Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C269/08—Separation; Purification; Stabilisation; Use of additives
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring

Definitions

• the invention relates to carrier materials containing nitrogen, especially organically bonded nitrogen, to the preparation thereof and to the use thereof for stabilizing iodine-containing compounds, and to binder formulations comprising them and to the use thereof for the protection of industrial materials.
• Iodine-containing biocides are used for providing industrial materials, coating materials being an example, with protection from infestation, decomposition, destruction and visual alteration by fungi, bacteria and algae, preferentially by fungi. Furthermore, iodine-containing biocides, both alone and in combination with biocides from other classes of active ingredient, are used as components of biocidally active materials protection compositions such as wood preservatives. Besides iodoalkynyl compounds, the active ingredients used here include compounds in which one or more atoms of iodine are attached to double-bond systems, but also to singly bonded carbon atoms.
• a behaviour common to many iodine-containing biocides is that on exposure to light even in bulk or as a component of an industrial material (coating material, for example) they lead to yellowing with breakdown of the active compound. This feature hinders or prevents the use of iodine-containing biocides in materials having such sensitivity, such as in light-coloured or white coating materials, for example.
• these instability qualities are described in WO00/16628 for example.
• transition metal compounds examples being cobalt, lead, manganese and vanadium octoates, function as dryers (siccatives) for the alkyd resin-containing binder system.
• transition metal compounds are also used as pigments, and in some cases have destructive properties comparable with the siccatives.
• iodine-containing biocides in certain water-based industrial materials (e.g. coating materials and preservatives such as wood preservative stains and primers).
• coating materials and preservatives such as wood preservative stains and primers.
• film formation and film hardening of a water-based coating material is based, for example, on the oxidative crosslinking of water-soluble or emulsified alkyd resins
• transition metal compounds are employed as siccatives in these systems as well, and their use is accompanied by destruction of the iodine-containing biocides present.
• transition-metal-containing, solvent-based alkyd-resin paints where halopropargyl compounds are stabilized by means of organic epoxides cf. WO 00/16628.
• iodine-containing biocides are stabilized with 2-(2-hydroxyphenyl)benzotriazoles.
• Addition of epoxy compounds is said to reduce the discoloration of iodoalkyne compounds, such as IPBC (cf. U.S. Pat. No. 4,276,211 and U.S. Pat. No. 4,297,258).
• IPBC iodoalkyne compounds
• WO 2007/101549 describes the stabilization of iodine-containing biocides by means of azole compounds.
• the stabilizing action of the aforementioned stabilizers is not always sufficient, and carries performance disadvantages.
• the drying times of the paints are markedly prolonged, and in many cases this is unacceptable to the user.
• the inhibition of discoloration is not always sufficient.
• nitrogen-containing inorganic carrier materials makes it possible to provide iodine-containing biocides, particularly in solvent-based and water-based systems, with protection against both chemical and light-induced degradation, and hence to prevent the above-described disadvantages of unstabilized iodine-containing compounds, such as alterations to colour and loss of active compound/activity. It has been found, moreover, that using nitrogen-containing carrier materials to stabilize iodine-containing biocides in the aforementioned systems engenders no performance disadvantages, such as the prolongation of the drying time of a coating system, for example.
• Aziridine compounds are employed, for example, in US2004/0077783 A1 as part of polymerization initiators which as further ingredients comprise organoborane compounds, carrier materials and optionally fillers. The latter are present as a concomitant of the preparation process, but as mixtures with the other components, and not as carrier materials surface-modified with aziridine.
• liquid, iodine-containing formulations e.g. solutions and dispersions, such as, for example, low concentration and hence unnecessary transport of solvent, are improved still further.
• this form compared with iodine-containing solutions, this form possesses, in particular, stability advantages, particularly in storage, preferably at elevated temperatures.
• the invention relates to nitrogen-containing inorganic carrier materials.
• Nitrogen-containing inorganic carrier materials in the context of the invention are inorganic carrier materials comprising at least one absorptively or covalently bonded, nitrogen-containing compound.
• nitrogen-containing inorganic carrier materials also encompasses those inorganic carrier materials which comprise in each case absorptively and covalently bonded nitrogen-containing compounds, and also those inorganic carrier materials comprising different nitrogen-containing compounds, of which at least one is covalently bonded and at least one is adsorptively bonded.
• the nitrogen-containing inorganic carrier materials comprise the nitrogen in organically bonded form, where, for the purposes of the invention, organically bonded nitrogen means nitrogen which has at least one bond to a carbon atom, with the exception of cyanide and isocyanate ions and of prussic acid and isocyanic acid.
• nitrogen-containing inorganic carrier materials also encompasses those materials in which the inorganic carrier materials comprise covalently bonded nitrogen-containing compounds in which the nitrogen is organically bonded.
• the nitrogen-containing inorganic carrier materials of the invention are preferably solid at room temperature.
• the nitrogen-containing inorganic carrier materials of the invention are prepared preferably by reaction of inorganic carrier materials with at least one nitrogen-containing compound, the nitrogen-containing compounds preferably being organic compounds.
