EP2440043A1 - Inorganic carrier materials containing heterocyclic 3-ring compounds - Google Patents

Abstract

The invention relates to inorganic carrier materials containing at least one adsorptive or covalently bound heterocyclic 3-ring compounds.

Description

 - -

Inorganic heterocyclic compounds containing 3 Rϊngverbindungen

The invention relates to heterocyclic 3-ring compounds containing inorganic support materials, their preparation and their use for the stabilization of iodine-containing compounds, as well as these binder formulations and their use for the protection of industrial materials

Iodine-containing biocides are used to protect engineering materials (e.g., paints) from infestation, decomposition, destruction, and optical change by fungi, bacteria, and algae, preferably fungi. In addition, iodine-containing biocides, also in combination with biocides of other classes of active ingredients, are used as components of biocidal active material protection agents such as wood preservatives. Besides iodoalkynyl compounds, active substances are also used here in which one or more iodine atoms are bound to double bond systems, but also to singly bonded carbon atoms.

Many iodine-containing biocides have in common that, when exposed to light, even in bulk or as a component of a technical material (e.g., paints), they lead to yellowing with drug degradation. This feature impedes or prevents the use of iodine-containing biocides in correspondingly sensitive materials, e.g. in light or white paints. Described are these destabilizing properties for the IPBC, for example in WO00 / 16628.

Many iodine-containing biocides, in particular iodoalkynyl compounds, are destroyed particularly rapidly by metal compounds. This fact prevents the use of e.g. Iodoalkynyl compounds in solvent-based paints, e.g. Paints, varnishes and glazes, or biocidal protection agents, such as. Wood preservation primers, wood preservatives and wood stains, since these alkyd based coating and protection systems are regularly equipped with metal compounds. Here, transition metal compounds, e.g. Cobalt, lead, manganese and Vanadiumoctoate, as a dryer (desiccant) of the alkyd resin-containing binder system. In addition, transition metal compounds are also used as pigments, some of which have comparable destructive properties with the siccatives.

In addition to the dryers, there are a number of other constituents in the abovementioned solvent-based systems which lead to degradation of iodine-containing biocides to varying degrees. While the destabilizing effect of the commonly used solvents is still relatively weak, the other conventional components of a color formulation, such as process additives, plasticizers, color pigments, anti-settling agents, thixotropic agents, corrosion inhibitors, skin inhibitors and binders show more or less pronounced destabilizing effects. - -

In addition to the solvent-based systems described above, the use of iodine-containing biocides in certain water-based engineering materials (e.g., paints and preservatives such as wood preservatives and primers) is also problematic. Based e.g. the film formation and film hardening of a water-based paint on the oxidative crosslinking of water-soluble or emulsified alkyd resins, so also in these systems transition metal compounds are used as siccatives, which is accompanied by destruction of the contained iodine-containing biocides.

Methods are already known for preventing the degradation of halopropargyl compounds in transition metal-containing, solvent-based alkyd resin paints. For example, WO 98/22543 describes the addition of chelating reagents.

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

Methods are also already described for suppressing light-induced degradation of antifungal agents, such as iodopropargyl butylcarbamate, by addition of tetraalkylpiperidine compounds and / or UV absorbers (cf EP-A 0083308).

According to WO 2007/028527, iodine-containing biocides are stabilized with 2- (2-hydroxyphenyl) benzotriazoles.

The addition of epoxy compounds is said to reduce the discoloration of iodoalkyne compounds such as IPBC (see US-A 4,276,211 and US-A 4,297,258).

Furthermore, synergistic mixtures of epoxides with UV absorbers (compare WO 99/29176) and with benzylidene camphor derivatives (compare US Pat. No. 6,472,424), which likewise have a reduced yellow coloration.

In addition, the stabilization of iodine-containing biocides by azole compounds is described in WO 2007/101549.

However, the stabilizing effect of the abovementioned stabilizers is not always sufficient and has disadvantages in terms of performance. In particular, the drying times of the colors are significantly extended, which in many cases is not acceptable to the user. In addition, the inhibition of discoloration is not always sufficient. - -

Surprisingly, it has now been found that the use of specific heterocyclic 3-ring compounds, in particular aziridines on inorganic support materials, protects iodine-containing biocides, in particular in solvent- and water-based systems, from both chemical and light-induced degradation and thus does not impair the described disadvantages. stabilized iodinated compounds such as color changes and drug or loss of activity can be prevented. In addition, it has been found that with the use of such equipped carrier materials for stabilizing iodine-containing biocides in the abovementioned systems, there are no disadvantages associated with use, such as an extension of the drying time of a paint system.

Aziridine compounds are used for example in US2004 / 0077783 A1 constituent of polymerization initiators, which contain as further constituents organoborane compounds, support materials and optionally fillers. The latter are due to the production but as mixtures with the other components and not as with aziridine surface-modified support materials.

By employing adsorptively or chemically bound aziridines on an inorganic support material, the specific properties of liquid iodine-containing formulations, e.g. Solutions and dispersions, such as, for example, low concentration and thus unnecessary transport of solvent even further improved. In particular, this form has stability advantages over iodine-containing solutions, in particular during storage, preferably at elevated temperatures.

The invention therefore relates to an inorganic carrier material comprising at least one adsorptively or covalently bonded heterocyclic 3-ring compound.

The support material according to the invention is preferably solid at room temperature.

As the inorganic support materials to be used are preferably silicas such as precipitated silicas, such as silica gels, mesoporous silicates, xerogels, aerogels, fumed silicas, silicic acids modified with inorganic, organic or organometallic radicals, for example silicic acids modified with dichlorodialkylsilanes, kieselguhr, porosils, for example zeosils, clathrasils or dealuminated zeolites, aluminosilicates, zeolites, natural or synthetic tectosilicates, natural silicates such as, vermiculite, mica or pyrogenic metal oxides for example. TiÜ _2, including fumed metal mixed oxides. - -

Preference is given to pyrogenic silicic acids, in particular hydrophilic or hydrophobic, for example those which are commercially available under the name Aerosil from Evonik-Degussa, the product Aerosil 200 being particularly preferred.

It is also preferable that the inorganic carrier material does not contain organoborane in the case where the heterocyclic 3-ring compound is an aziridine.

Also preferred hydrophilic or hydrophobic precipitated silicas, in particular hydrophilic or hydrophobic, for example, under the name Sipernat ^® from Evonik-Degussa are commercially available. Here, the products Sipernat ^® 22S and Sipernat ^® 50S are particularly preferred.

The support materials according to the invention preferably have a particle size of 0.001 to 1000 .mu.m, in particular from 0.005 to 500 microns.

The support materials according to the invention are preferably distinguished by the ability to absorb liquids, measured by their DBP absorption capacity (DBP = dibutyl phthalate, see DIN 53601 or ISO 4656) in grams per 100 g of support material. The DBP absorption capacity of the support materials according to the invention is preferably 0.1 to 800 g / 100 g, more preferably 1 to 500 g / 100 g of support material.

The support materials according to the invention preferably have a specific surface [m ² / g], determined on the basis of the method of Brunauer, Emmett and Teller (BET surface, J. Am. Chem. Soc., 60, 309 (1938)) according to ISO 5794/1 (Annex D) from 1 to 1200 m ² / g, particularly preferably from 50 to 900 m ² / g.

In the production methods of the carrier materials according to the invention which are in particular adsorber materials described below, the coating or impregnation of the carrier material with the heterocyclic 3-ring compound was carried out adsorptively or by forming covalent bonds. The proof that a heterocyclic 3-ring compound is adsorbed or bound to the inorganic support material in accordance with the invention is generally determined by the analytical determination of the heterocyclic 3-ring groups, for example the aziridine groups, by suitable methods, for example solid-state NMR (MAS - NMR). If a heterocyclic 3-ring compound can e.g. in the MAS-NMR determination of the inorganic support material, it is an inventive inorganic support material according to the present invention.

Preferred heterocyclic 3-ring compounds are those having a 3-ring function which have, as the heteroatom in the 3-membered ring, O, NR, S or Se, where R is hydrogen or a organic residue stands. Preferred heterocyclic 3-ring compounds are epoxides or azirindines, in particular aziridines.

