Classifications

• • 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
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
  • A61P31/04—Antibacterial agents
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
  • A61P31/10—Antimycotics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0206—Polyalkylene(poly)amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0206—Polyalkylene(poly)amines
  • C08G73/0213—Preparatory process
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

• the invention relates to the preparation of nitrogen-containing polymers from aziridines, the use of these nitrogen-containing polymers for stabilizing iodine-containing compounds, compositions comprising at least the nitrogen-containing polymers and iodine-containing compounds and the use of these compositions as biocides or for controlling microorganisms.
• Iodine containing biocides are used to protect engineering materials such as paints from infestation, decomposition, destruction and visual change by fungi, bacteria and algae.
• 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.
• active substances are also used here in which one or more iodine atoms are bound to sp 2 -hybridized carbon atoms of olefinic double bonds, but also to sp 3 -hybridized carbon atoms.
• iodine-containing biocides have in common that they decompose under the action of light even in substance or as a component of a technical material under yellowing, which massively affects both the biocidal equipment and the feel of the material to be protected.
• iodine-containing biocides in particular iodoalkynyl compounds, are destroyed particularly rapidly by transition metal compounds. This fact prevents the use of iodine-containing biocides such as, in particular, iodoalkynyl compounds in solvent-borne paints such as paints, varnishes and glazes, or biocidal protectants such as wood preservative primers, wood preservatives and wood stains because these alkyd resin-based coating and protection systems typically contain transition metal compounds.
• the transition metal compounds such as cobalt, lead, manganese and vanadium octoates act as dryers (siccatives) of the alkyd resin-containing binder system.
• transition metal compounds are also used as coloring pigments, and have comparable destructive properties with the siccatives.
• the film formation and film hardening of a water-based paint based on the oxidative crosslinking of water-soluble or emulsified alkyd resins, as well as in these systems transition metal compounds are used as siccatives, which is associated with destruction of iodine-containing biocides.
• EP 2 236 033 A now describes stabilization by stabilizers containing aziridine groups. However, no storage-stable concentrates of iodine-containing biocides can be produced in this way.
• nitrogen-containing polymers are suitable for effectively protecting iodine-containing compounds, in particular in (organic) solvent- and water-based systems, from both chemical and light-induced degradation and thus can prevent color changes and loss of activity.
• the invention therefore relates to the use of nitrogen-containing polymers for the stabilization of iodine-containing compounds and to a process for the stabilization of iodine-containing compounds by contacting with nitrogen-containing polymers.
• stabilization is understood to mean the protection of iodine-containing compounds from chemical and / or light-induced degradation.
• Compounds containing iodine include, for example, iodoalkynyl compounds and compounds in which one or more iodine atoms are bonded to sp 2 -hybridized carbon atoms of olefinic double bonds, or to sp 3 -hybridized carbon atoms.
• such compounds have biocidal activity.
• iodine-containing compounds having biocidal activity are, for example, N- (Ci-Ci2) alkyl- iodotetrazoles, N- (C6-Ci 5) -aryl-iodotetrazoles, N- (C6-Ci 5) arylalkyl iodotetrazoles diiodomethyl-p-tolylsulfone , Diiodomethyl-p-chlorophenylsulfone, 3-bromo-2,3-diiodo-2-propenyl alcohol, 2,3,3-triiodoallyl-a 1 koho 1, 4-chloro-2- (2-chloro-2-methylpropyl) - 5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone (CAS-RN: 120955-77-3), iodoffen, 3-iod
• 2-propynyl-oxy-ethanol-phenyl-c-arbamate 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 and 3-iodo-2-propynylcyclohexylcarbamate.
• Preferred iodine-containing compounds having biocidal activity are 3-iodo-2-propynyl-2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenylformal (IPCF), N-iodopropargyloxycarbonylalanine, 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-chlor
• Particularly preferred iodine-containing compounds having biocidal activity are 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-oxy-ethanol-phenyl -carbamate, 3-iodo-2-propynylthioxo-thioethylcarbamate, 3-iodo-2-propynyl-c arb-amine acid ester (IP C), 3-bromo-2,3-diiodo-2-prop
• the nitrogen-containing polymers preferably have a weight-average molecular weight greater than 1,000 g / mol, preferably from 2,000 to 100,000 g / mol, and more preferably from 3,000 to 60,000 g / mol as determined by gel permeation chromatography against polystyrene standard (unless otherwise stated: Polystyrene / PSS polymer kit)
• the nitrogen-containing polymers preferably have a nitrogen content of 1 to 20% by weight, preferably 2 to 15% by weight N, and more preferably 5 to 12% by weight N as determined by elemental analysis Nitrogen-containing polymers are particularly suitable for those having structural units derived from aziridines.
