, 4,S-trimethylenedithiazolinone, N- hlorobenzoylethyl)hexaminium chloride, 2-oxo(4-hydroxyphenyl)acetohydroxycinnamoyl chloride, tris-N-(cyclohexyldiazeniumdioxy)-aluminium, N—(cyclohexyldiazeniumdioxy)-tributyltin or its potassium salts, bis-N-(cyclohexyldiazeniumdioxy) copper, iprovalicarb, fenhexamide, spiroxamine, carpropamid, diflumetorin, quinoxyfen, famoxadone, polyoxorim, acibenzolar S-methyl, furametpyr, thifluzamide, axyl-M, benthiavalicarb, metrafenon, namid, il, tea tree oil, yethanol, Ag, Zn or Cu-containing zeolites alone or incorporated into polymeric materials.

Very especially preferred are mixtures with azaconazole, bromuconazole, cyproconazole, dichlobutrazol, diniconazole, diuron, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet, methfuroxam, carboxin, N—cyclohexyl-benzo[b]thiophenecarboxamide oxide, fenpiclonil, 4-(2,2-difluoro-l,3-benzodioxol—4—yl)-1H-pyrrolecarbonitrile, butenafine, imazalil, N-methyl- isothiazolin-S-one, 5-chloro-N-methylisothiazolinone, N-octylisothiazolinone, dichloro- N—octylisothiazolinone, mercaptobenzothiazole, thiocyanatomethylthiobenzothiazole, thiabendazole, benzoisothiazolinone, N-(2-hydroxypropyl)aminomethanol, benzyl alcohol (hemi)formal, ylol- chloroacetamide, N-(2-hydroxypropyl)aminemethanol, glutaraldehyde, omadine, Zn-omadine, dimethyl dicarbonate, 2-bromonitro-l,3-propanediol, bethoxazin, o-phthalialdehyde, 2,2-dibromo- 3-nitrilepropionamide, l ,2-dibromo-2,4-dicyanobutane, 1 ,3—bis(hydroxymethy1)-5,5- dimethylimidazolidine-Z,4-dione ), tetramethylolacetylenediurea , ethylene glycol hemiformal, p-hydroxybenzoic acid, carbendazim, chlorophen, 3-methylchlorophenol, o- phenylphenol.

Apart from with the abovementioned fungicides and bactericides, mixtures with a good efficacy are, er, also prepared with other active ingredients: insecticides / acaricides / nematicides: abamcctin, 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)(ethoxymethyl)-5—(trifluoromethyl)- lH-pyrrole-S-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthn'n, bifenthrin, methrin, bioallethrin, lfluron, bromophos A, bromophos M, bufencarb, ezin, butathiophos, butocarboxim, butoxycarboxim, P001 00659A cloethocarb, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, quinomethionate, chlormephos, N-[(6-chloro- chlordane, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, uazuron, 3-pyridiny1)methyl]-N'-cyano-N-methylethaneimidamide, icrin, chlorpyrifos A, chlorpyrifos M, coumaphos, hos, cis-resmethrin, clocythrin, azoben, cypophenothr'm, clofentezin, cycloprothrin, cyfluthrin, thrin, cyhexatin, cypermethrin, cyromazin, thiuron, dialiphos, decamethxin, deltamethrin, demeton M, dcmeton S, demeton-S-methyl, 1,2-dibenzoyl-1(l,l-dimethyl)hydrazine, DNOC, dichlofenthion, dichlorvos, dicliphos, diazinon, methylcarbamate, dicrotophos, difethialone, diflubenzuron, dimethoate, 3,5-dimethylphenyl dimethyl(pheny1)si1ylmethylphenoxybenzyl ether, dimethyl(4>ethoxyphenyl)silylmethyl—3- phenoxybenzyl ether, dimethylvinphos, dioxathion, disulfoton, ethiofencarb, eflusilanate, tin, empenthrin, endosulfan, EPN, esfenvalerate, ethion, ethofenprox, etn'mphos, etoxazole, etobenzanid, fenbutalin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenamiphos, fenazaquin, fenthjon, fenvalerate, fipronil, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fensulfothion, oxuron, flucythrinate, flufencrim, flufenoxuron, flonicamid, fluacrypyrim, fluazuron, flupyrazofos, flufenzine, flumethrin, flufenprox, fluvalinate, fonophos, formethanate, formothion, fosmethilan, azate, filbfenprox, furathiocarb, hydramethylnon, halofenozide, HCH (CAS RN: 9), heptenophos, hexaflumuron, hexythiazox, hydroprene, isoamidophos, isofenphos, imidacloprid, imiprothrin, indoxycarb, iprinomectin, iprobenfos, isazophos, isoprocarb, isoprothiolane, isoxathjon, ivermectin, kadedrin, lambda-cyhalothrin, lufenuron, malathion, am, mervinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, moxiectin, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, naled, N1 125, nicotine, yram, noviflumuron, omethoate, oxamyl, oxydemethon M, oxydeprofos, ethylcarbamate, ion A, parathion M, penfluron, permethrin, 2-(4—phenoxyphenoxy)ethyl phosalon, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, phenthoate, phorate, pirimiphos A, prallethrin, profenophos, promecarb, propaphos, propoxur, prothiophos, ate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethn'n, pyrethrum, pyridaben, pyridalyl, pyrimidifen, pyriproxifen, pyrithiobac-sodium, quinalphos, resmethn'n, rotenonc, salithion, sebufos, silafluofcn, spinosad, spirodiclofen, spiromcsifen, sulfotep, sulprofos, tau-fluvalinate, tar oils, tebufenozide, npyrad, tebupin'mphos, teflubcnzuron, tcfluthn’n, temephos, terbam, terbufos, tetrachlorvinphos, ethrin, tetramethacarb, thiacloprid, thiafenox, thiamethoxam, thiapronil, thiodicarb, thiofanox, thiazophos, thiocyclam, thiomethon, thionazin, thuringicnsin, tralomethrin, uthrin, triarathen, triazophos, triazamate, triazuron, orfon, triflumuron, tn'mcthacarb, vamidothion, xylylcarb, zctamethrin; molluscicides: fentin acetate, ehyde, methiocarb, niclosamide; herbicides and algicides: acetochlor, acifluorfen, aclom'fen, in, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamatc, anilofos, asulam, atrazine, azafenidin, aziptrotryne, azimsulfuron, lin, benfluralin, benfuresatc, bcnsulfuron, bensulfide, bentazone, benzofcncap, benzthiazuron, bifenox, bispyribac, ibac-sodium, borax, bromacil, bromobutide, enoxim, bromoxym'l, butachlor, butamifos, butralin, butylate, bialaphos, l-prop, bromobutide, butroxydim, carbetamide, trazone-ethyl, strole, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol, chloridazon, chlorimuron, itrofen, chloroacetic acid, nsulam-methyl, n-ethyl, ohlorotoluron, chloroxuron, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinosulfuron, clefoxydim, clethodim, clomazone, chlomcprop, clopyralid, cyanamide, cyanazine, cycloate, cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron, oxyfen, cyhalofop, cyhalofop-butyl, clopyrasuluron, cyclosulfamuron, diclosulam, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufem'can, diflufcnzopyr, dimefuron, dimepiperate, dimethachlor, dimethipin, dinitramine, dinoseb, dinoseb acetate, dinoterb, diphcnamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, DSMA, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba, dichlobenil, dimethamid, dithiopyr, dimethametryn, cglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, cthobenzam'd, ethoxyfen, ethametsulfuron, ethoxysulfuron, fenoxaprop, fenoxaprop-P, fenuron, p, flamprop-M, flazasulfuron, op, fluazifop-P, fuenachlor, fluchloralin, flufenacet, flumeturon, fluorocglycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluroxypyr, fen, fosamine, fosametine, flamprop-isopropyl, flamprop-isopropyl-L, flufenpyr, flumiclorac-pcntyl, opyn, flumioxzim, flurtamone, flumioxzim, ulfilron-methyl, fluthiacet-methyl, glyphosate, glufosinate—ammonium haloxyfop, hexazinone, imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, ulfuron, imazomox, isoxaflutole, imazapic, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-hydrazide, MCPA-thioethyl, MCPB, meooprop, mecoprop-P, mefenacet, mefluidide, mesosulfiaron, metam, metamifop, metamitron, chlor, methabenzthiazuron, methazole, methoroptryne, methyldymron, methyl isothiocyanate, metobromuron, metoxuron, metribuzin, metsulfuron, molinate, manolide, monolinuron, MSMA, metolachlor, metosulam, nzuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, sodium chlorate, oxadiazon, oxyfluorfen, oxysulfuron, orbencarb, oryzalin, oxadiargyl, amide, prosulfocarb, pyrazolate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, ticarb, pyridate, paraquat, te, pendimethalin, pentachlorophenol, pentoxazone, pentanochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, mine, profoxydim, prometryn, propachlor, propanil, propaquizafob, propazine, propham, ochlor, pyriminobacmethyl , pelargonic acid, pyrithiobac, pyraflufen-ethyl, quinmerac, quinocloamine, quizalofop, ofop-P, quinchlorac, rimsulfuron, P001 00659A sethoxydim, sifuron, simazine, simetryn, sulfosulfuron, sulfometuron, sulfentrazonc, rionc, sulfosate, tar oils, TCA, TCA-sodium, tebutam, tcbuthiuron, tcrbacil, terbumeton, terbuthylazine, terbutryn, triasulfuron, tribenuron, thiazafluoron, thifensulfuron, ncarb, thiocarbazil, tralkoxydim, ate, triflusulfuron, pyr, tridiphane, trietazinc, trifluoralin, tycor, thdiazimin, pyr, vemolate. industrial The biocidal itions to are especially suitable for imparting biocidal properties varnishes, s, materials such as, more particularly, coating materials such as, for example, paints, impregnating systems and stains. if they include transition metal Particularly in binder formulations comprising alkyd resin, especially dryers and/or transition metal compounds as pigments, is the izing effect of the nitrogen biocidal action manifested in a containing polymers on the iodine containing compounds with a particularly advantageous way.