Suitable aziridines are those which contain one or more aziridine groups.

For example, aziridine compounds of the formula (I) are preferred.

in which

R ^{1 is} hydrogen, alkyl or cycloalkyl, which are each unsubstituted or substituted and / or mono- or polyethylenically unsaturated, in each case substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl, arylcarbonyl, alkanoyl, carbamoyl or oxomethylene,

R ² , R ³ , R ⁴ and R ⁵ independently of one another have the same meaning as R ¹ and additionally independently halogen, hydroxyl, carboxyl, alkylsulfonyl, arylsulfonyl, nitrile, isonitrile or the radicals

R ² and R ⁴ or R ³ and R ⁵ 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.

Examples of suitable monofunctional aziridines of the formula (I) are those in which R ² and R ⁴ or R ³ and R ⁵ 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.

In particular, these are those of the formula (II)

- - wherein the carbocyclic ring is unsubstituted or substituted by one or more substituents selected from the group halogen, hydroxyl, oxo, carboxyl, alkylsulfonyl, arylsulfonyl, nitrile, isonitrile, alkyl or cycloalkyl, each unsubstituted or substituted and / or singly or multiply ethylenically unsaturated, substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl or alkanoyl, and

n is a number from 0 to 6, preferably 0 to 1.

Also preferred are those monofunctional aziridine compounds of formula (I) wherein R ^{1 is} a radical of formula

or

stands,

wherein

R ^{24 is} -H or alkyl, preferably -H, -CH ₃ , -C ₂ H ₅ , particularly preferably -CH ₃ , -C ₂ H ₅ ,

g is a number from 1 to 4, preferably 1 to 3, particularly preferably 1 to 2,

h is a number from 1 to 11, preferably 1 to 5 and particularly preferably 1 to 3

and the remaining radicals having the above meaning.

In particular, those compounds of the formula (I) which correspond to the compound of the formula (III) or (IV) are preferred.

in which

R is -H or alkyl, preferably -H or -CH ₃ , particularly preferably -CH ₃ ,

R ^ 25 is -H or alkyl, preferably -H or -CH ₃ , more preferably -CH ₃ and the remaining radicals have the above significance.

Particularly preferred are aziridines which have two or more aziridine functions. For example, compounds of formula (V) are mentioned.

wherein

A is an m-valent aliphatic, cycloaliphatic or aromatic radical which is optionally substituted,

m is a number from 2 to 5, in particular 2 to 3, and

Each R ³⁰ is independently hydrogen or C 1 -C ₄ -alkyl, in particular CH ₃ or CH ₂ CH ₃ .

When m = 2, A is preferably C ₂ -C 10 -alkylene,

especially for

- (CH ₂ ) ₆ ) -, -C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₂ CH ₂ - or

- C (CH ₃ ) ₂ CH ₂ CH (CH ₃ ) CH ₂ - or

for a phenylene, in particular for the bivalent radical of the formula

At m = 3, A is preferably the trivalent radical of the formula

Preference is given to those compounds of the formula (V) which correspond to the formulas (Va) - (Vd).

Also preferred as polyfunctional aziridine Michael addition products of optionally substituted ethyleneimine to esters of polyhydric alcohols with α, ß- - - unsaturated carboxylic acids and the addition products of optionally substituted ethyleneimine to polyisocyanates.

Suitable alcohol components are, for example, trimethylolpropane, neopentyl glycol, glycerol, pentaerythritol, 4,4'-isopropylidenediphenol, 4,4'-methylenediphenol and polyvinyl alcohols. As α, ß- unsaturated carboxylic acids are, for example, acrylic and methacrylic acid, crotonic acid and cinnamic acid in question. Particularly preferred is acrylic acid. The corresponding polyhydric alcohols of the .alpha.,. Beta.-unsaturated carboxylic acid esters may optionally be alcohols which, in their OH functions, are partly or completely extended with alkylene oxides. These may be, for example, the above-mentioned alcohols which have been singly or multiply extended with alkylene oxides. In this regard, reference is also made to US 4,605,698, the disclosure of which is incorporated by reference into the present invention. Particularly suitable alkylene oxides according to the invention are ethylene oxide and propylene oxide.

Examples of suitable for reacting with optionally substituted ethyleneimine polyisocyanates are those mentioned on page 4, lines 33-35 of WO2004 / 050617.

Examples of aziridines suitable according to the invention are those on S. 3, lines 29-34 of WO2004 / 050617 mentioned.

Also preferred are such aziridines as described for example in US 3,225,013 (Fram), US 4,490,505 (Pendergrass) and US 5,534,391 (Wang).

Also preferred are those aziridines of the formula (I) which have at least three aziridine groups, for example trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate] , Trimethylolpropane tris [2-aziridinyl butyrate], tris (1-aziridinyl) phosphine oxide, tris (2-methyl-1-aziridinyl) phosphine oxide, pentaerythritol tris [3- (1-aziridinyl) propionate] and pentaerythritol tetrakis [ 3 - (1-aziridinyl) propionate].

Of these, trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate], trimethylolpropane tris [2-aziridinyl butyrate], pentaerythritol tris- [3 - (1-aziridinyl) propionate] and pentaerythritol tetrakis [3 - (1-aziridinyl) propionate].

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

Also preferred are polyfunctional aziridines of the formula (VI) - -

wherein

B is the residue of an aliphatic polyol having at least x OH functions, where x

OH functions are substituted by the remainder of the above parenthesis,

f is a number from 0 to 6, in particular from 1 to 3,

x is a number greater than or equal to 2, in particular represents 2 to 500,000 and

R ³⁸ , R ³⁹ , R ⁴⁰ and R ^{41 have} the identical meaning as the radicals R ² - R ⁵ in the formula (I).

Particular preference is given to those aziridines of the formula (VI) in which x is 3 or 4 and B is a 3- or 4-membered OH-functional polyol.

Particular preference is given to aziridines of the formula (VI) which correspond to the formula (VIa) - (VIc)

38

R

- -

R ³⁸

wherein

R ^{38 is} hydrogen or CH ₃ .

The aziridine compound of the formula (VIa), also known as DSM crosslinker CX-100, with R ³⁸ = methyl and also the product "Corial Hardener AN" from BASF, which is the aziridine of the formula (VIa) where R ^{38 is} hydrogen, is particularly preferred contains.

Epoxides are all compounds which contain one or more oxirane rings.

Preference is given, for example, to epoxides of the general formula (VII):

wherein

R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ independently of one another are hydrogen, alkyl or cycloalkyl, which are each unsubstituted or substituted and / or mono- or polyethylenically unsaturated, in each case substituted or unsubstituted fullerenyl, aryl, alkoxy, aryloxy, alkanoyl, alkoxycarbonyl , Arylcarbonyl, alkanoyl, carbamoyl or oxomethylene, halogen, hydroxyl, carboxyl, alkylsulfonyl, arylsulfonyl, nitrile, isonitrile

or the radicals

R ⁴³ and R ⁴⁴ or R ⁴⁵ and R ⁴⁶ 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.

Preferred "alkyl" is a linear or branched alkyl radical having 1 to 20, preferably 1 to 12 carbon atoms Examples of alkyl radicals according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Pentyl, iso-amyl, hexyl, octyl, etc. The abovementioned alkyl radicals may be preferably substituted by the following radicals; alkoxy, - - preferably Ci-C ₂ alkoxy, nitro, monoalkylamino, preferably Dialkylamino, preferably di [Ci-Ci ₂ -] alkylamino, cyano, halo, haloalkyl, preferably trifluoromethyl, alkanoyl, aminocarbonyl, monoalkylaminocarbonyl, dialkylaminocarbonyl, alkylamido, preferably Ci-Ci ₂ -Alkylamido, alkoxycarbonyl, preferably C ₁ -C ₁₂ - alkoxycarbonyl , Alkylcarbonyloxy, preferably Ci-Ci ₂ -alkylcarbonyloxy, aryl, preferably phenyl or by halogen, Ci-Ci ₂ alkyl or Ci-Ci _2- Alkoxy substituted aryl, heterocyclic 3-ring groups, in particular Aziridin or Epxoygruppen, or substituents, like the above, which contain these groups.