• nitrogen-containing inorganic carrier materials of the invention have a nitrogen content of 0.05% to 10% by weight, preferably of 0.1% to 10% by weight. Unless indicated otherwise, nitrogen contents are determined quantitatively by elemental analysis using a combustion method.
• the invention also encompasses nitrogen-containing inorganic carrier materials comprising compounds obtainable through reaction of inorganic carrier materials with nitrogen-containing compounds, where the preference ranges specified for nitrogen-containing inorganic carrier materials in general apply in the same way
• Suitable inorganic carrier materials are for example and preferably silicas such as, for example, precipitated silicas, such as silica gels, mesoporous silicates, xerogels, aerogels, fumed silicas, silicas modified with organic, inorganic or organometallic radicals, examples being dichlorodialkylsilane-modified silicas, kieselguhr, porosils, e.g.
• precipitated silicas such as silica gels, mesoporous silicates, xerogels, aerogels, fumed silicas, silicas modified with organic, inorganic or organometallic radicals, examples being dichlorodialkylsilane-modified silicas, kieselguhr, porosils, e.g.
• zeosils clathrasils or dealuminated zeolites, aluminosilicates, zeolites, natural or synthetic tectosilicates, natural silicates such as, e.g., vermiculite, mica or pyrogenic metal oxides, for example TiO 2 , including pyrogenic mixed metal oxides.
• fumed silicas Preference is given to fumed silicas, more particularly hydrophilic or hydrophobic ones, as for example those in commerce under the name Aerosil® from Evonik-Degussa, the product Aerosil® 200 being particularly preferred.
• the inorganic carrier material in the event that the heterocyclic 3-membered-ring compound is an aziridine, does not comprise any organoborane.
• hydrophilic or hydrophobic precipitated silicas more particularly hydrophilic or hydrophobic ones, examples being those in commerce under the name Sipernat® from Evonik-Degussa.
• Sipernat®22S and Sipernat®50S are particularly preferred.
• the nitrogen-containing inorganic carrier materials of the invention preferably have a particle size of 0.001 to 1000 ⁇ m, more particularly of 0.005 to 500 ⁇ m.
• DBP dibutyl phthalate
• the DBP absorbency of the carrier materials of the invention is preferably 0.1 to 800 g/100 g, more preferably 1 to 500 g/100 g of carrier material.
• the nitrogen-containing inorganic carrier materials of the invention preferably possess a specific surface area [m 2 /g], determined in a method based on that of Brunauer, Emmett and Teller (BET surface area; J. Am. Chem. Soc. 60, 309 (1938)), in accordance with ISO 5794/1 (Annex D), of 1 to 1200 m 2 /g, more preferably of 50 to 900 m 2 /g.
• BET surface area Brunauer, Emmett and Teller
• suitable nitrogen-containing compounds are those in which the nitrogen is organically bonded.
• Such compounds include, for example, mononitrogen compounds and polynitrogen compounds
• Mononitrogen compounds are, for example, those of the formula (Ia)
• Compounds of the formula (Ia) are, for example, aminoethanol and (2-[(1-methylpropyl)amino]ethanol.
• Polynitrogen compounds are, for example, polyamines such as, for example,
• Particularly suitable nitrogen-containing compounds are aziridines.
• Aziridines contemplated are those which comprise one or more aziridine groups.
• Preferred aziridines are, for example to aziridine compounds of the formula (I)
• Monofunctional aziridines of the formula (I) that are contemplated are, for example, 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.
• carbocyclic ring is unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, hydroxyl, oxo, carboxyl, alkylsulphonyl, arylsulphonyl, nitrile, isonitrile, alkyl or cycloalkyl, each of which is unsubstituted or substituted and/or mono- or polyethylenically unsaturated, or substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl or alkanoyl, and n is a number from 0 to 6, preferably 0 to 1.
• R 24 is —H or alkyl, preferably —H, —CH 3 , —C 2 H 5 , more preferably —CH 3 , —C 2 H 5
• g is a number from 1 to 4, preferably 1 to 3, more preferably 1 to 2
• h is a number from 1 to 11, preferably 1 to 5 and more preferably 1 to 3, and the remaining radicals have the above definition.
• Particularly preferred aziridines are those having two or more aziridine functions.
• Examples include compounds of the formula (V)
• A is preferably the trivalent radical of the formula
• Preferred compounds of the formula (V) are those conforming to the formulae (Va)-(Vd).
• polyfunctional aziridine compounds are Michael adducts of optionally substituted ethylenimine with esters of polyhydric alcohols with ⁇ , ⁇ -unsaturated carboxylic acids and the adducts of optionally substituted ethylenimine with polyisocyanates.
• Suitable alcohol components are, for example, trimethylolpropane, neopentylglycol, glycerol, pentaerythritol, 4,4′-isopropylidenediphenol, 4,4′-methylenediphenol and polyvinyl alcohols.
• suitable ⁇ , ⁇ -unsaturated carboxylic acids include acrylic acid and methacrylic acid, crotonic acid and cinnamic acid. Particular preference is given to acrylic acid.