The invention therefore further provides binder formulations comprising a) at least one binder, action and b) at least one iodine containing compound having a biocidal c) at least one nitrogen containing polymer and preference the individual components being subject in the same way to abovementioned ranges ranges. resin containing binders, Preferred binders are oxidatively drying binders, such as, for example, alkyd such as r latices in particular. or s which film by means of coalescents, resins in general, polycondensation resins formed from The polybasic alkyd are, polyols and fatty acids. The carboxylic acids and/or their anhydrides, and fats, oils or free natural and/or synthetic especially water- alkyd resins may ally also be modified chemically with hydrophilic groups, emulsifiable or as a water-soluble soluble groups, in order that they can be used, for example, as an alkyd resin.

The stated polyols are preferably glycerol, pentaerythritol, trimethylolethane, trimethylolpropane s diols such as ethane-/propanediol, diethylenc glycol and neopentyl glycol.

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

The stated oils or fatty acids are generally linseed oil, oiticica oil, tung oil, soya oil, sunflower oil, safflower oil, ricinene oil, tall oil, castor oil, t oil, peanut oil, their fatty acids, and also synthetic monocarboxylic acids.

The alkyd resins can optionally also be modified with, for example, natural resins, phenolic resins, alkoxides. acrylic resins, styrene, epoxy resins, silicone resins, nates, polyamides or aluminium to 100 000 g/mol, preferably of 1000 to The alkyd resins generally have a molar mass of 500 laser 50 000 gmol, more particularly of 1500 to 20 000 g/mol, determined preferably by light Round Robin scattering; see, for example, c Light Scattering of Polystyrene Reference Materials: 1999 Test”, U.Just, hmann International Journal of Polymer Analysis and Characterization, Vol. 5, pages 195 — 207. 2% to 70% The binder formulations of the invention comprise preferably 1% to 80%, more preferably and with particular preference 3% to 60% by weight of , preferably alkyd resin.

The binder formulation of the invention preferably further comprises at least one tion metal transition dryer. Transition metal dryers for the purposes of this specification are more particularly resin—based metal nds which enable or accelerate the drying and curing of alkyd containing binders.