Preferably, the radicals R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ^{46 are} each independently hydrogen or aralkyl, aryloxyalkyl, alkoxyalkyl such as epoxy-di-alkoxyalkyl, for example, 2,3-epoxy-l-propoxyethoxymethyl, 2,3-epoxy-1 Butoxyethoxyethyl or 3,4-epoxy-l-butoxyethoxyethyl, for the rest of the formula

or

in which

Z is a straight or branched Ci-Cio alkylene, preferably propylene, butylene, pentylene, hexylene, or heptylenes, halogenated straight or branched C ₁ -C ₁ 0-alkylene such as, 2,2-Dichloromethylpropylen is

and

Q is Ci-C / pAlkylen, Carbonylarylcarboxy such as. Carbonylphenylcarboxy.

Preferred epoxides include the compounds in which

R ^{46 is} hydrogen, alkoxy, alkyl or 2,3-epoxy-1-propoxyethoxymethyl,

R ^{43 is} hydrogen or alkyl and

R ⁴⁴ and R ^{45 is} hydrogen, and additionally R ⁴³ and R ⁴⁴ or R ⁴⁵ and R ⁴⁶ 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 ,

Particularly preferred epoxides include glycidyl ethers. These compounds are characterized in that they contain one or more 2,3-epoxypropanoxy groups and can be represented by the general formula (VIII):

in which

R ^{47 has} the same meaning as R ⁴³ , R ⁴⁴ , R ⁴⁵ or R ⁴⁶ .

Many of these glycidyl ethers are commercially available. In principle, all glycidyl ethers are suitable, in particular those obtained by reaction of 1-chloro-2,3-epoxypropane with alcohols, or by reaction of glycidyl alcohol with suitable electrophiles, e.g. Halides, can be produced.

Also particularly preferred are epoxy-containing products obtainable by reaction of epichlorohydrin (1-chloro-2,3-epoxypropane) with polyhydric alcohols, in particular polyhydric phenols such as BSW. Bisphenol A, including oligomeric and polymeric reaction products. Particularly preferred are those having an average molecular weight of less than 2000 g / mol, in particular less than 1000 g / mol.

The preferred epoxides also include the following compounds:

- -

in which

R ^{48 is} C 1 -C ₂₀ -alkyl

R, 49 H, alkyl, substituted alkyl,

R ^5υ halogen,

R ^{51 is} C 1 -C ₂₀ -alkyl and

R is C 1 -C ₂₀ -alkyl, preferably methyl or ethyl. - 5 -

The inorganic support material according to the invention may additionally contain other compounds, for example solvents such as esters of mono- or polybasic carboxylic acids (eg mixtures containing diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate), preferably VOC-free or low-VOC solvents, VOC (volatile organic compounds ) volatile organic compounds having a boiling point of less than 250 ⁰ C is understood, emulsifiers such as castor oil ethoxylates, dispersants such as polyvinyl alcohols, Chelatisierungsreagentien such as in WO 98/22543 mentioned, one or more stabilizers from the series of antioxidants, radical scavenger , UV stabilizers and / or UV absorbers (examples see below). In many cases, synergistic effects are observed here. The loading of the inorganic carrier material can also be carried out for these compounds, preferably analogously to the processes a) -d) (see above).

The support materials according to the invention preferably contain

0.001 to 80 wt .-%, preferably 0.005 to 60 wt .-%, in particular 0.01 to 50 wt .-% of at least one heterocyclic 3-ring compound, in particular an aziridine compound and

20 - 99.999 wt .-%, preferably 40 - 99.995 wt .-%, particularly preferably 50 - 99.99 wt .-% of at least one inorganic carrier material.

As preferred further constituents, the inorganic support material according to the invention contains from 0.0001 to 8% by weight, preferably from 0.0005 to 6% by weight, in particular from 0.001 to 5% by weight, of emulsifiers. In addition, the inorganic support material according to the invention may contain from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, in particular from 1 to 6% by weight, of a dispersing assistant.

The invention further relates to the use of azirdines for the preparation of aziridine-containing inorganic support materials.

The invention further relates to a process for the preparation of the inorganic support materials according to the invention, which is characterized in that

a) at least one preferably a liquid heterocyclic 3-ring compound, in particular aziridines, or solutions of at least one preferably liquid heterocyclic 3-ring compound in an organic solvent, preferably in a VOC-free or low-VOC solvent, with an inorganic solvent Carrier mixes, or

b) dissolves at least one heterocyclic 3-ring compound, in particular aziridines in an organic solvent and with an inorganic support material optionally with addition - - Mixed suitable dispersing aid and isolated with at least one heterocyclic 3-ring compound-loaded inorganic support material, or

c) an emulsion containing at least one heterocyclic 3-ring compound, in particular aziridines, water, at least one organic solvent and optionally emulsifiers mixed with an inorganic support material and the with at least one heterocyclic 3-ring

Compound loaded inorganic carrier material isolated, or

d) an aqueous dispersion of an inorganic carrier material containing optionally dispersing aid with an emulsion comprising at least one heterocyclic 3-ring compound, in particular aziridines, water, at least one organic solvent and optionally emulsifiers and mixed with at least one heterocyclic 3-ring - compound loaded inorganic carrier material isolated,

wherein the isolation of the loaded carrier material, obtained after steps b) to d) is preferably carried out by complete or partial removal of the solvent, in particular by

- Filtration and optionally subsequent drying or

- Evaporation of the solvent, eg. By fluidized bed drying, spray drying or rotary evaporation, if appropriate under reduced pressure.

Spray drying is a gentle process where the temperatures occurring only act swiftly on the slurry and also not directly burden the scale Inlettemperaturen of about 160 ⁰ C due to the heat of evaporation of water the product.

Preferably, according to the inventive method, preferably when the drying is a spray drying, available inorganic support materials, as described above.

In the process alternative a) is preferably at room temperature (22 ⁰ C) liquid heterocyclic 3-ring compounds, in particular pasty masses or dry powders are formed.

In process alternative b), nonionic and anionic emulsifiers are suitable as preferred dispersants.

Particular preference is given to the process according to the invention, in particular according to the procedure b) available carrier materials containing a dispersant, preferably Anionic emulsifiers such as, for example, alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, in particular the alkali metal and alkaline earth metal salts, for example sodium, potassium, magnesium , Calcium, and ammonium and triethanolamine salts or ionic emulsifiers such as alkylaryl polyglycol ethers such as Polyoxyethylenoctylphenolether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol or Tributylphenylpolyglycolether, Tris-sterylphenyletherethoxylate, Alkylarylpolyetheralkohole, Isotridecylalkohol, polyoxyethylene fatty alcohol ether, Polyoxyethylene fatty acid esters such as ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene, Laurylalkoholpolyglycoletheracetat, sorbitol esters or block copolymers based on ethylene and / or propylene oxide.

In the procedure c) are preferably used as the preferred organic solvent for the oil-water emulsion, the above.

Preference is given to the preparation according to process alternative d). In particular, a dispersion of the inorganic carrier material in water is first produced using preferably low shear energy, for example by using a vane blade stirrer.

The preparation of the O / W emulsion of the heterocyclic 3-ring compound, in particular an aziridine, dissolved in a suitable, inert organic solvent is optionally carried out with the addition of suitable emulsifiers and preferably using high shear forces (for example Ultraturrax).

The addition of the O / W emulsion of the heterocyclic 3-ring compound, especially the aziridine, to the dispersion of the inorganic carrier is preferably carried out under a low shear force (e.g., blade agitator). The loading of the inorganic support with the heterocyclic 3-ring compound, in particular with an aziridine, is preferably carried out by stirring the resulting low shear shear suspoemulsion (e.g., blade agitator) for at least 12 hours. The subsequent isolation of the heterocyclic 3-ring compound, in particular aziridines and optionally solvent-loaded inorganic support material is preferably carried out by fluidized bed drying or spray drying. If appropriate, the inorganic support material according to the invention thus obtained may be further deaggregated by using a screen sieve mill and then converted into a homogeneous solid mixture using a mixer, for example a Lödige mixer.