• the corresponding polyhydric alcohols of the ⁇ , ⁇ -unsaturated carboxylic esters may optionally be alcohols which have been extended on their OH functions in some cases completely with alkylene oxides, singly or multiply.
• Alkylene oxides which are particularly suitable in accordance with the invention are ethylene oxide and propylene oxide.
• polyisocyanates suitable for reaction with optionally substituted ethylenimine are those specified at page 4 lines 33-35 of WO 2004/050617.
• aziridines that are suitable in accordance with the invention are those specified at page 3 lines 29-34 of WO 2004/050617.
• aziridines of the formula (I) which possess at least three aziridine groups, such as, for example, trimethylolpropane tris[3-(1-aziridinyepropionate], trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate], trimethylolpropane tris[2-aziridinylbutyrate], 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].
• trimethylolpropane tris[3-(1-aziridinyepropionate] trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate
• aziridines of the formula (VI) are those in which x is 3 or 4 and B is a trebly or quadruply OH-functional polyol.
• aziridines of the formula (VI) are those conforming to the formulae (VIa)-(VIc)
• alkyl is a linear or branched alkyl radical having 1 to 20, preferably 1 to 12, carbon atoms.
• 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 nitrogen-containing inorganic carrier materials of the invention may further comprise additional compounds, examples being solvents such as, for example, esters of mono- or polybasic carboxylic acids (e.g. mixtures comprising diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate), preferably VOC-free or low-VOC solvents, where VOC (volatile organic compounds) are compounds having a boiling point of less than 250° C.; and emulsifiers such as, for example, castor oil ethoxylates, dispersing assistants such as, for example, polyvinyl alcohols, chelating reagents such as, for example, those specified in WO 98/22543, one or more stabilizers from the series of the antioxidants, free-radical scavengers, UV stabilizers and/or UV absorbers (for examples see below). In many cases, synergistic effects are observed here.
• solvents such as, for example, esters of mono- or
• the nitrogen-containing inorganic carrier materials of the invention are prepared using, for example,
• the nitrogen-containing inorganic carrier materials of the invention contain 0.0001% to 8%, preferably 0.0005% to 6%, more particularly 0.001% to 5%, by weight, of emulsifiers.
• the nitrogen-containing inorganic carrier materials of the invention may additionally contain 0.1% to 15%, preferably 0.5% to 10%, more particularly 1% to 6%, by weight, of a solvent.
• the invention further relates to a process for producing the nitrogen-containing inorganic carrier materials of the invention, which is characterized in that
• Process alternative a) relates preferably to heterocyclic 3-membered-ring compounds which are liquid at room temperature (22° C.), with, in particular, pastelike compositions or dry powders being formed.
• carrier materials obtainable by the process of the invention, more particularly in accordance with procedure b), that comprise a dispersant, preferably anionic emulsifiers such as, for example, alkyl sulphates, alkyl ether sulphates, alkylarylsulphonates, alkyl succinates, alkyl sulphosuccinates, N-alkoylsarcosinates, acyltaurates, acylisethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulphonates, more particularly the alkali metal and alkaline earth metal salts, e.g.
• anionic emulsifiers such as, for example, alkyl sulphates, alkyl ether sulphates, alkylarylsulphonates, alkyl succinates, alkyl sulphosuccinates, N-alkoylsarco
• alkylaryl polyglycol ethers such as polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol or tributylphenyl polyglycol ethers, trissteryl phenyl ether ethoxylates, alkylaryl polyether alcohols, isotridecyl alcohol, polyoxyethylene-fatty alcohol ethers, polyoxyethylene-fatty acid esters such as, for example, ethoxylated castor oil, polyoxyethylenealkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters or block copolymers based on ethylene oxide and/or propylene oxide.
• alkylaryl polyglycol ethers such as polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nony
• preferred organic solvents used for the oil-in-water emulsion are preferably those specified above.
• a dispersion of the inorganic carrier materials in water is prepared with the use preferably of low shearing energy, as for example by using a paddle stirrer.
• the process alternatives according to the invention take place preferably at a temperature from 0 to 35° C., more particularly at room temperature (22° C.).
• the invention further relates to the use of the nitrogen-containing inorganic carrier materials of the invention for stabilizing iodine-containing compounds, more particularly biocides.
• Iodine-containing compounds contemplated are preferably iodoalkynyl compounds or compounds in which one or more iodine atoms are attached to double bonds or in which one or more iodine atoms are attached to singly bonded carbon atoms.
• the iodine-containing compounds are, for example, diiodomethyl p-tolyl sulphone, diiodomethyl p-chlorophenyl sulphone, 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), iodofenfos, 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl 4-chlorophenyl formal (IPCF), N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine ethyl ester
• the iodine-containing compounds are preferably 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl 4-chlorophenyl formal (IPCF), N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine 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 propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate
• IPCF 3-i
• the iodine-containing compounds are 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-propynyl phenylcarbamate, di(3-iodo-2-propynyl)hexyldicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl thioxothioethylcarbamate, 3-iodo-2-propynyl carbamate (IPC), 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 3-iododo
• the particularly preferred iodine-containing compounds are N-alkyl-iodotetrazoles, N-aryl-iodotetrazoles and N-aralkyl-iodotetrazoles, as described, for example, in (EP1773125).