Preference is given to the salts of transition metals of groups Vb, VIb, VIIb, VIII and Ib of the chemical periodic system. These are more particularly the salts of cobalt, manganese, vanadium, nickel, copper and iron, more ably cobalt, manganese, iron and vanadium. They need not metal necessarily be used alone, but instead can also be employed in ation with non-transition salts, such as lead, calcium or zirconium, for example.

The preferred transition metal salts are soluble in white spirit at 20°C in an amount of more than have high compatibility g/l. The salts in question are preferably the salts of carboxylic acids, which salt. Preference is with the alkyd resins and at the same time ensure sufficient solubility of the metal resin acids such as given to using transition metal salts of fatty acids such as oleates or ates, acid (octoates). red transition metal dryers are cobalt tes, or salts of 2-ethylhexanoic 3O octoate and cobalt naphthenate, e.g. Octasoligen®-Coba1t 12 from Borchers.

The binder formulations of the invention preferably comprise the transition metal dryers in an amount of 0.001% to 1%, preferably 0.005% to 0.5% and very preferably 0.01% to 0.1% by weight, based in each case on the binder, preferably alkyd resin.

In one preferred embodiment the binder ations comprise at least one polar organic t, preferably a polar protic organic solvent. Examples of suitable polar protic organic solvents e are those such as dipropylene glycol thyl ether (e.g. Dowanol DPM from Dow Chemical) and also, alternatively, preferably in addition thereto, polar aprotic organic solvents, such as dimethylformamide and dimethyl sulphoxide, and also, for example, fied s, oligoglycols and polyglycols, etherified polyols and esterified polyols, esters of monobasic and polybasic earboxylic acids, e.g. diisobutyl adipate, diisobutyl maleate (e.g. Rhodiasolv DIB).

Particular preference is given to a binder ation sing 1% to 80%, ably 2% to 70%, more preferably 3% to 60% by weight of alkyd resin 0% to 50%, preferably 0% to 45%, more preferably 0% to 40% by weight ofpigments 0.01% to 5%, preferably 0.05% to 3%, more preferably 0.1% to 2% by weight of iodine containing compounds with a biocidal action, preferably IBPC 0.001% to 5%, preferably 0.005% to 3%, more preferably 0.01% to 2% by weight of nitrogen containing polymer 2% to 97% by weight of solvent(s), preferably those as described above for the al compositions and 0.001% to 3% by weight of a transition metal dryer.

The binder formulation may further comprise or not se the following, in each case independently of one another: fillers, anti-skinning agents, rheological additives such as, for example, anti-settling agents and thixotropic agents, further antimicrobially active compounds, fungicides, bactericides, herbicides, icides or other active ients; for the antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients, the statements made above in respect of the biocidal compositions apply equally here.

The binder formulation may further comprise or not comprise the following, in each case independently of one another: solvents, process additives, plasticizers, heat stabilizers, and corrosion inhibitors.

P001 00659A of the invention may also further Furthermore, the biocidal compositions or binder formulations of the antioxidants, radical scavengers, UV comprise one or more auxiliaries from the series such cases synergistic effects are observed. stabilizers, ing agents and UV absorbers. In some the following: UV stabilizers that may be mentioned e, by way of example, ally hindered phenols, such as 2,6-di-tert-butyl—4-methylphenol, 2-tert-buty1-4,6>dimethy1phenol, 2,6-di-cyclopentylmethylphenol, ethy1cyclohexyl)-4,6-dimethy1phenol, 2,6-di-octadecy1methylphenol or 2,6-di-tert-buty1methoxymethy1phenol, diethyl i-tert-buty1—4-hydroxybenzy1)phosphonate, 2,4-dimethyl(l -methy1pentadecyl)phenol, 2-methyl-4,6-bis[(octylthio)methyl]phenol, 2,6-di-tert-butylmethoxyphenol, 2,5-di-tert-buty1hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-dipheny1-4~octadecyloxyphenol, 2,2'-thiobi5(6-tert-buty1methy1phenol), 2,2'-thio- bis(4-octylphenol), 4,4'-thiobis(6-tert-butylmethylphenol), 4,4'-thiobis(6-te1t-buty1methyl- phenol), 2,2'-methylenebis(6-tert-butylmethy1phenol), 2,2'-methylenebis(4-methyl~6-cyclohexyl- phenol), 2,2‘-methylenebis(4,6-di-tert-buty1phenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 4,4'-methy1enebis(2,6»di-tert-buty1phenol), 4,4'-methylenebis(6-text-buty1methy1phenol), 1 ,1,3-tris(5-tert-butylhydroxymethyl- 1 l -bis(5-tert-buty1hydroxymethylphenyl)butane, isooctyl )butane, 1,3,5-tri(3,S-di-tert-butyl—4-hydroxybenzyl)-2,4,6-trimethylbenzene, 3,5-di-tert—buty1hydroxybenzylmercaptoacetate, 1,3,5-tris(3,5—di-tert-buty1hydroxybenzyl) isocyanurate, l,3,5-tris[(3,5-di- isocyanurate, tris(4-tert-buty1-3 -hydroxy-2,6-dimethylbenzy1) ten-butylhydroxyphenyl)propionyloxyethyl] isocyanurate, dioctadecyl —tert-butylhydroxy- N,N'- benzylphosphonate, calcium monoethyl 3,5-di-tert-butylhydroxybenzy1phosphonate, di-(3,S-di-tert-butyl-4—hydroxyphenylpropionyl)hexamethylenediamine, N,N'-di-(3,5-di-tert-butylhydroxyphenylpropionyl)trimethylenediamine, 3 [ 1 ,l -dimethy1[(3 -tert-butyl- N,N'-di-(3 ,S-di-tert-buty1hydroxypheny]propionyl)hydrazine, bis[3 ,3-bis(4'— 4-hydroxymethylphenyl)propionyloxy]ethyl]-2,4,8, 1 0—tetraoxaspiro[5.5]undecane, hydroxy-3'—tert-butylphenyl)butanoic acid]ethy1ene glycol ester, 2,6-bis[[3-(1,l-dimethylethyl) hydroxy-S-methy1pheny1]octahydro-4,7-methano-1H-indenyl]methylphenol (= Wingstay L), 2,4- bis(n-octylthio)-6—(3,5-di-tert—butylhydroxyphenylamino)-s-triazine, N-(4-hydroxy- (benzoic acid, phenyl)octadecaneamide, 2,4-di-tert-butylphenyl 3',5'-di-tert-butyl-4'-hydroxybenzoate, 3,5-bis(1,1~dimethylethyl)hydroxy-, cyl ester), 3-hydroxyphenyl benzoate, 2,2‘— methylenebis(6-tert-butylmethy1phenol) monoacrylate, 2—(1 ,1-dimethylethyl)—6-[l-[3-( l ,1 - l -dimethylpropyl)phenyl ester, dimethylethyl)-5 -(1 , 1 -dimethylpropyl)hydroxypheny1]ethyl](1 , acid with monohydric or polyhydric alcohols esters of B-(3,5-di-tert-butylhydroxypheny1)propionic glycol, thiodiethylene such as, for example, with methanol, octadecanol, 1,6-hexanediol, neopentyl P_Ofll_0_0_6_59A glycol, diethylene , triethylene glycol, pentaerythritol, trishydroxyethyl isocyanurate or oxyethyloxalamide, esters of 13~(5—tert-butylhydroxymethylpheny1)propionic acid with monohydric or polyhydric alcohols such as, for example, with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodicthylene , diethylene glycol, triethylene glycol, pentaerytbritol, trishydroxyethyl isocyanurate or dihydroxyethyloxalamide.