Further additives can be added in all procedures in solid, liquid or in dissolved, dispersed or emulsified form. - -

The novel process alternatives are preferably carried out at a temperature of 0 to 35 ⁰ C, in particular at room temperature (22 ° C).

The invention further relates to the use of the support materials according to the invention for the stabilization of iodine-containing compounds, in particular biocides.

As the iodine-containing compounds are preferably iodoalkynyl compounds or compounds in question, in which one or more iodine atoms are bonded to double bonds or in which one or more iodine atoms are bonded to single bonded carbon atoms.

The iodine-containing compounds, in particular biocides, are, for example, diiodomethyl-p-tolylsulfone, diiodomethyl-p-chlorophenylsulfone, 3-bromo-2,3-diiodo-2-propenyl alcohol, 2,3,3-triiodoallyl alcohol, 4-chloro 2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone (CAS-RN: 120955-77-3) iodoffen, 3-iodo 2-propynyl-2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenylformal (IPCF), N-iodopropargyloxycarbonyl-α 1 -in, N-iodopropargyloxycarbonyl-alanine ethyl ester, 3- (3-iodopropargyl ) -benzoxazol-2-one, 3- (3-

Iodopropargyl) -6-chlorobenzoxazol-2-one, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-iodo-2-propynyl-propyl carbamate, 3-iodo-2-propynyl Butyl carbamate (IPBC), 3-iodo-2-propynyl-m-chlorophenyl c arb amate, 3-iodo-2-propynyl-phenyl-c arb amate, di- (3-iodo-2-propynyl) hexyl dicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyl-oxyethanol-phenyl-carbamate, 3-iodo-2-propynyl-thioxo-thioethylcarbamate, 3-iodo-2-propynyl-carbamic acid ester ( IPC), 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate or 3-iodo-2-propynylcyclohexylcarbamate.

The iodine-containing compounds, in particular biocides, are preferably 3-iodo-2-propynyl-2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenyl phosphate (IP CF), N-iodopropargyloxycarbonyl-alanine, N-iodopropargyloxycarbonyl-alanine ethyl ester, 3- (3-iodopropargyl) -benzoxazol-2-one, 3- (3-iodopropargyl) -6-chlorobenzoxazol-2-one, 3-iodo-2- propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-iodo-2-propynyl-propyl carbamate, 3-iodo-2-propynyl-butyl-carbamate (IPBC), 3-iodo-2-propynyl-m -chlorophenyl carbamate, 3-iodo-2-propynylphenyl carbamate, di (3-iodo-2-propynyl) hexyl dicarboxylate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo 2-propynyl-oxyethanol-phenyl-c arb on at, 3-iodo-2-propynyl-thioxo-thi-ethylcarbamate, 3-iodo-2-propynyl-carbamic acid ester (IPC), 3-bromo-2,3-diiodo 2-propenylethylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate or 3-iodo-2-propynylcyclohexylcarbamate.

The iodine-containing compounds, in particular biocides, are more preferably 3-iodo-2-propynyl-propyl-carbamate, 3-iodo-2-propynyl-butyl-carbamate (IPBC), 3-iodo-2-propynyl m-chlorophenyl c arb amate, 3-iodo-2-propynylphenyl c arb amate, di- (3-iodo-2-propynyl) hexyl dicarbamate, - -

3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyl-oxyethanol-phenyl-carbamate, 3-iodo-2-propynyl-thioxo-thioethylcarbamate, 3-iodo-2-propynyl-carbamic acid ester (IPC), 3 Bromo-2,3-diiodo-2-propenylethylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate or 3-iodo-2-propynylcyclohexylcarbamate.

In addition, the particularly preferred iodine-containing compounds, in particular biocides, are N-alkyl-iodotetrazoles, N-aryl-iodo-terazoles and N-aralkyl-iodo-terazoles, as described, for example, in (EP 1773125).

The iodine-containing compounds, in particular biocides, can be used individually or in mixtures together with a plurality of iodine-containing compounds, in particular biocides. Particularly preferred is IPBC.

The carrier materials according to the invention to be used according to the invention are preferably suitable for stabilizing iodine-containing compounds, in particular biocides in binder formulations, for example in alkyd resin-based systems such as paints containing transition metal dryers, especially in the presence of transition metal dryers. Preferred binder formulations and transition metal driers are described in more detail below.

In the context of this application, stabilization is preferably understood to mean the stabilization of iodine-containing compounds both from chemical and light-induced degradation, in particular from chemical degradation.

In particular, the support materials according to the invention can be used to suppress or at least slow down the chemical degradation of compounds containing iodine, in particular biocides in active ingredient formulations, in particular paints such as paints, lacquers, primers, impregnations, glazes and other technical materials. The support materials according to the invention which can be used according to the invention for stabilizing iodine-containing compounds, in particular biocides, have a good stabilizing action, especially in alkyd resin-based systems such as paints containing transition metal dryers.

The stabilization is preferably realized by the fact that the iodine-containing compounds, in particular biocides and the support materials according to the invention are present together in a mixture or in a medium.

Preferably, a composition is used, containing

a) at least one inorganic carrier material according to the invention and - - b) at least one iodine-containing biocide.

The composition is also an object of the present invention.

With regard to the preferred iodine-containing compounds, in particular biocides and the preferred support materials according to the invention, the abovementioned preferred forms also apply to the preferred compositions according to the invention.

Particularly preferred compositions contain

a) at least one inorganic support material containing adsorbed or covalently bound aziridine of formula (VI) and

b) IPBC.

The compositions according to the invention generally contain 0.01-70% by weight, preferably 0.05-60% by weight, more preferably 0.1-50% by weight of at least one iodine-containing biocide and at least one support material according to the invention, such that the content of all heterocyclic 3-ring compounds present in the composition according to the invention, in particular aziridine compounds, is 0.001-50% by weight, preferably 0.005-40% by weight, particularly preferably 0.01-30% by weight.

The composition according to the invention preferably contains the iodine-containing biocide and an aziridine compound in the total amount of from 40 to 99% by weight.

In the use according to the invention, preferably the carrier material according to the invention is used so that the content of all heterocyclic 3-ring compounds present in the composition according to the invention, in particular aziridines, is generally 1 to 280% by weight, preferably 2 to 225% by weight, in particular 5 to 110 wt .-%, based on the iodine-containing biocide.

It is preferred to use, based on the iodine-containing compound, 0.05 to 5, preferably 0.1 to 4, in particular 0.25 to 2 equivalents of the heterocyclic 3-ring functions present in the inventive carrier material, in particular aziridine functions.

The erfmdungsgemäße composition may be in various forms, for example. As a solvent-based dispersion, water-based dispersion, solid mixture, etc. are present. - -

The composition according to the invention is particularly preferably present as a solid mixture, for example as a powder, granules, in particular with an average particle size of 50 to 2000 μm, or as a compact, such as, for example, compacted powder such as pellets, tablets, etc.

Likewise particularly preferably, the composition according to the invention is in the form of a solvent-based dispersion, it being possible to add, for example, alkyd resins, modified alkyd resins, thixotropic resins, etc., and other additives, such as skin inhibitors (antioxidants), pigments, crystallization stabilizers, etc., to adjust the rheological properties of the dispersion.

Furthermore, the composition according to the invention can be used as further ingredients adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids and mineral and vegetable oils. In addition, it may contain 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, and also for heterocyclic 3-ring compounds, in particular aziridine compounds Stabilizers, for example tetramethylethylenediamine (TMEDA), triethylenediamine and the known from WO2004 / 050617 1,4-diazabicyclo [2.2.2] octane (DABCO) included.

The invention further relates to a process for the preparation of the composition according to the invention.