• the nitrogen-containing inorganic carrier materials of the invention for use in accordance with the use are suitable preferentially for stabilizing iodine-containing compounds, more particularly biocides, in binder formulations, such as in alkyd-resin-based systems such as coating materials which comprise transition metal dryers, in particular in the presence of transition metal dryers.
• binder formulations and transition metal dryers are described in more detail later on below.
• Stabilization in the context of this specification means preferably the stabilization of iodine-containing compounds against both chemical and light-induced degradation, particularly against chemical degradation.
• the nitrogen-containing inorganic carrier materials of the invention may more particularly be used for suppressing or at least retarding the chemical degradation of iodine-containing compounds, more particularly biocides in active-compound formulations, more particularly coating materials such as paints, varnishes, primers, impregnating systems, stains and other industrial materials.
• the nitrogen-containing inorganic carrier materials of the invention that can be used in accordance with the invention for stabilizing iodine-containing compounds, more particularly biocides have a good stabilizing action especially in alkyd-resin-based systems such as coating materials which comprise transition metal dryers.
• the stabilization is preferably realized by the iodine-containing compounds, more particularly biocides, and the nitrogen-containing inorganic carrier materials of the invention being present together in a mixture or in a medium.
• composition is likewise provided by the present invention.
• compositions of the invention contain generally 0.01-70%, preferably 0.05%-60%, more preferably 0.1%-50% by weight of at least one iodine-containing biocide and at least one nitrogen-containing inorganic carrier material of the invention, and so the amount of all of the nitrogen-containing inorganic carrier materials present in the composition of the invention is 0.001%-80%, preferably 0.005%-60%, more preferably 0.01-50% by weight.
• composition of the invention preferably comprises the iodine-containing biocide and nitrogen-containing inorganic carrier materials in total from 40% to 99% by weight.
• the nitrogen-containing inorganic carrier material of the invention is preferably employed, and the amount of all of the nitrogen-containing inorganic carrier materials present in the composition of the invention is generally 1% to 280%, more preferably 2% to 225%, more particularly 5% to 180%, by weight, based on the iodine-containing biocide.
• composition of the invention may be present in a variety of forms—for example, as a solvent-based dispersion, water-based dispersion, solids mixture, etc.
• the composition of the invention takes the form of a solid mixture, such as, for example, a powder or granules, more particularly having an average particle size of 50 to 2000 ⁇ m, or a compacted formulation, such as, for example, compacted powder such as, for example, pellets, tablets, etc.
• the composition of the invention takes the form of a solvent-based dispersion, where, in order to adjust the rheological properties of the dispersion, for example, alkyd resins, modified alkyd resins, thixotropic resins, etc., and also further additives such as anti-skinning agents (antioxidants), pigments, crystallization stabilizers, etc., may be added.
• alkyd resins for example, alkyd resins, modified alkyd resins, thixotropic resins, etc.
• further additives such as anti-skinning agents (antioxidants), pigments, crystallization stabilizers, etc.
• composition of the invention may be included are adhesives such as carboxymethylcellulose, natural and synthetic polymers in powder, particle or latex form, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospho-lipids, such as cephalins and lecithins, and synthetic phospholipids, and also mineral and vegetable oils.
• adhesives such as carboxymethylcellulose, natural and synthetic polymers in powder, particle or latex form, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospho-lipids, such as cephalins and lecithins, and synthetic phospholipids, and also mineral and vegetable oils.
• adhesives such as carboxymethylcellulose, natural and synthetic polymers in powder, particle or latex form, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospho-lipids, such as cephalins and lecithins, and synthetic phospholipids, and also mineral and vegetable oils.
• colorants such
• TEDA tetramethylethylenediamine
• DABCO 1,4-diazabicyclo[2.2.2]octane
• the invention further provides a process for preparing the composition of the invention.
• the composition of the invention may be prepared, for example, by mixing the individual components, i.e. the nitrogen-containing inorganic carrier material and the iodine-containing compound, optionally with extenders and optionally using further adjuvants such as, for example, flow improvers, additives for increasing the electrical conductivity, additives for adjusting the dusting characteristics, etc.
• further adjuvants such as, for example, flow improvers, additives for increasing the electrical conductivity, additives for adjusting the dusting characteristics, etc.
• suitable solids mixers such as, for example, Lödige mixers, paddle mixers, tumble mixers, drum mixers with disruptors, etc.
• resultant solids mixtures into further embodiments, such as granules, compacted forms such as pillows, tablets, etc., for example is possible with use of fluid-bed granulation, use of mechanical compacting systems, optionally with addition of further additives such as binders, for example.
• composition of the invention is a solvent-based dispersion comprising an iodine-containing compound, in particular IPBC, and at least one nitrogen-containing inorganic carrier material of the invention, in particular one in which the heterocyclic 3-ring compound is at least one aziridine compound.