Hindered amines, such as bis(l ,6-pentamethyl—4-pipexidyl) 2-(3,5-di-tert-butyl—4-hydroxybenzyl)butylmalonate, 2,6,6-tetramethyl-4—piperidyl)decancdioate, dimethyl succinate-l-(2-hydroxyethy1)hydroxy- 2,2,6,6-tetramethylpiperidine copolymer, poly[[6-[(1 ,1 ,3 ,3-tetramethylbutyl)amino]-1 ,3 ,5-triazine-2,4- diyl] [(2,2,6,6-tetramethylpiperidy1)imino]hexamethylene[(2,2,6,6-tetramethylpiperidyl)imino]] (CAS No. 718788), 1,5,8,12-tetrakis[4,6-bis(n-buty1-n-1,2,2,6,6-pentamethylpiperidylamino)- 1,3,5-triazinyl]-l,5,8,12-tetraazadodecane (CAS No. 6), bis(l,2,2,6,6-pentamethyl piperidyl)decanedioate, bis(l ,2,2,6,6-pentamethylpiperidyl) 2-(3,5-di-tert-butylhydroxybenzyl)- 2-butylmalonate, decanedioic acid, bis(2,2,6,6-tetramethylpiperidinyl) ester, reaction products with tert-butyl eroxide and octane (CAS No. 1297571), Chimasorb 2020 (CAS No. 192268 7), poly[[6-morpholino-1 ,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethy1piperidiny1)imino] -1 ,6-hexane- diyl[(2,2,6,6-tetramethy1—4-piperidinyl)imino]], poly[[6-(4-morpholinyl)—l ,3,5-triazine-2,4-diy1]- [(1 ,6-pentamethylpiperidinyl)imino]-1 anediy1 [(1 ,2,2,6,6-pentamethylpiperidinyl)- imino]] (9CI), cy1(2,2,6,6-tetramethylpiperidyl)pyrrolidine-2,5-dione, 3-dodecyl (1 ,2,2,6,6-pentamethylpiperidinyl)pyrrolidine-2,5-dione, 4-octadecanoyloxy-2,2,6,6-tetmiethyl- piperidine, poly[[6-(cyclohexylamino)-1 ,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethy1piperidiny1)- imino]-1,6-hexanediyl[(2,2,6,6-tetramethylpiperidiny1)imino]], 5H,8H-2,3a,4a,6,7a,8a- hexaazacyclopenta[def]fluorene-4,8-dione, hexahydro-2,6-bis(2,2,6,6-tetramethylpiperidinyl)- (CAS No. 1094239), N,N'-bis(formyl)-N,N'-bis(2,2,6,6-tetramcthylpiperidyl)-1,6-hexane- diamine, N-(tetramethylpipcridinyl)maleimide-CZOcL-olefin copolymer (CAS No. 199237 3), tetrakis(1,2,2,6,6-pentamethylpiperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6—tet1a- methylpiperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pcntamethy1pipefidinyl tridecyl 1,2,3,4-butanetetracarboxylate, (l,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethylpiperidinyl yl ester), (2,4,8, 1 0-tetraoxaspiro[5.5]undecane-3,9-diethanol, B,B,[3',B'—tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid) (CAS No. 1150556), 2,2,4,4-tetramethy1oxooxa-3,20- diazadispiro[5.1 .1 l .2]heneicosane, (7-oxa-3,20-diazadispiro[5 .l .1 1 .2]heneicosanepropanoic acid, 2,2,4,4-tetramethyl-2 1 -oxo-, tetradecyl ester), (7-oxa-3,20-diazadispiro[5 . 1 . l 1 .2]heneicosan-21 -one, 2,2,4,4-tetramethyl-20—(oxiranylmcthy1)-), (propanamide, N-(2,2,6,6-tetramethy1—4-piperidinyl) P001 00659A [(2,2,6,6-tetramethy1-4~piperidinyl)amino]-), (1,3-propanediamine, N,N"'-l ,2-ethanediylbis-, r with 2,4,6-trichloro-l ,3,S-triazine, reaction products with N-butyl-Z,2,6,6-tetramethylpiperidin- amine) (CAS No. 1365046), l,1‘-ethy1enebis(3,3,5,5-tetramethylpiperazinone), (piperazinone, 1,1',1 "-[l ,3,5-ttiazine-2,4,6-triyltfis[(cyclohexylimino)~2,l -ethanediyl]]t1is[3,3,5,5-tetramethyl-), (7-oxa-3,20-diazadispiro[5.1.11.2]heneicosanepropanoic acid, 2,2,4,4-tetramethyloxo-, dodecyl ester), 1 , l-bis(1 ,6-pentamethylpipen'dyloxycarbonyl)-2~(4-methoxyphenyl)ethene, (2-propenoic acid, 2-methyl-, methyl ester, r with 2,2,6,6-tetramethylpiperidinyl 2— propenoate) (CAS No. 1546361), (propanamide, y1-N-(2,2,6,6-tetramethy1—4-piperidinyl)— 2-[(2,2,6,6-tetramethy1—4-piperidinyl)amino]-), (D-glucitol, l,3:2,4-bis-O-(2,2,6,6-tetmmethyl piperidinylidene)—) (CAS No. 994732), N,N'-bis(2,2,6,6-tetramethylpiperidinyl)isophthalamide, 4—hydroxy-2,2,6,6-tetramethylpiperidine, 1-a11y1-4~hydroxy-2,2,6,6-tetramethylpiperidine, l-benzyl- 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(4-text-butylbutenyl)hydroxy-2,2,6,6-tetramethy- lpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 1-ethylsalicyloyloxy-Z,2,6,6-tetramethyl- piperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethy1piperidine, 1,2,2,6,6-pentamethylpiperidin—4-y1 fi-(3,5-ditert-butylhydroxyphenyl)propionate, 1-benzy1-2,2,6,6-tetramethylpiperidinyl maleate, (di—2,2,6,6-tetramethylpipefidinyl) adipate, (di-2,2,6,6-tetramethylpiperidin-4—yl) sebacate, (di-l ,6-tetramethyl-2,6-diethylpiperi'dinyl) sebacate, (di-l -allyl-2,2,6,6-tetramethyl- piperidiny1) phthalate, 1-propargyl-4—B-cyanoethyloxy—2,2,6,6-tetramethylpiperidine, l-acetyl- 2,2,6,6-tetramethylpiperidinyl acetate, trimellitic acid tri(2,2,6,6-tetramethylpiperidin—4-yl) ester, l-acryloylbenzyloxy-2,2,6,6-tetramethylpiperidine, dibutyl-malonic acid di(1,2,2,6,6-pentamethyl- piperidinyl) ester, buty1(3,5-di-tert-buty1hydroxybenzyl)malonic acid di(1,2,2,6,6-pentamethyl- piperidinyl) ester, dibenzylmalonic acid di(l ,6-pentamethylpiperidinyl) ester, dibenzylmalonic acid di(l,2,3,6-tetramethyl-2,6-diethylpiperidinyl) ester, hexane-1',6'-bis- (4-carbamoyloxyn—butyl-2,2,6,6-tetramethylpiperidine), toluene-2',4’-bis(4-carbamoyloxy- 1-n—propyl-2,2,6,6-tetramethylpiperidine), dimethyl-bis(2,2,6,6—tetramethylpiperidine—4-oxy)silane, phenyl-tris(2,2,6,6-tetra1nethylpipe1idineoxy)silane, tris(1 -propy1-2,2,6,6-tetramethylpiperidin—4-yl) phosphite, -propy1-2,2,6,6-tetramethylpiperidinyl) phosphate, phenyl[bis(l ,2,2,6,6-penta- methylpiperidinyl)phosphonate, di(1,2,2,6,6-pentamethylpiperidinyl) te, N,N'-bis(2,2,6,6— tetramethylpiperidin—4-yl)hexamethylene-l ,6-diamine, N,N’-bis(2,2,6,6-tetramethy1piperidinyl)- hexamethylene-l ,6-diacetamide, l-acetyl(N-cyclohexylacetamido)-2,2,6,6-tetramethy1piperidine, 4-benzylamino-2,2,6,6-tetramethylpiperidine, N,N'—bis(2,2,6,6—tetramethylpiperidin-4—yl)- N,N'—dibutyladipamide, N,N'-bis(2,2,6,6-tetramethylpiperidinyl)-N,N'—dicyclohexyl(2-hydroxy- propylene), is(2,2,6,6-tetramethylpiperidinyl)-p-xylylenediamine, 4—(bishydroxy- ethyl)amino-1,2,2,6,6-pentamethylpiperidine, 4-(3-methylhydroxytert-buty1-benz-amido)- 2,2,6,6-tetramethylpiperidine, 4-methacrylamino-1 ,2,2,6,6-pentamethylpiperidine, 9-aza-8,8,10,1 0- tetramethyl-l ,5 -dioxaspiro[5 .5]undecane, 9-aza-8,8, l 0,1 0-tetramethylethy1-l ,5-dioxaspiro[5 .5]~ P001 OQ§§2A .29- undecane, 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane, 9-azahydroxymethyl- 3-ethy1-8,8,9,10,10-pcntamethyl-1 dioxaspiro[5 .5]undecane, 9-aza-3 ethyl-3 xymethyl- 9—acetyl-8,8,l 0, 10-tetramethy1-1 ,5-dioxaspiro[5.5]undecane, 2,2,6,6-tetramethy1piperidine- o-2'-(l',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4"—(2"',2"‘,6"',6"‘-tetramcthyl- pipcridine)benzy1-l ,3,8-triaza-7,7,9,9-tetramethyl-spiro[4.5]decane-2,4-dione, 3-n-octyl- 1 ,3,8-triaza-7,7,9,9-tetramethyl-spiro[4.5]decane-2,4-dione, 3-a11y1-1,3,8-triaza-1,7,7,9,9-penta— methyl-spiro[4.5]decane-2,4-dione, 3-glycidy1-l ,3,8-triaza-7,7,8,9,9-pentamethyl-spiro[4.5]- decane-2,4-dione, 2-isopropyl-7,7,9,9-tetramethyloxa-3,8-diazaoxyspiro[4.5]decane, 2-butyl- 7,7,9,9-tetramethyl- 1 ~0xa-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-l -oxa-4,8-diaza—3-oxyspiro[4.5]decane, bis[B-(2,2,6,6-tetramethy1piperidino)cthyl] sebacate, (it-(2,2,6,6-tetramethylpipcridino)acetic acid l ester, 1,4-bis(2,2,6,6-tetramethylpiperidino)butene, oxymcthyl-N'-2,2,6,6-tetra~ methylpiperidinylurea, oxymethyl-N'-2,2,6,6-tetramethylpiperidinylurea, N-methoxy- methyl-N’-n-dodecyl-N'-2,2,6,6-tetramethy1piperidinylurea, O»(2,2,6,6-tetramethyl- piperidinyl)-N-methoxymethy1urethane.