The composition according to the invention can be prepared, for example, by mixing the individual components, ie the support material according to the invention and the iodine-containing compound optionally with extenders and optionally using further additives such as flow improvers, additives for increasing the electrical conductivity, additives for adjusting the dusting behavior, etc. , For the preparation of the compositions according to the invention in the form of solid mixtures, suitable solid mixers such as Lödige mixers, paddle mixers, tumble mixers, drum mixers with disruptive bodies, etc. are used here, optionally after pretreatment of the components to be mixed with, for example, screen mills such as the Bauermeister mill , The transfer of thus prepared solid mixtures in other embodiments, such as. Granules, compacts such as pillows, tablets, etc. is using fluidized bed granulation, use mechanical compaction, possibly with the addition of other additives such as. Binder, possible. - -

A further embodiment of the composition according to the invention is a solvent-based dispersion comprising an iodine-containing compound, in particular IPBC, and at least one excipient according to the invention, in particular one in which the heterocyclic-3-ring compound is at least one aziridine compound. Here, the iodine-containing compound, in particular IPBC and erfmdungsgemäße carrier material are preferably under high shear in an inert organic solvent as a continuous phase (eg isoparaffins such as Isopar "L (isoparaffin from Exxon) or so-called." White spirits "such as" Shellsol " ground D60) optionally with the addition of processing aids and stabilizers, such as, rheological additives (thixotropic resins such as. WORLÉETHIX S6358, a thixotropic alkyd resin from. Worlee) and optionally anti-skinning agents such as. Antiskin ^® 444 (Fa. Borchers) and disp added (eg bead mill).

The effectiveness and spectrum of activity of the compositions according to the invention or of the iodine-containing compound used can be increased if, if appropriate, further antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients are added or used to increase the spectrum of action or to achieve particular effects become. 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) -cycloheptane o 1, 2- (1-tert-butyl ) -l- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) -propan-2-ol, tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol, trivolizol, triticonazole, uniconazole, and the like 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, pyroxyfor, triamirole;

Succinate dehydrogenase inhibitors such as:

Benodanil, Carboxim, Carboximsulfoxide, Cyclafluramid, Fenfuram, Flutanil, Furcarbanil, Furmecyclox, Mebenil, Mepronil, Methfuroxam, Metsulfovax, Nicobifene, Pyrocarbolide, Oxycarboxine, Shirlan, Seedvax;

Naphthalene derivatives such as:

Terbinafine, naftifm, butenafm, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-yne);

Sulphenamides like:

Dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Capto fol;

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:

Benzofblthiophen-SjS-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-chloro-ethyl) -3 , 5,7-triaza-1-azoniaad amide chloride, 1- [l, 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- (hydroxymethyl) glycinate, N Methylolchloroacetamide, oxazolidines, paraformaldehyde, tauroline, tetrahydro-1,3-oxazine, N- (2-hydroxypropyl) -amine-methanol, tetramethylol-acetylenediurea (TMAD);

Isothiazolinones such as:

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octyrisothiazolin-3-one, 5-chloro-N-octylisothiazolinone, N-octylisothiazolin-3 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 tris (albesilate);

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, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, octyl p-hydroxybenzoate, o-phenylphenol, m-phenylphenol o 1, p-phenylphenol, 4- (2-tert-butyl-4-methyl-phenoxy) -phenol, 4- (2-tert. 2-isopropyl-4-methyl-phenoxy) phenol, 4- (2,4-dimethyl-phenoxy) -phenol and their alkali and alkaline earth metal salts; - 5 -

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, 1,3-dibromo-4,4,5,5-tetrametyl-2-imidazoledione, dichloramine T, 3,4-dichloro (3H) -l, 2 dithiol-3-one, 2,2-dibromo-3-nitrile-propionamide, 1, 2-dibromo-2,4-dicyanobutane, halanes, halazone, mucochloric acid, phenyl (2-chloro-cyan-vinyl) 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 (CA S 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, CU2O, 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) acethydroximic acid chloride,

Tris-N- (cyclohexyldiazeniumdioxy) -aluminum, N- (cyclo-hexyldiazeniumdioxy) -tributyltin or

K-salts, bis-N- (cyclohexyldiazenium-dioxy) -copper, iprovalicarb, fenhexamide, spiroxamine,

Carpropamid, 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, benzofb-thiophene-SjS-dioxide-carboxylic cyclohexylamide, fenpiclonil, 4- (2,2-difluoro -l, 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, benzisothiazole inon, N- (2-hydroxypropyl) -amino-methanol, benzylalcohol (hemi) -formal, N-methylolchloroacetonate, N- (2 -Hydroxypropyl) -amine-methanol, glutaraldehyde, omadine, Zn-omadine, dimethyldicarbonate, 2-bromo-2-nitro-1,3-propanediol, bethoxazine, o-phthalaldehyde, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, 1,3-bis (hydroxymethyl) -5,5-dimethylimidazolidine-2,4-dione (DMDMH), tetramethylol-acetylene-diharnsto ff (TMAD), Ethylene glycol hemiformal, p-hydroxybenzoic acid, carbendazim, chlorophene, 3-methyl-4-chlorophenol, o-phenylphenol. - 7 -

Furthermore, in addition to the above-mentioned fungicides and bactericides, also effective mixtures with other active ingredients are 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, cisethocarb, chlordane, chloroethoxyfos, chlorfenapyr, chlorfenvinphos, chlorofluorazuron, chlormephos, N- [(6-chloro-3-pyridinyl) -methyl] -N'-cyano -N-methyl-ethanimidamide, chloropicrine, chlorpyrifos A, chlorpyrifos M, cis-resmethrin, clocythrin, clothiazoben, cypophenothrin clofenetine, coumaphos, cyanophos, cycloprothrin, cyfluthrin, 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, disulfonyl,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethion, 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,

Halo fenocid, HCH (CA S RN: 58-89-9), heptenophos, hexaflumuron, hexythiazox, hydramethylnone, hydroprene, - -

Imidacloprid, Imiprothrin, Indoxycarb, Iprinomectin, Iprobenfos, Isazophos, Isoamidophos, Isofenphos, Isoprocarb, Isoprothiolane, 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, Benzthiazuron, Bifenox, Bispyribac, Bispyribac 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, flampropisopropyl-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, methyldymrone, 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, pyribenzoxime, pyributicarb, pyridate, paraquat, pebulate, pendimethalin, pentachlorophenol, pentoxazone, pentanochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, pro-diamines, 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.

The invention further relates to a binder formulation containing

at least one binder,

- At least one iodine-containing compound, in particular biocide and - at least one inventive carrier material.

The binder formulation preferably contains the components iodine-containing compound, in particular biocide and, according to the invention, carrier material in the form of the composition according to the invention. Preferred binders include oxidatively drying binders, - - Preferably alkyd resin-based binder or by coalescing agent filming binder, in particular latices in question.

Of the alkyd resin-based binders are preferably alkyd resins and modified alkyd resins in question.

The alkyd resins are generally polycondensation resins of polyols and polybasic carboxylic acids or their anhydrides and fats, oils or free natural and / or synthetic fatty acids. If appropriate, the alkyd resins may also be chemically modified with hydrophilic groups, in particular water-soluble groups, in order to be usable, for example, as an emulsifiable or water-soluble alkyd resin.

The polyols mentioned are preferably glycerol, pentaerythritol, trimethylolethane, trimethylolpropane and various diols, such as ethane / propanediol, diethylene glycol and 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 also synthetic saturated, unsaturated or polyunsaturated monocarboxylic acids or mixtures of these components ,

The alkyd resins may optionally be modified, for example, 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 from 500 to 100,000 g / mol, preferably from 1,000 to 50,000 g / mol, in particular from 1,500 to 20,000 g / mol (determined by laser light scattering, see, for example, "Static Light Scattering of Polystyrene Reference Materials : Round Robin Test ", U. Just, B. Werthmann International Journal of Polymer Analysis and Characterization, 1999 Vol.5, pages 195-207).

The binder formulations of the invention preferably contain 1 to 80 wt .-%, preferably 2 to 70 wt .-% and particularly preferably 3 to 60 wt .-% of alkyd resin. - -

The binder formulation according to the invention preferably contains an alkyd resin-based binder and, for oxidative drying, a transition metal dryer. In the context of this application, transition metal dryers are understood in particular to mean transition metal compounds which accelerate the drying and hardening of the alkyd resin-based binder.

Preference is given to the salts of transition metals of groups Vb, VIb, VIIb, VIII and Ib of the Periodic Table. In particular, it is the salts of cobalt, manganese, vanadium, nickel, copper and iron, more preferably cobalt, manganese, iron and vanadium. They do not necessarily have to be used alone, but can also be used in combination with non-transition metal salts, such as lead, calcium or zirconium.