• the iodine-containing compound, in particular IPBC, and the nitrogen-containing inorganic carrier material of the invention are ground and dispersed (e.g. bead mill), preferably with strong shearing in an inert organic solvents as the continuous phase (e.g.
• isoparaffins such as Isopar® L (isoparaffin from Exxon) or “white spirits” such as, for example, Sheilsol® D60), optionally with addition of process auxiliaries and stabilizers such as, for example, rheological additives (thixotroping resins such as, for example, WorleeThix S6358, a thixotroped alkyd resin from Worlee) and optionally anti-skinning agents such as, for example, Antiskin® 444 (from Borchers).
• rheological additives thixotroping resins such as, for example, WorleeThix S6358, a thixotroped alkyd resin from Worlee
• anti-skinning agents such as, for example, Antiskin® 444 (from Borchers).
• compositions of the invention and/or of the iodine-containing compound employed may be increased by adding, optionally, further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active compounds, so as to widen the spectrum of activity or to obtain particular effects, or by using such compounds at the same time. These mixtures may possess an even broader spectrum of action.
• 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, simeconazole, ( ⁇ )-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol, 2-(1-tert-butyl)-1-(2-
• metal soaps such as: salts of the metals tin, copper and zinc with higher fatty acids, resin acids, naphthenic acids and phosphoric acid, such as, for example, tin naphthenate, tin octoate, tin 2-ethylhexanoate, tin oleate, tin phosphate, tin benzoate, copper naphthenate, copper octoate, copper 2-ethylhexanoate, copper oleate, copper phosphate, copper benzoate, zinc naphthenate, zinc octoate, zinc 2-ethylhexanoate, zinc oleate, zinc phosphate, zinc benzoate; metal salts such as: salts of the metals tin, copper, zinc, and also chromates and dichromates, such as, for example, copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulphate,
• azaconazole bromuconazole, cyproconazole, dichlobutrazol, diniconazole, diuron, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet, methfuroxam, carboxin, N-cyclohexyl-benzo[b]thiophenecarboxamide S,S-dioxide, fenpiclonil, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile, butenafine, imazalil, N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, dichloro-N-octylisothiazolinone,
• 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, bistrilfluoron, bromophos A, bromopho
• the invention further provides a binder formulation comprising
• the binder formulation preferably comprises the ‘iodine-containing compound, more particularly biocide’, and ‘nitrogen-containing inorganic carrier materials of the invention’ components in the form of the composition of the invention.
• Preferred binders contemplated include oxidatively drying binders, preferably alkyd-resin-based binders, or binders which form films by means of coalescents, especially lattices.
• alkyd-resin-based binders contemplated are preferably alkyd resins and modified alkyd resins.
• the alkyd resins are, in general, polycondensation resins formed from polyols and polybasic carboxylic acids and/or their anhydrides, and fats, oils or free natural and/or synthetic fatty acids.
• the alkyd resins may optionally also be modified chemically with hydrophilic groups, especially water-soluble groups, in order that they can be used, for example, as an emulsifiable or as a water-soluble alkyd resin.
• the stated polyols are preferably glycerol, pentaerythritol, trimethylolethane, trimethylolpropane and various dials such as ethane-/propanediol, diethylene glycol and neopentyl glycol.
• the stated polybasic carboxylic acids and/or their anhydrides are preferably phthalic acid, phthalic anhydride, maleic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, adipic acid, azelaic acid or sebacic acid.
• the stated oils or fatty acids are generally linseed oil, oiticica oil, tung oil, soya oil, sunflower oil, safflower oil, ricinene oil, tall oil, castor oil, coconut oil, peanut oil, their fatty acids, and also synthetic saturated, unsaturated or polyunsaturated monocarboxylic acids or mixtures of these components.
• the alkyd resins can optionally also be modified with, for example, natural resins, phenolic resins, acrylic resins, styrene, epoxy resins, silicone resins, isocyanates, polyamides or aluminium alkoxides.
• the alkyd resins generally have a molar mass of 500 to 100 000 g/mol, preferably of 1000 to 50 000 g/mol, more particularly of 1500 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 comprise preferably 1% to 80%, more preferably 2% to 70% and with particular preference 3% to 60% by weight of alkyd resin.
• the binder formulation of the invention preferably comprises an alkyd-resin-based binder and a transition metal dryer for oxidative drying.
• Transition metal dryers for the purposes of this specification are more particularly transition metal compounds which accelerate the drying and curing of the alkyd-resin-based binder.
• the salts of transition metals of groups Vb, VIb, VIIb, VIII and Ib of the chemical periodic system are more particularly the salts of cobalt, manganese, vanadium, nickel, copper and iron, more preferably cobalt, manganese, iron and vanadium. They need not necessarily be used alone, but instead can also be employed in combination with non-transition metal salts, such as lead, calcium or zirconium, for example.
• the preferred transition metal salts are soluble in organic solvents, for example, white spirit at 20° C. in an amount of more than 10 g/l.