Phosphites and phosphonates, such as tris(nony1phenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphitc, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butylmethylphenyl)pentacrythritol diphosphitc, 2,2'-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, tetrakis(2,4-di-tert-butylpheny1)- [1,1'-biphenyl]-4,4'-diy1bisphosphonite, 2,2‘-ethylidenebis(4,6-di-tert-buty1pheny1) fluorophosphite, dioctadecyl pentaerythritol diphosphonite, 2-[[2,4,8 , 1 O-tetrakis(1 ,1 -dimethylethy1)dibenzo [d,f] [1 ,3 ,2]- dioxaphosphin—é-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1 ,1-dimethylethyl)dibenzo[d,t][1,3 ,2] - dioxaphosphin-é-yl]oxy]ethyl]ethanamine (CAS No. 804109), bis(2,4-di-teIt-butylmethyl- ) ethyl phosphite, 2,4,6-tri-tert-butylphenyl 2-buty1ethyl-1,3-propanediol phosphite, bis(2,4— dicumylphenyl) pentaerythritol diphosphite, hydroxylamines, such as amines, bis(hydrogenated tallow , oxidized, secondary arylamincs, such as aphthy1)-N—phenylamine, 2,2,4-trirnethyl-1,2-dihydroquinolinc polymer (CAS No. 26780 1), Npropyl-N'-phcnyl-p-phenylenediamine, N-(l -naphthy1)-N-pheny1amine, (benzenamine, N-phcnyl-, on products with 2,4,4-trimethylpentene) (CAS No. 68411-46—1), 4-(1-methy1- l -pheny1ethy1)-N—[4—(l -methyl-1 -phenylethy1)phenyl]aniline.