The preferred transition metal salts are soluble in organic solvents, for example. White spirit, at 20 ⁰ C in an amount of more than 10 g / l. Preferably, it is the salts of carboxylic acids, which have a good compatibility with the alkyd resin binders and at the same time ensure sufficient solubility of the metal salt. 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 driers are cobalt octoate and cobalt naphthenate example Octasoligen -cobalt ^® 12 from Borchers.

The binder formulations according to the invention preferably contain the transition metal dryers in an amount of 0.001 to 1 wt .-%, preferably 0.005 to 0.5 wt .-% and most preferably 0.01 to 0.1 wt .-%, each based on binder.

The binder formulations in a preferred embodiment contain at least one polar organic solvent, preferably a polar aprotic solvent. As such, there are, for example, polar protic and dipropylene glycol monomethyl ethers (for example Dowanol DPM from Dow Chemical) and, preferably in combination, polar aprotic solvents such as dimethylformamide and dimethyl sulfoxide, and also e.g. etherified glycols, oligoglycols and polyglycols, etherified polyols and esterified polyols, esters of mono- and polybasic carboxylic acids, e.g. Adipic diisobutyl ester, diisobutyl maleate (e.g., Rhodiasolv DIB).

Particularly preferred is the binder formulation containing

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

0 to 50 wt .-%, preferably 0 to 45 wt .-%, particularly preferably 0 to 40 wt .-%. color pigments

From 0.01 to 5% by weight, preferably from 0.05 to 3% by weight, particularly preferably from 0.1 to 2% by weight, of iodine-containing compound, in particular biocide,

0.001 to 5% by weight, preferably 0.005 to 3% by weight, particularly preferably 0.01 to 2% by weight, of the heterocyclic 3-ring compound, in particular aziridine compounds,

From 2 to 97% by weight of solvent, in particular nonpolar or polar solvents, preferably up to 10% by weight, in particular from 0.01 to 7.5% by weight, based on the binder preparation of polar aprotic solvents, and

0.001 to 3 wt .-% of a transition metal dryer.

Particular preference is given to binder formulations according to the invention comprising at least one alkyd resin, at least one transition metal dryer, IPBC, at least one solvent and at least one support material according to the invention containing at least one adsorptively or covalently bonded aziridine compound.

The binder formulation may also contain fillers, skin preventatives, rheology additives such as anti-settling agents and thixotropic agents, other biocides such as fungicides, bactericides, antifoulants and algicides, solvents, process additives, plasticizers, UV and heat stabilizers, and corrosion inhibitors in conventional amounts.

In addition, further stabilizers may be added to the binder formulations, such as the chelating reagents mentioned in WO 98/22543 or other heterocyclic 3-ring compounds, in particular those having a heteroatom other than what was used in the loaded 3-membered ring compound on the inorganic support. In the case of aziridines, these are preferably the organic epoxides mentioned in WO 00/16628. In many cases, synergistic effects are observed here.

In addition, one or more stabilizers from the series of antioxidants, free-radical scavengers, UV stabilizers, chelators and UV absorbers can also be added in the inventive use, which have partially synergistic effects.

By way of example, other UV stabilizers may be mentioned:

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'-methylene-bis (6-tert-butyl-2-methylphenol), 1, 1 - Bis (5-tert-butyl) 4-hydroxy-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-methyl-phenol (= Wingstay L ), 2,4-bis (n-octylthio) -6- (3,5-di-tert-butyl-4-hydroxyphenylamino) -s-triazines, N- (4-hydroxyphenyl) octadecanamides, 2,4-di- tert-butylphenyl 3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, (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-dimethyl-ethyl) -6- [1 - [3 - (1, 1-dimethyl-ethyl) -5- (1 , 1-dimethylpropyl) -2-hydroxyphenyl] ethyl] -4- (l, 1-dimethylpropyl) phenyl ester, esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with a or polyhydric alcohols such as 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 mono- or polyhydric alcohols, such as, for example, with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, - 5 -

Thiodiethylenglycol, 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-morpholino-l, 3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -l, 6-hexanediyl [ (2, 2,6,6-tetramethyl-4-piperidmyl) imino]], poly [[6- (4-morpholinyl) -l, 3,5-triazine-2,4-diyl] [(1, 2,2,6 , 6-pentamethyl-4-piperidinyl) imino] -l, 6-hexanediyl [(1, 2,2,6,6-pentamethyl-4-piperidinyl) imino]] (9CI), 3-dodecyl-1- (2 , 2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethylpiperidin-4-yl) pyrrolidine-2,5- dione "4-octadecanoyloxy-2,2,6,6-tetramethylpiperidines, 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-Hexaacacyclopenta [def] fluorenene-4,8-dione, hexahydro-2,6-bis (2,2,6,6-tetramethyl-4-piperidinyl) - (CAS No. 109423-00-9), N , N'-bis (formyl) -N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-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-butane etetracarboxylates, 1,2,6,6-pentamethyl-4-piperidinyl tridecyl 1,2,3,4-butanetetracarboxylates, (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-oxo) 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) -), (propanamide, 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-l , 3,5-triazines, reaction products with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine) (CAS No. 136504-96-6), 1-ethylene-bis (3,3, 5,5-tetramethyl-2-piperazinone), (piperazinone, 1, r, 1 "- [l, 3,5-tri azine-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), l, l-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-hydroxy-2,2,6,6-tetramethylpiperidines, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6- tetramethylpiperidines, 1 - (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 1-ethyl

4-salicyloyloxy-2,2,6,6-tetramethylpiperidines, 4-methacryloyloxy-l, 2,2,6,6-pentamethylpiperidines, 1,2,2,6,6-pentamethylpiperidin-4-yl-β- (3 , 5-di-tert-butyl-4-hydroxyphenyl) -propionate, 1-benzyl-2,2,6,6-tetramethyl-4-piperidinylmaleinate, (di-2,2,6,6-tetramethyl-piperidin-4-yl) -adipate, (di-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (di-1, 2,3,3,6-tetramethyl-2,6-di-ethyl-piperidine-4- yl) sebacate, (di-1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, 1-propargyl-4-beta-cyanoethyloxy-2,2,6,6-tetramethylpiperidine, l Acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, (trimellitic acid tri (2,2,6,6-tetramethylpiperidin-4-yl) ester), 1-acryloyl-4-benzyloxy -2,2,6,6-tetramethylpiperidines, dibutyl malonic acid di (l, 2,2,6,6-pentamethylpiperidin-4-yl) ester, butyl (3,5-di-tert-butyl) butyl-4-hydroxybenzyl) -malonic acid di- (1,2,2,6,6-pentamethylpiperidin-4-yl) ester, dibenzyl malonic acid di- (1,2,2,6,6-pentamethylpiperidine -4-yl) ester, dibenzyl malonic acid di- (l, 2,3,6-tetramethyl-2,6-diethyl -piperidin-4-yl) esters, hexanes-1 ', 6'-bis-

(4-carbamoyloxy-in-butyl-2,2,6,6-tetramethylpiperidines), toluene-2 ', 4'-bis (4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine ), 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 (l, 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-tetramethylpiperidines, 4-benzylamino-2,2,6,6-tetramethylpiperidines, N, N'-bis (2,2,6,6-tetramethylpiperidine-4- yl) -N, N'-dibutyladipamide, N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dicyclohexyl- (2-hydroxypropylene), NN'-bis - (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylenediamine, 4- (bis-2-hydroxyethyl) -ami no-1, 2,2,6,6-pentamethylpiperidines, 4- (3-methyl-4-hydroxy-5-tert-butylbenzoicacidamido) -2,2,6,6-tetramethylpiperidines, - 7 -

4-Methacrylamino-1, 2,2,6,6-pentamethylpiperidines, 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane, 9-aza-8,8, 10, 1-O-tetramethyl-3-ethyl-1,5-dioxaspiro [5.51-undecane, 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro [4.5] decane, 9-aza- 3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1 -5-dioxaspiro [5.5] undecane, 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8, 10,10-tetramethyl-l, 5-dioxaspiro [5.5] undecane, 2,2,6,6-tetramethylpiperidme-4-spiro-2 '- (l', 3'-dioxane) 5'-spiro-5 "- (1", 3 "-dioxane) -2" -spiro4 "- (2" ', 2 "', 6" ', 6 "' - tetramethylpiperidine), 3-benzyl-l, 3,8-triaza -7,7,9,9-tetramethyl-spiro [4.5] decane-2,4-dione, 3-n-octyl-l, 3,8-triaza-7,7,9,9-tetramethyl-spiro [4.5 ] decane-2,4-diones, 3-allyl-l, 3,8-triazal-l, 7,7,9,9-pentamethyl-spiro [4.5] decane-2,4-diones, 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-1-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, I, 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 or bis (2,4-dicumylphenyl) pentaerythritol diphosphite,

Hydroxylamines like,

N, N-bis (2-carboxyethyl) hydroxylamine, N, N-bis (benzylthiomethyl) hydroxylamine, N, N-diethylhydroxylamine, etc.