• nitrogen-containing polymers are those obtainable by reacting aziridines in the presence of water.
• the aziridine ring In the reaction of aziridines in the presence of water, the aziridine ring can be opened by nucleophilic reaction with water to give a beta-aminoalcohol.
• the amino group itself as a strong nucleophile, may then effect, for example, the nucleophilic ring opening of another aziridine ring, thereby forming a dimer containing a beta-aminoamine function, which in turn may further react to form higher polymers.
• nitrogen-containing polymers are those which have at least one, preferably several, beta-aminoamine functions,
• nitrogen-containing polymers are those obtainable by reacting such aziridines in the presence of water containing one or more unsubstituted or substituted aziridine groups. Preference is given to aziridine compounds of the formula (I)
• 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 or alkanoyl,
• R 2 , R 3 , R 4 and R 5 independently have the same meaning as R 1 and additionally independently halogen, hydroxyl, carboxyl, alkylsulfonyl, arylsulfonyl, nitrile, isonitrile and
• 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.
• 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.
• carbocyclic ring is unsubstituted or having 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 mono- or polyethylenically unsaturated are substituted, substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl or alkanoyl and n is a number from 0 to 6, preferably from 0 to 1. Also preferred are those monofunctional aziridine compounds of formula (I) wherein R 1 is a radical of formula
• 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, more 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 significance.
• R is -H or alkyl, preferably -H or -CH 3 , particularly preferably -CH 3 , R is -H or alkyl, preferably -H or -CH 3 , more preferably -CH 3 and the remaining radicals have the above significance.
• aziridines which have two or more aziridine functions.
• examples are compounds of the formula (V) to name
• m-valent aliphatic, cycloaliphatic or aromatic radical which is optionally substituted, is a number from 2 to 5, in particular 2 to 3, and for each m-unit each independently is hydrogen or C 1 -C 4 - Alkyl, in particular CH 3 or CH 2 CH 3 is.
• A is preferably C 2 -C 10 -alkylene, in particular
• A is preferably the trivalent radical of the formula
• polyfunctional aziridine compounds are Michael addition products of optionally substituted ethyleneimine with esters of polyhydric alcohols with ⁇ , ⁇ -unsaturated carboxylic acids and the addition products of optionally substituted ethyleneimine with polyisocyanates.
• suitable alcohol components are trimethylolpropane, neopentyl glycol, glycerol, pentaerythritol, 4,4'-isopropylidenediphenol and 4,4'-methylenediphenol.
• ⁇ , ⁇ -unsaturated carboxylic acids are, for example, acrylic and methacrylic acid, crotonic acid and cinnamic acid in question.
• composition according to the invention particularly preferably contains acrylate esters.
• the corresponding polyhydric alcohols of the .alpha.,. Beta.-unsaturated carboxylic acid esters may optionally be alcohols which, in their OH functions, are partially 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.
• Particularly suitable alkylene oxides according to the invention are ethylene oxide and propylene oxide.
• polyisocyanates suitable for reaction with optionally substituted ethyleneimine are those mentioned on page 4, lines 33-35 of WO2004 / 050617 A.
• aziridines suitable according to the invention are those on S. 3, lines 29-34 of WO2004 / 050617 A mentioned.
• aziridines as described for example in US 3,225,013 (Fram), US 4,490,505 (Pendergrass) and US 5,534,391 (Wang).
• 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- (l-aziridinyl) propionate].
• 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]
• pentaerythritol tetrakis- [3- (1-aziridinyl) propionate pentaerythritol tetrakis- [3- (1-aziridinyl) propionate].
• trimethylolpropane tris [3- (1-aziridinyl) propionate]
• trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate]
• pentaerythritol tetrakis [3- (1-aziridinyl) propionate].
• B is the residue of an aliphatic polyol having at least x OH functions, wherein x OH functions are substituted by the remainder of the above parenthesis, f is a number from 0 to 6, especially from 1 to 3, x is a number greater or equal to 2, in particular for 2 to 100,000 stands and
• R 38 and R 39 or R 40 and R 41 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.
• B is particularly preferably the radical of a polyvinyl alcohol. 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.
• R 38 is hydrogen or CH 3 .
• the nitrogen-containing polymers are obtained by reacting aziridines, such as those mentioned above, in the presence of water and optionally in the presence of cosolvents. Therefore, the invention also includes a process for the preparation of nitrogen-containing polymers, which is characterized in that aziridines are reacted in the presence of water and optionally cosolvents.
• the amount of water used can be varied within a wide range. In general, at least 10% by weight of water is used, based on the aziridines used.