Emu OOQQQA Lactones and benzofuranones, such as Irganox HP 136 (CAS No. 1813147) Thioethers and thioesters, such as distearyl 3,3-thiodipropionate, dilauryl 3,3'-thiodipropionate, ditetradecyl thiodipropionate, ctadecyl disulphide.

UV absorbers, such as none, [methylenebis(hydroxymethoxyphenylene)]bis[pheny1-), (methanone, [1,6-hexanediyl- y(2-hydroxy-4,l-pheny1ene)]]bis[phenyl-), oylmethoxyphenol, 2,4-dihydroxybenzo- phenone, 2,2'-dihydroxymethoxybenzophenone, 2-hydroxyoctyloxybenzophenone, 2-hydroxy- 4-dodecyloxybenzophenone, 2-(2-hydroxyhexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4-bis- (2,4-dimethy1phenyl)(2-hydroxyoctyloxyphenyl)-l,3,5-triazine, 2-ethoxy-2'-ethyloxalic acid bisanilide, N-(5-tert-butyl—2-ethoxyphenyl)-N'—(2-ethylphenyl)oxamide, dimethyl (p-methoxy- benzylidene)malonate, 2,2'-(1,4-phenylene)bis[3,1-benzoxazinone], N‘-(4-ethoxycarbonylphenyl)— N-methy1-N-phenylformamidine, 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid isoamyl ester, 2-phenylbenzimidazolesulphonic acid, 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester, 2-ethy1hexyl salicylate, 3-(4-methylbenzylidene)bornanone, chelators, such as ethylenediaminetetraacetate (EDTA), ethylenediamine, acetylaoetone, nitrotriacetic acid, ethylene glycol bis(B-aminoethyl ether)-N,N-tetraacetic acid, 2,2'-bipyfidine, 4,4'-dimethyl-2,2'-bipyridine, 2,2',6',2"-terpyridine, 4,4‘-dipheny1-2,2'-bipyridine, 2,2'-bipyridine-3,3'-diol, henanthroline, 4-methyl-1 , 1 0-phenanthroline, 5-methy1-1 ,1 0-phenanthroline, 4,7-dimethyl-l , 1 0-phenanthroline, ,6-dimethy1-1,lO-phenanthroline, 3,4,7,8-tetramethyl-l,10-phenanthroline, 4,7—diphenyl-1,10-phen- line, 9-tetramethyl-l ,1 0-phenanthroline, N,N,N',N'-tctramethylethy1enediamine, 2-hydroxyquinoline, 8-hydroxyquinoline, 2-hydroxymethquuinaldine, 5-chlorohydroxy- quinoline, 5,7-dichlorohydroxyquinoline, 2,4-quinolinediol, 2-quinolinethiol, 8-quinolinethiol, 8-aminoquinoline, iquinoline, 2-quinoxa1inol, 3-methylquinoxalinol, 2,3-dihydroxy— aline, 2-mercaptopyridine, thylaminopyridine, 1,2-bis(dimethy1phosphino)ethane, 1,2- bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4—bis(diphenylphosphino)- butane, polyaspartic acid, iminodisuccinate.

P001 00659A The binder formulations of the invention are especially suitable for use as coating materials, more ularly for use as paint, varnish, primer, impregnating system or stain. entioned uses are likewise ed by the ion.

The binder formulations of the invention sing transition metal dryers themselves, relative to binder formulations in which the iodine containing compounds, more particularly IPBC, have not been stabilized, do not exhibit any lengthening in the drying time, like that frequently ed when stabilizers are added.

The ion further provides for the use of the biocidal compositions of the invention for protecting industrial materials against destruction or infestation by microorganisms.

The biocidal compositions of the invention are le for biocidally treating industrial materials.

Industrial materials in the present context are non-living materials which have been prepared for use in industry. The industrial materials are, for example, adhesives, sizes, paper and cardboard, textiles, leather, wood, wood-based materials, coating materials and plastics articles, cooling lubricants and other materials which may be infested or decomposed by rganisms.

Examples of microorganisms which may bring about degradation or alteration of the industrial materials include bacteria, fungi, yeasts, algae and slime organisms. The active ingredients of the invention act preferably against fungi, more particularly moulds, wood-discolouring and wood- destroying fungi (Basidiomycetes) and also against slime organisms and bacteria.

Microorganisms of the following genera may be mentioned by way of example: Alternaria, such as Altemaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as mium globosum, Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus us, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, EQQI QQQS9A Sclerophoma, such as Sclerophoma pityophila, Trichoderrna, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas nosa, Staphylococcus, such as Staphylococcus aureus.

The invention further provides the industrial materials comprising at least one iodine ning compound having a biocidal action and also a nitrogen containing polymer.