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) or 4- (l -Methyl-1-phenylethyl) -N- [4- (1-methyl-1-phenylethyl) phenyl] anüine.

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,

(Methanone, [methylene bis (hydroxymethoxyphenylenes)] to [phenyl], (methadone, [1,6-hexanediylbis [oxy (2-hydroxy-4, 1-phenylene)]] to [phenyl], 2 Benzoyl-5-methoxyphenol, 2,4-dihydroxybenzenes, 2,2'-dihydroxy-4-methoxybenzophenones, 2-hydroxy-4-octyloxybenzophenones, 2-hydroxy-4-dodecyloxybenzophenones, 2- 2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 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 '- (1,4-phenylene) bis [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 or 3- (4-methylbenzylidene) bornan-2-one .

Chelators like,

Ethylenediaminetetraacetate (EDTA), ethylenediamine, acetylacetone, nitrilotriacetic acid, ethylene glycol bis (β-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-1, 10-phenanthrolines, 4,7-dimethyl-1, 10-phenanthrolines, 5,6-dimethyl-1, 10-phenanthrolines, 3,4,7,8-tetramethyl-1 , 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-methyl-quinaldine, 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-dihydroxyquinoxalines, 2-mercapto - - pyridine, 2-dimethylaminopyridine, 1, 2-bis (dimethylphosphino) ethane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane,

Polyaspartic acid or iminodisuccinate.

Iodine-containing compounds, in particular biocides, are broken down, especially in the presence of the dryers 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

Effect on iodine-containing compounds, in particular biocides. To name here are inorganic and organic pigments, fillers, anti-skinning agents, rheology additives such as

Anti-settling and thixotropic agents, other compounds, especially biocides such as fungicides, bactericides, antifouling agents and algicides, solvents, process additives, plasticizers, UV and

Heat stabilizers, corrosion inhibitors, etc. The support materials of the invention also show a strong stabilizing effect here.

The compositions according to the invention used in oxidatively drying binder preparations or the binder preparations according to the invention themselves show a marked reduction in the drying time or no lengthening of the drying time compared to the systems not equipped with IPBC compared to unstabilized iodine-containing systems, in particular IPBC-containing systems (so-called Blank formulations).

Thus, without the applicant's intention to be scientifically based on it, presumably a mechanism other than removal of metal ions, as described, for example, with polymers of aziridines for the removal of heavy metal ions from waste water in DE-A1-19927909. Removal of heavy metal ions would mitigate the effect of the siccatives used for this purpose and thus lengthen the drying time accordingly.

The novel binder formulations are preferably used as paints, in particular as paints, lacquers, primers, impregnations and glazes. Accordingly, the invention also relates to the use of the binder formulations according to the invention as paints.

The invention further relates to the use of the inventive composition for the protection of industrial materials against destruction or infestation by microorganisms.

The inventive compositions are suitable for the protection of industrial materials. Technical materials as used herein mean non-living materials prepared for use in the art. For example, it is - - technical materials include adhesives, glues, paper and cardboard, textiles, leather, wood, wood-based materials, paints and plastics, coolants and other materials that may be attacked or decomposed 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.

The invention further relates to technical materials containing at least one iodine-containing compound, in particular biocide and at least one inorganic support material according to the invention. - -

Examples:

In the following examples, accelerated stability tests are performed by storage at elevated temperature. The content of the IPBC was in all cases by HPLC.

Examples 1-5

Examples 1 to 5 describe the preparation of inorganic support materials according to the invention with adsorbed or covalently bonded aziridine compounds and compositions according to the invention comprising IPBC and such support materials.

Example 1 Inorganic Support Material with Aziridines I

The oil phase consisting of 9.0 g CX-100 crosslinker from DSM (trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate] and 2.5 g Rhodiasolv "DIB from Rhodia (mixture consisting of

Diisobutyl adipate, diisobutylglutarate, diisobutylsuccinate) was combined with a solution of the emulsifier of 0.575 g Tanemul "KS from Tanatex (castor oil ethoxylate with 30 eq. EO) in 25 g of water

Exposure of an Ultraturrax (24,000 rpm * ¹ ) emulsified for 10 minutes

Emulsion was added to a dispersion of 27.0 g Aerosil "200 from Evonik (fumed silica having a BET surface area of 200 m ² / g and a DBP absorption capacity of 300 g / 100 g)

300 g of water metered under a paddle blade and then stirred for 24 hours.

The Aerosil loaded with the aziridine and Rhodiasolv DIB was isolated from the resulting dispersion by spray drying (Büchi B-290 spray drier, pump power 45%, N ₂ flow 35 l-TnUi ¹ , Inlet 160 ⁰ C, outlet 73 ° C). 33 g of a very fine, colorless solid were obtained (84% of theory).

Example 2 inorganic carrier material with aziridines II

The oil phase consisting of 18.0 g CX-100 crosslinker from DSM (trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate] and 5.0 g Rhodiasolv "DIB from Rhodia (mixture consisting of Diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate) was treated with a solution of the emulsifier of 1.15 g Tanemul "KS from Tanatex (castor oil ethoxylate with 30 eq. EO) in 50 g water under the action of an Ultraturrax (24,000 rpm * ¹ ). emulsified for 10 minutes. the colorless emulsion was added to a dispersion of 54.0 g of Aerosil "200 from. Evonik (fumed silica) in 600 g of a solution of 24 g of the dispersing Mowiol ^® 3-85 (polyvinyl alcohol of the company. Kuraray) metered into 576 g of water under wing blade stirring, added 600 g of water and then stirred for 24 hours. - -

The Aerosil loaded with the aziridine and Rhodiasolv "DIB was isolated from the resulting dispersion by filtration, drying gave 75.4 g of a very fine, colorless solid (98% of theory),

Example 3 Solid IPBC Composition I According to the Invention

90.0 g of IPBC are homogenized with 128.4 g of the support material from Example 2 (containing 23.2% of aziridine, which means the weight ratio of IPBC to aziridine is 4: 1) with the addition of ceramic spheres (0 40 mm) to the drum mixer. It is a fine, colorless and homogeneous powder obtained (IPBC content 41%).

Example 4 Solid IPBC Composition II According to the Invention

90.0 g of IPBC are homogenized with 96.9 g of the aziridine formulation from Example 2 (containing 23.2% of aziridine, which means the weight ratio of IPBC to aziridine is 3: 1) with the addition of ceramic balls (0 40 mm) to the drum mixer. A fine, colorless and homogeneous powder is obtained (IPBC content 48%).

Example 5 Solid IPBC Composition III According to the Invention

90.0 g of IPBC are homogenized with 128.4 g of the aziridine formulation from Example 1 (containing 23.03% of aziridine, the weight ratio of IPBC to azirides being 4: 1) with the addition of ceramic balls (0 40 mm) to the drum mixer. It is a fine, colorless and homogeneous powder obtained (IPBC content 41%).