• the salts in question are preferably the salts of carboxylic acids, which have high compatibility with the alkyd resin binders and at the same time ensure sufficient solubility of the metal salt.
• Preferred transition metal dryers are cobalt octoate and cobalt naphthenate, e.g. Octasoligen®-Cobalt 12 from Borchers.
• the binder formulations of the invention preferably comprise the transition metal dryers in an amount of 0.001% to 1%, preferably 0.005% to 0.5% and very preferably 0.01% to 0.1% by weight, based in each case on binder.
• the binder formulations comprise at least one polar organic solvent, preferably a polar aprotic solvent.
• suitable such polar protic solvents are those such as dipropylene glycol monomethyl ether (e.g. Dowanol DPM from Dow Chemical) and also, preferably, in combination thereto, polar aprotic solvents, such as dimethylformamide and dimethyl sulphoxide, and also, for example, etherified glycols, oligoglycols and polyglycols, etherified polyols and esterified polyols, esters of monobasic and polybasic carboxylic acids, e.g. diisobutyl adipate, diisobutyl maleate, (e.g. Rhodiasolv DIB).
• dipropylene glycol monomethyl ether e.g. Dowanol DPM from Dow Chemical
• polar aprotic solvents such as dimethylformamide and dimethyl sulphoxide
• binder formulation comprising
• solvent(s) more particularly non-polar or polar solvents, including preferably up to 10%, more particularly 0.01% to 7.5%, by weight, based on the binder preparation
• binder formulations of the invention are those comprising at least one alkyd resin, at least one transition metal dryer, IPBC, at least one solvent and at least one nitrogen-containing inorganic carrier material of the invention.
• the binder formulation may further comprise fillers, anti-skinning agents, rheological additives such as, for example, anti-settling agents and thixotropic agents, further biocides such as fungicides, bactericides, anti-fouling agents and algicides, solvents, process additives, plasticizers, UV stabilizers and heat stabilizers, and also corrosion inhibitors, in customary amounts.
• rheological additives such as, for example, anti-settling agents and thixotropic agents
• biocides such as fungicides, bactericides, anti-fouling agents and algicides
• solvents solvents
• process additives such as plasticizers, UV stabilizers and heat stabilizers, and also corrosion inhibitors, in customary amounts.
• one or more stabilizers from the group consisting of antioxidants, free-radical scavengers, UV stabilizers, chelators and UV absorbers, which in some cases exhibit synergistic effects.
• UV stabilizers include, by way of example, the following:
• sterically hindered phenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -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)phosphonate, 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-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-
• Hindered amines such as bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)decanedioate, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine copolymer, poly[[6-[(1,1,3,3-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.
• N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)isophthalamide 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 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-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 1,2,2,6,6-pentamethylpiperidin-4-yl ⁇ -(3,5-ditert-butyl-4-hydroxyphenyl)propionate, 1-benzyl-2,2,6,6-tetramethyl-4-isophthalamide,
• Phosphites and phosphonates such as tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2′-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1′-biphenyl]-4,4′-diylbisphosphonite, 2,2′-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite, dioctadecyl pent
• hydroxylamines such as N,N-bis(2-carboxyethyl)hydroxylamine, N,N-bis(benzylthiomethyl)hydroxylamine, N,N-diethylhydroxylamine, etc.
• secondary arylamines such as N-(2-naphthyl)-N-phenylamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer (CAS No. 26780-96-1), N-2-propyl-N′-phenyl-p-phenylenediamine, N-(1-naphthyl)-N-phenylamine, (benzenamine, N-phenyl-, reaction products with 2,4,4-trimethylpentene) (CAS No. 68411-46-1) or 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl)phenyl]aniline. Lactones and benzofuranones, such as
• Thioethers and thioesters such as distearyl 3,3-thiodipropionate, dilauryl 3,3′-thiodipropionate, ditetradecyl thiodipropionate, di-n-octadecyl disulphide.
• UV absorbers such as (methanone, [methylenebis(hydroxymethoxyphenylene)]bis[phenyl-), (methanone, [1,6-hexanediylbis[oxy(2-hydroxy-4,1-phenylene)]]bis[phenyl-), 2-benzoyl-5-methoxyphenol, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 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-triazine, 2-ethoxy-2′-ethyloxalic acid bisanilide, N-(5-tert-butyl-2-ethoxypheny
• Iodine-containing compounds are degraded in particular in the presence of the dryers described in more detail above. Although the strongest effects are observed in the presence of these dryers, a series of further paint components also have a destabilizing effect on iodine-containing compounds, more particularly biocides.
• these include organic and inorganic pigments, fillers, anti-skinning agents, rheological additives such as, for example, anti-settling agents and thixotropic agents, further compounds, particularly biocides such as fungicides, bactericides, anti-fouling agents and algicides, solvents, process additives, plasticizers, UV stabilizers and heat stabilizers, corrosion inhibitors, etc.
• the nitrogen-containing inorganic carrier materials of the invention also display a strongly stabilizing effect here.