The invention is elucidated below by examples but is not restricted thereto. _33_ Examples: Example 1 g of trimethylolpropane tris[3-(2-methy1-l -aziridinyl)propionate] (Crosslinker CX-lOO from DSM) were introduced in 50 ml of water and d with 30 g of butyl diglycol while stirring with the magnetic stirrer. This was followed by stirring at 80°C for 6 hours. A solution was obtained which afier cooling was clear and was slightly yellowish.

Determination of lar weight: g of the sample prepared above were freed fi'om water at 50°C under an oil pump vacuum (about 0.35 mbar). This gave 12.85 g of a highly viscous oil. 1 g of this oil was stirred with 3 times 5 g of THF, and the residue was dried overnight in a desiccator and ed by GPC (Standard: polystyrene/PSS Polymer kit). A polymer was identified which had an average molecular weight of 12,238 g/mol. The only component detectable in the THF washing liquid by GC-MS was butyl diglycol.

No aziridine functionalities were detectable.

Example 2 g of trimethylolpropane tris[3-(2—methy1—l -aziridinyl)propionate] (Crosslinker CX-lOO from DSM) were introduced in 20 ml of water and admixed with 30 g of butyl diglycol while stirring with the magnetic stirrer. This was followed by stirring at 80°C for 6 hours. A solution was obtained which after cooling was clear and was slightly yellowish.

Refractive index no = 1.4115 (23°C) A fraction < 50 ppm of the Crosslinker CX-lOO starting product was found in this solution by quantitative LC-MS.

Example 3: Production ofan inventive biocidal ition 40 g of trimethylolpropane tris[3-(2-methylaziridinyl)propionate] (Crosslinker CX-lOO from DSM) were introduced in 100 ml of water and admixed with 60 g of butyl ol while stirring with the magnetic stirrer. This was followed by stining at 80°C for 6 hours. A solution was obtained which after g was clear and was slightly yellowish. This solution was admixed while stirring with a r 320 g l diglycol and 120 g of [PEG (iodopropargyl butylcarbamate) and the mixture was P001 00659A solution having an stirred with a magnetic stirrer for 45 s. This gave 640 g of a slightly yellow IPBC content of 18.8% by weight. of formic acid and the 150 g of the solution ed above was admixed while stirring with 0.3 g biocidal ition mixture was stirred further for 5 minutes more. The IPBC containing, stabilized was pale yellow and clear.

Refractive index 119 = 1.4375 (23°C) Example 4: Binder formulations in a The compounds/compositions ed ing to Examples 1, 2 and 3 were incorporated of a transition typical, alkyd resin containing coating system (alkyd stain A/Table 1) in the presence and 2, metal dryer (Co) and of a metal oxide pigment (iron oxide). In the case of Examples] IPBC is containing no IPBC, an IPBC concentrate in Table 2 is additionally added. As a ative incorporated directly bilized IPBC) or as a concentrate in Table 3 (stabilized IPBC according EP 2236033). The composition of the completed stains can be seen from Table 4.

In all of the examples the IPBC concentration in the stains is 0.7%.

Table 1 (Formula of alkyd stain A) l gredients Amount [% by weight] Alkyd stain A Vialkyd VAF 4349, 80 SD 60, Cytec .

Polar solvent Texanol, Eastman 5.0 Rheology additive BYK E411, BYK Shellsol D60, Shell Chemicals 67.8 MK-Solcolor red iron oxide 130M (pigment 4.0 preparation), MK Chemicals Octa-Soligen® 69 (containing 6% Co), Borchers P001 00659A Table 2 — IPBC concentrate (unstabilized) IPBC 21% by weight Texanol -trimethyl—1,3-pentanediol monoisobutyrate) 79% by weight Table 3 — IPBC/aziridine concentrate/comparative IPBC 30% by weight Crosslinker CX-100** 15% by weight Rhodiasolv DIB“ 55% by weight Rhodia.

*Mixture ting of diisobutyl adipate, diisobutyl glutarate, utyl succinate, "Trimethylolpropane tris[3-(2-methy1aziridiny1)propionate] this test the armoured The stabilization is determined by performing an accelerated ageing test. For minimal remaining colour system is introduced into y closing 200 m1 glass bottles, leaving only a stain.

Table 4 — Formula of a pigmented, IPBC-armoured alkyd resin containing stain A-IV [%] A-III [%] Comparative 1 IPBC solution in Texanol (21% IPBC/79% Texanol; Table 1) Stabilizer from Example 2 Table 4 — Formula of a pigmented, IPBC-armoured alkyd resin containing stain. stain A-II [%] (Table 3) 1) Corresponding in each case to 0.7% by weight of IPBC, based on the stain.

Table 5 — Stability ofIPBC in the alkyd stains A (-I) to (-V) at 40°C -Residual IPBC content [%] based on the ng value -“-— 1) Unstabilized sample 2) IPBC stabilized with aziridine, without hydrolysis (in accordance with EP 2 236 033 A) From Table 5 it is clear that the nitrogen containing polymers in relation to the stabilization of IPBC exhibit much higher stability than the unstabilized sample A-IV. A marked ement is also evident in relation to the IPBC sample stabilized with unreacted aziridine (stain A-V).

Claims (28)

What we claim is:

1. Use of nitrogen containing polymers for stabilizing iodine containing compounds, characterized in that the nitrogen containing polymers are polymers obtained by on of aziridines in the ce of water and have a on of 5 % or less of aziridine nitrogen, 5 based on the total nitrogen content.

2. Method for stabilizing iodine containing compounds by ting the iodine containing compounds with nitrogen containing polymers, characterized in that the en containing polymers are rs obtained by reaction of aziridines in the presence of water and have a fraction of 5 % or less of aziridine nitrogen, based on the total nitrogen content. 10

3. Use according to Claim 1 and method according to Claim 2, characterized in that the iodine containing compounds are iodoalkynyl compounds and also compounds in which one or more iodine atoms are bonded to sp2-hybridized carbon atoms of olefinic double bonds or to sp3- hybridized carbon atoms.