Example 6 IPBC Additive IV According to the Invention as Solvent-Based Dispersion

To 75.0 g of the rheological additive WORLÉETHIX ^® S6358 (a thixotropic alkyd resin from. Worlee) are Dissolverrührung (3700 Umin ^"1) 8.0 g of anti-skinning agent Antiskin ^® 444 (Fa. Borchers), 80 g IPBC, 1 13, 1 g of the support material according to the invention from Example 2 (containing 23.2% aziridine) and 225.9 g of Isopar "L (isoparaffin from Exxon) are metered. After completion of the addition, stirring is continued for a further 40 minutes on the dissolver and the resulting predispersion is finely ground using a bead mill.

Example 7 Use of Inventive Support Materials in Binder Formulations

The IPBC compositions of Examples 3 and 4, respectively, are incorporated in a typical alkyd-based paint system (Alkydlasur A) in the presence of a transition metal drier (Co) and a metal oxide pigment (iron oxide). To equip the paint system, the above Each of Examples 3 or 4 mentioned above and an IPBC concentrate containing IPBC and an aziridine in the ratio 2: 1 (see Table 1) without inorganic carrier material are used.

Mixture consisting of diisobutyl adipate, diisobutyl glutarate, diisobutylsuccinate, Fa. Rhodia.

"Trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate]

The formulation of the alkyd glaze A used is shown in Table 2.

To determine the stabilization, an accelerated aging test is carried out. For this purpose, the equipped color system is filled in tight-fitting 200ml glass bottles, leaving only a minimal residual amount of air in the container, and stored at 40 ⁰ C. The results are shown in Table 3.

- -

) corresponds to 0.7 wt .-% IPBC, based on the glaze.

It is clear from Table 3 that the inorganic support materials coated with a 3-ring compound have a significantly higher stability compared to the unstabilized sample A-III with regard to the stabilization of IPBC (see glazes AI and All). Even compared to the aziridine-stabilized IPBC sample without inorganic support material (glaze A-IV), there is still a clear improvement, although the glaze A-IV has a larger aziridine / IPBC ratio (1/2 vs. 1/3 or 1/4). - 5 -

) unstabilized sample) aziridine stab. IPBC without anorg. Support Material Example 8 Use of Support Materials According to the Invention in Binder Formulations

The IPBC composition of Examples 3, 4 and 5 are incorporated in a commercial wood thick-layer varnish "Alkydlasur B" (containing alkyd resin, white spirit, iron oxide pigment, dryer, butanone oxime, UV absorber and additives) to equip the paint system with each 0 , 7% IPBC, based on the glaze, the compositions of Examples 3, 4, 5 and unstabilized IPBC are used in each case (see Table 4):

- -

corresponds in each case to 0.7% by weight of IPBC based on glaze

The to be examined, each equipped with 0.7% IPBC thick-film glazes (Alkydlasur B-I to Alkydlasur B-IV) were prepared by mixing the weight percentages of Alkydlasur B shown in Table 4 and said IPBC-containing compositions.

To determine the stabilization, an accelerated aging test is carried out. For this purpose, the equipped color system is filled into tight-fitting 200 ml glass bottles, leaving only a minimal residual amount of air in the container, and stored at 40 ⁰ C. The results can be found in Table 5, according to which only the inventively equipped with the Alkydlasuren BI to B-III after 4 weeks storage at 40 ⁰ C show no significant degradation of IPBC. Even after 8 weeks of storage at 40 ⁰ C a good stability of IPBC is noted for Alkydlasur I and II.

- 7-

unstabilized sample

Claims

- Patent claims

1. Inorganic carrier material containing at least one adsorptively or covalently bonded heterocyclic 3-ring compound.

2. Inorganic support material according to claim 1, characterized in that the heterocyclic 3-ring compound is an epoxide or an aziridine, in particular an azirine.

3. Inorganic support material according to claim 1, characterized in that the inorganic support material is silica, in particular pyrogenic silicas, kieselguhr, porosils, clathrasils, dealuminated zeolites, aluminosilicates, zeolites, natural or synthetic tectosilicates, natural silicates, mica or pyrogenic metal oxides.

4. Inorganic support material according to claim 1, characterized in that the heterocyclic 3-ring compound is an azirindine of the formula I.

R ¹

in which

R ^{1 is} hydrogen, alkyl or cycloalkyl, which are each unsubstituted or substituted and / or mono- or polyethylenically unsaturated, in each case substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl, arylcarbonyl, alkanoyl, carbamoyl or oxomethylene,

R ² , R ³ , R ⁴ and R ⁵ independently of one another have the same meaning as R ¹ and additionally independently halogen, hydroxyl, carboxyl, alkylsulfonyl, arylsulfonyl,

Nitrile, isonitrile or the radicals

R ² and R ⁴ or R ³ and R ⁵ 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.

5. A process for the preparation of inorganic support materials according to claim 1, characterized in that one - - a) at least one preferably a liquid heterocyclic 3-ring compound, in particular aziridines or solutions of at least one heterocyclic 3-ring compound in an organic solvent mixed with an inorganic carrier, or

b) dissolving at least one heterocyclic 3-ring compound, in particular aziridines, in an organic solvent and mixing with an inorganic support material, if appropriate with the addition of suitable dispersing aids, and isolating the inorganic support material loaded with at least one heterocyclic 3-ring compound, or

c) an emulsion comprising at least one heterocyclic 3-ring compound, in particular aziridines, water, at least one organic solvent and optionally

Mixing emulsifiers with an inorganic carrier material and isolating the inorganic carrier material loaded with at least one heterocyclic 3-ring compound, or

d) an aqueous dispersion of an inorganic carrier material containing, if appropriate, dispersing aid with an emulsion comprising at least one heterocyclic

Ring compound, in particular aziridines, water, at least one organic solvent and optionally emulsifiers mixed and isolated with at least one heterocyclic 3-ring compound loaded inorganic support material.

6. Use of inorganic support materials according to claim 1 for the stabilization of iodine-containing compounds.

7. Composition containing

a) at least one inorganic support material according to claim 1 and

b) at least one iodine-containing compound.

8. A composition according to claim 7, containing as iodo-containing compound at least diiodomethyl-p-tolylsulfone, diiodomethyl-p-chlorophenylsulfone, 3-bromo-2,3-diiodo-2-propenyl alcohol, 2,3,3-triiodoallyl alcohol, 4- Chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone (CAS-RN: 120955-77-3) iodoffen, 3- Iodo-2-propynyl-2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenylformal (IPCF), N-iodopropargyloxycarbonyl-alanine, N-iodopropargyloxycarbonyl-alanine ethyl r, 3- (3-iodopropargyl ) -benzoxazol-2-one, 3- (3-iodopropargyl) -6-chlorobenzoxazol-2-one, 3-iodo-2- - 5 - propynyl-a 1-koho-1, 4-chlorophenyl-3-iodopropargylformal, 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-c-arbamate, di- (3-iodo-2-propynyl) hexyl-dicarbamate, 3-iodo-2-propynyloxyethanol-ethylcarbamate, 3 Iodo-2-propynyl-oxyethanol-phenyl-carbamate, 3-iodo-2-propynyl-thioxo-thioethylcarbamate, 3-iodo-2-propynyl-carbamic acid ester (IPC), 3-bromo-2,3-diiodo-2 propenylethylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate or 3-iodo-2-propynylcyclohexylcarbamate.

9. A composition according to claim 7, containing as the iodine-containing compound at least

IPBC.

10. Binder formulation containing

at least one binder

at least one iodine-containing compound and

at least one inorganic carrier material according to claim 1.

11. Binder formulation according to claim 10, comprising at least one oxidatively drying binder.

12. A binder formulation according to claim 10, comprising at least one transition metal dryer.

13. Binder formulation according to claim 10, comprising

1 to 80 wt .-% Alkydharzbinder

0 to 50 wt .-% of colored pigments

0.01 to 5 wt .-% iodine-containing compound

0.001 to 5 wt .-% of anorg. Support material according to claim 1

From 2 to 97% by weight of solvent and

0.001 to 3 wt .-% of a transition metal dryer.

14. Use of the composition according to claim 7 for the protection of industrial materials against destruction or infestation by microorganisms. - 5 -

15. Technical materials containing at least one iodine-containing compound and at least one inorganic carrier material according to claim 1.

16. Use of aziridines for the production of inorganic carrier materials according to one of claims 1 to 4.