• compositions of the invention used in oxidatively drying binder preparations, and the binder preparations of the invention themselves exhibit a significant reduction in drying time as compared with unstabilized iodine-containing systems, particularly systems containing IPBC or no increase in drying time as compared with the systems not equipped with IPBC (known as blank formulations).
• the binder formulations of the invention are used preferably as coating materials, more particularly as paints, varnishes, primers, impregnating systems and stains. Accordingly, the invention also provides for the use of the binder formulations of the invention as coating materials.
• the invention further provides for the use of the composition of the invention for protecting industrial materials against destruction or infestation by microorganisms.
• compositions of the invention are suitable for protecting industrial materials.
• Industrial materials in the present context are non-living materials which have been prepared for use in industry.
• the industrial materials are, for example, adhesives, sizes, paper and cardboard, textiles, leather, wood, wood-based materials, coating materials and plastics articles, cooling lubricants and other materials which may be infested or decomposed by microorganisms.
• microorganisms which may bring about degradation or alteration of the industrial materials include bacteria, fungi, yeasts, algae and slime organisms.
• the active compounds of the invention act preferably against fungi, more particularly moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and also against slime organisms and bacteria.
• Alternaria such as Alternaria tenuis, Aspergillus , such as Aspergillus niger, Chaetomium , such as Chaetomium globosum, Coniophora , such as Coniophora puetana, Lentinus , such as Lentinus tigrinus, Penicillium , such as Penicillium glaucum, Polyporus , such as Polyporus versicolor, Aureobasidium , such as Aureobasidium pullulans, Sclerophoma , such as Sclerophoma pityophila, Trichoderma , such as Trichoderma viride, Escherichia , such as Escherichia coli, Pseudomonas , such as Pseudomonas aeruginosa, Staphylococcus , such as Staphylococcus aureus.
• Coniophora such as Coniophora puet
• the invention further provides industrial materials comprising at least one iodine-containing compound, in particular biocide, and at least one inorganic carrier material of the invention.
• Examples 1-5 describe the preparation of inventive nitrogen-containing inorganic carrier materials from inorganic carrier materials and nitrogen-containing compounds, and inventive compositions comprising IPBC and aforesaid carrier materials. Nitrogen contents were determined by means of combustion analysis on the Leco TruSpec CHN instrument.
• the oil phase consisting of 9.0 g of Crosslinker CX-100 from DSM (trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate]) and 2.5 g of Rhodiasolv® DIB from Rhodia (mixture consisting of diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate) was emulsified 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 under the action of an Ultraturrax (24 000 r*min ⁇ 1 ) for 10 minutes.
• the colourless emulsion obtained was metered into a dispersion of 27.0 g of Aerosil® 200 from Evonik (fumed silica having a BET surface area of 200 m 2 /g and a DBP absorbency of 300 g/100 g) in 300 g of water with paddle stirring, followed by stirring for 24 hours.
• Aerosil loaded with the aziridine and Rhodiasolv DIB was isolated from the resultant dispersion by spray drying (Büchi B-290 spray dryer, pump output 45%, N 2 flow rate 35 l*min ⁇ 1 , inlet 160° C., outlet 73° C.). This gave 33 g of a very fine, colourless solid (84% of theory).
• the oil phase consisting of 18.0 g of Crosslinker CX-100 from DSM (trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate]) and 5.0 g of Rhodiasolv® DIB from Rhodia (mixture consisting of diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate) was emulsified with a solution of the emulsifier of 1.15 g Tanemul® KS from Tanatex (castor oil ethoxylate with 30 eq. EO) in 50 g of water under the action of an Ultraturrax (24 000 r*min ⁇ 1 ) for 10 minutes.
• the colourless emulsion obtained was metered into 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 assistant Mowiol® 3-85 (polyvinyl alcohol from Kuraray) in 576 g of water, with paddle stirring, followed by addition of 600 g of water and then by stirring for 24 hours.
• Aerosil® 200 from Evonik fumed silica
• Mowiol® 3-85 polyvinyl alcohol from Kuraray
• Aerosil loaded with the aziridine and Rhodiasolv® DM was isolated from the resultant dispersion by filtration. Drying gave 75.4 g of a very fine, colourless solid (98% of theory).
• IPBC 90.0 g
• IPBC 90.0 g
• the nitrogen-containing inorganic carrier material from Example 2 containing 23.2% of aziridine, so making the weight ratio of IPBC to aziridine 4:1
• ceramic beads ⁇ 40 mm
• IPBC 90.0 g
• IPBC 90.0 g
• Example 2 containing 23.2% of aziridine, so making the weight ratio of IPBC to aziridine 3:1
• ceramic beads ⁇ 40 mm
• IPBC 90.0 g
• IPBC 90.0 g
• 128.4 g of the aziridine formulation from Example 1 containing 23.03% of aziridine, so making the weight ratio of IPBC to aziridine 4:1
• ceramic beads ⁇ 40 mm
• IPBC compositions from Example 3 and 4 are incorporated in a typical, alkyd-based coating system (alkyd stain A) in the presence of a transition metal dryer (Co) and a metal oxide pigment (iron oxide).