4. Use and method according to Claim 3, characterized in that iodine ning compounds 15 have biocidal ty and are as follows: C12)-alkyl-iodotetrazoles, N-(C6-C15)-aryliodotetrazoles , N-(C6-C15)-arylalkyl-iodotetrazoles, diiodomethyl p-tolyl sulphone, diiodomethyl p-chlorophenyl sulphone, 3-bromo-2,3-diiodopropenyl alcohol, 2,3,3- triiodoallyl alcohol, 4-chloro(2-chloromethylpropyl)[(6-iodopyridinyl)methoxy]- 3(2H)-pyridazinone (CAS RN: 1209553), nphos, 3-iodopropynyl 2,4,5- 20 trichlorophenyl ether, 3-iodopropynyl 4-chlorophenyl formal (IPCF), N-iodopropargyloxycarbonyl-alanine, N-iodopropargyloxycarbonyl-alanine ethyl ester, 3-(3- iodopropargyl)benzoxazolone, 3-(3-iodopropargyl)chlorobenzoxazolone, 3-iodo propynyl l, 4-chlorophenyl 3-iodopropargyl formal, 3-iodopropynyl propylcarbamate, 3-iodopropynyl butylcarbamate (IPBC), 3-iodopropynyl 25 m-chlorophenylcarbamate, 3-iodopropynyl phenylcarbamate, di-(3-iodopropynyl)hexyl dicarbamate, 3-iodopropynyloxyethanol ethylcarbamate, 3-iodopropynyloxyethanol phenylcarbamate, 3-iodopropynyl thioxothioethylcarbamate, 3-iodopropynyl-carbamic ester (IPC), 3-bromo-2,3-diiodopropenyl arbamate, 3-iodopropynyl nhexylcarbamate and 3-iodopropynyl cyclohexylcarbamate. 30

5. Use according to any of Claims 1 and 3 to 4 and method according to any of Claims 2 to 4, characterized in that the nitrogen containing polymers possess a weight-average molecular weight of more than 1000 g/mol ined by gel permeation chromatography against polystyrene standard.

6. Use according to any of Claims 1 and 3 to 5 and method according to any of Claims 2 to 5, characterized in that the nitrogen containing polymers possess a weight-average molecular weight of 2000 to 100,000 g/mol determined by gel permeation tography against yrene standard. 5

7. Use according to any of Claims 1 and 3 to 6 and method according to any of Claims 2 to 6, characterized in that the nitrogen containing polymers s a weight-average molecular weight of 3000 to 60,000 g/mol determined by gel permeation chromatography against polystyrene standard.

8. Use according to any of Claims 1 and 3 to 7 and method according to any of Claims 2 to 7, 10 terized in that the en containing polymers have a nitrogen content of 1% to 20% by weight N, determined by elemental analysis.

9. Use according to any of Claims 1 and 3 to 8 and method according to any of Claims 2 to 8, characterized in that the nitrogen containing polymers have a nitrogen content of 2% to 15% by weight N, determined by elemental analysis. 15

10. Use according to any of Claims 1 and 3 to 9 and method according to any of Claims 2 to 9, characterized in that the en containing polymers have a en content of 5% to 12% by weight N, determined by elemental analysis.

11. Use according to any of Claims 1 and 3 to 10 and method according to any of Claims 2 to 10, characterized in that the nitrogen containing polymers are polymers sing at least one 20 beta-aminoamine functions.

12. Use according to any of Claims 1 and 3 to 11 and method according to any of Claims 2 to 11, characterized in that the nitrogen containing polymers are polymers possessing two or more beta-aminoamine functions.

13. Use according to any of Claims 1 and 3 to 12 and method according to any of Claims 2 to 12, 25 terized in that the aziridines are aziridine compounds of the formula (I) R2 R4 (I) R3 R5 where R1 is hydrogen, alkyl or cycloalkyl, each of which is unsubstituted or substituted and/or mono- or polyethylenically unsaturated, or in each case substituted or unsubstituted fullerenyl, aryl, alkoxy, carbonyl, arylcarbonyl or alkanoyl, R2, R3, R4 and R5 independently of one r have the same definition as R1 and additionally 5 ndently are halogen, yl, carboxyl, alkylsulphonyl, arylsulphonyl, nitrile, isonitrile, and R2 and R4 or R3 and R5, together with the carbon atoms to which they are attached, form a 5- to 10-membered yclic ring which is unsubstituted or substituted and/or mono- or polyethylenically unsaturated. 10

14. Biocidal compositions comprising at least a) at least one iodine containing compound having a biocidal action b) at least one en containing polymer, characterized in that the nitrogen containing polymers are polymers obtained by reaction of aziridines in the presence of water and have a fraction of 5 % or less of aziridine nitrogen, 15 based on the total nitrogen content.

15. Biocidal composition ing to Claim 14, characterized in that the nitrogen containing polymers are polymers as specified in any of Claims 5 to 13 and their dependency references to one another.

16. Biocidal composition according to Claim 14 or 15, characterized in that it further comprises 20 acid.

17. Biocidal composition according to any of Claims 14 to 16, characterized in that it comprises further active ingredients selected from the group of antimicrobially active compounds, fungicides, bactericides, herbicides and insecticides.

18. Binder formulation comprising 25 a) at least one binder, b) at least one iodine containing compound with biocidal action and c) at least one nitrogen containing polymer, characterized in that the nitrogen containing polymers are rs obtained by reaction of aziridines in the presence of water and have a fraction of 5 % or less of aziridine nitrogen, based on the total nitrogen content.

19. Binder formulation according to Claim 18, characterized in that the nitrogen containing 5 polymers are polymers as specified in any of Claims 5 to 13 and their dependency references to one another.

20. Binder formulation according to Claim 18 or 19, characterized in that it further comprises at least one tion metal dryer.

21. Use of the biocidal compositions ing to any of Claims 14 to 17 for protecting industrial 10 materials against destruction or infestation by microorganisms.

22. Use of the binder formulations according to any of Claims 18 to 20 for protecting industrial materials against destruction or ation by microorganisms.

23. A use according to claim 1, substantially as herein described or exemplified.

24. A method according to claim 2, substantially as herein described or ified. 15

25. A biocidal composition ing to claim 14, substantially as herein described or exemplified.

26. A binder formulation according to claim 18, substantially as herein described or exemplified.

27. A use according to claim 21, ntially as herein described or exemplified.

28. A use according to claim 22, substantially as herein described or exemplified.