• alkyd stain A alkyd stain A
• Co transition metal dryer
• iron oxide iron oxide
• the above-mentioned compositions from Example 3 and 4, respectively, and, an IPBC concentrate containing IPBC and an aziridine in a ratio of 2:1 (see Table 1) without inorganic carrier material are used in each case.
• IPBC/aziridine concentrate (reference II) IPBC 30% by weight Crosslinker CX-100** 15% by weight Rhodiasolv DIB* 55% by weight *Mixture of diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate, Rhodia. **Trimethylolpropane-tris[3-(2-methy1-1-aziridinyl)propionate]
• IPBC compositions from Examples 3, 4 and 5 are incorporated in a commercial high-build wood stain “alkyd stain B” (containing alkyd resin, white spirit, iron oxide pigment, dryer, butanone oxime, UV absorber and additives).
• alkyd stain B containing alkyd resin, white spirit, iron oxide pigment, dryer, butanone oxime, UV absorber and additives.
• the compositions of Examples 3, 4 and 5 and also unstabilized IPBC are used in each case (see Table 4):
• an accelerated ageing test is carried out.
• the equipped paint system is introduced into tightly sealing 200 ml glass bottles, with only a minimum, residual amount of air remaining in the container, and stored at 40° C.
• Table 5 whereby only the alkyd stains B-I to B-III, equipped in accordance with the invention, exhibit no significant degradation of the IPBC after 4 weeks of storage at 40° C.
• the alkyd stains I and II a good stability of IPBC is found even after 8 weeks of storage at 40° C.
• Example 9a to 9f the preparation is described of inventive nitrogen-containing inorganic carrier materials from inorganic carrier materials and nitrogen-containing compounds which are not aziridines, and of inventive compositions comprising IPBC and aforesaid carrier materials. Nitrogen contents were again determined by means of combustion analysis on the Leco TruSpec CHN instrument.
• Aerosil with Lupasol FG Aerosil with Lupasol FG
• the oil phase consisting of 14 g of Lupasol FG from BASF (cationic polyethylenimine with branched spherical structure/CAS No. 9002-98-6/molecular weight approximately 800 g/mol) and 3.89 g of Rhodiasolv® DIB from Rhodia (mixture consisting of diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate) was emulsified with a solution of the emulsifier of 0.89 g Tanemul® KS from Tanatex (castor oil ethoxylate with 30 eq. EO) in 29.1 g of water under the action of an Ultraturrax (24 000 r*min ⁇ 1 ) for 10 minutes. The pale yellow emulsion obtained was added to a dispersion of 27.0 g of Aerosil® 200 from Evonik (fumed silica) in 600 g of water and stirred at room temperature for 14 hours.
• the oil phase consisting of 14 g of Lupasol WF from BASF (cationic polyethylenimine with branched spherical structure/CAS No. 9002-98-6/molecular weight approximately 25 000 g/mol) and 3.89 g of Rhodiasolv® DIB from Rhodia (mixture consisting of diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate) was mixed and emulsified with a solution of the emulsifier of 0.89 g Tanemul® KS from Tanatex (castor oil ethoxylate with 30 eq.
• Aerosil with Lupasol FG Aerosil with Lupasol FG
• Aerosil® 200 (27 g) from Evonik (fumed silica) was suspended by stirring in 591 g of water. Added to this suspension with stirring is a solution of 11.9 g of Lupasol FG from BASF (cationic polyethylenimine with branched spherical structure/CAS No. 9002-98-6/molecular weight approximately 800 g/mol) in 8.1 g of water, followed by stirring at room temperature for 12 hours.
• BASF cationic polyethylenimine with branched spherical structure/CAS No. 9002-98-6/molecular weight approximately 800 g/mol
• Aerosil® 200 (27 g) from Evonik (fumed silica) was suspended by stirring in 591 g of water.
• the oil phase consisting of 14 g of Alpamin N41 from Arkema (2-[(1-methylpropyl)amino]ethanol, CAS No. 35265-04-4) and 3.89 g of Rhodiasolv® DIB from Rhodia (mixture consisting of diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate) was emulsified with a solution of the emulsifier of 0.89 g Tanemul® KS from Tanatex (castor oil ethoxylate with 30 eq. EO) in 29.1 g of water under the action of an Ultraturrax (24 000 r*min ⁇ 1 ) for 10 minutes. The pale yellow emulsion obtained was added to a dispersion of 27.0 g of Aerosil® 200 from Evonik (fumed silica) in 600 g of water and stirred at room temperature for 14 hours.
• Aerosil® 200 (27 g) from Evonik (fumed silica) was suspended by stirring in 591 g of water. Added to this suspension with stirring is a solution of 11.9 g of Alpamin N41 from Arkema (2-[(1-methylpropyl)amino]ethanol, CAS No. 35265-04-4) in 8.1 g of water, followed by stirring at room temperature for 12 hours.
• the nitrogen-containing inorganic carrier materials from Examples 9a to 9f are incorporated in a typical, alkyd-based coating system (alkyd stain A) in the presence of a transition metal dryer (Co) and a metal oxide pigment (iron oxide).

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