• the amount of water is preferably from 20 to 1,000% by weight, more preferably from 30 to 300% by weight, based on the aziridines used.
• the usable amount of water is in principle not limited to the top, but cause high amounts of water naturally a higher isolation effort for the nitrogen-containing polymers.
• the reaction temperature is for example 30 to 100 ° C, preferably 40 to 90 ° C and most preferably 50 to 80 ° C.
• the reaction is carried out until 95% or more, preferably 98% or more, more preferably 99% or more of the aziridine used was reacted based on the proportion of aziridine rings. Most preferably, the reaction is conducted until no more aziridine rings are detectable.
• the nitrogen-containing polymers used according to the invention have a content of 5% or less, preferably 2% or less, more preferably 1% or less, most preferably no detectable levels of aziridine rings based on the aziridines used.
• the nitrogen-containing polymers used according to the invention have a content of 5% or less, preferably 2% or less, more preferably 1% or less, most preferably no detectable levels of aziridine nitrogen based on the total nitrogen content.
• the proportion of unreacted aziridine rings can be determined, for example, by means of 13C-NMR spectra in comparison to the aziridine used.
• reaction time is 2 to 48 hours, more preferably 3 to 24 hours.
• cosolvents Although the use of cosolvents is not absolutely necessary for achieving the desired stabilizers, it can be particularly helpful when using high aziridine concentrations, since in this way gel formation in the reaction batch is effectively prevented. As cosolvents, it is generally possible to use all compounds which are miscible with water and under the reaction conditions themselves do not react or react only slightly with the aziridines used.
• Preferred cosolvents are oligo- or polyalkylene glycols or triols, or ethers of the abovementioned compounds, in particular having a molecular weight of less than 1,000 g / mol.
• Particularly preferred are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, Polypropylenglcol, glycerol and mono-, di-methyl, ethyl, propyl or butyl ether of the aforementioned compounds and any mixtures of the aforementioned cosolvents.
• diethylene glycol butyl ether as cosolvent.
• the amount of cosolvents used can be varied within a wide range. In general, for example, at least 20% by weight of cosolvents are used, based on the amount of water used, preferably from 30 to 1, 000% by weight, particularly preferably from 50 to 300% by weight.
• the nitrogen-containing polymers prepared by the process according to the invention can be used directly in the form of the resulting solution for stabilizing iodine-containing compounds or, after separation of cosolvents and / or water, optionally in isolated form.
• the nitrogen-containing polymers such as, in particular, the nitrogen-containing polymers obtainable according to the invention or prepared by the process according to the invention, are suitable for common use with iodine-containing compounds in biocidal agents.
• the invention therefore also includes biocidal compositions comprising at least a) at least one iodine-containing compound having a biocidal effect, b) at least one nitrogen-containing polymer, the ranges and preferred ranges mentioned above for the individual components being applied in the same way.
• Preferred biocidal agents contain a) IPBC and b) nitrogen-containing polymers obtainable by reacting at least one preferably exactly one aziridine of the formula (VI) in the presence of water.
• the biocidal compositions according to the invention generally comprise a) from 0.01 to 70% by weight, preferably from 0.05 to 60% by weight, particularly preferably from 0.1 to 50% by weight, of iodine-containing compounds having a biocidal effect and b ) 0.001 to 50 wt .-%, preferably 0.005 to 40 wt .-%, particularly preferably 0.01 to 30 wt .-% of nitrogen-containing polymers.
• the biocidal compositions according to the invention contain the iodine-containing compounds having a biocidal effect, and the nitrogen-containing polymers in total from 0.011 to 100 wt .-%, preferably 0.05 to 80 wt .-%, particularly preferably 0.1 to 60 wt. -%.
• the biocidal compositions according to the invention comprise from 1 to 280% by weight of nitrogen-containing polymers, preferably from 2 to 225% by weight, in particular from 5 to 10% by weight, based on the iodine-containing compounds having a biocidal effect.
• the biocidal agents may or may not further contain solvents.
• solvents such solvents can be used as they have already been described above as cosolvents for the reaction to nitrogen-containing polymers.
• the areas and preferred areas apply here analogously.
• the biocidal agents may or may not contain acids such as organic and / or inorganic acids. It is clear to the person skilled in the art that due to the possible basicity of the nitrogen-containing polymers, in particular if they were obtained from aziridines, the acids are at least not completely present in free form in the biocidal agent. The amounts given below therefore refer to contents and amounts calculated in each case on the free acid.
• the inorganic acids which may be present may, in principle, be all inorganic acids which are soluble in the biocidal agent.
• Preferred inorganic acids are hydrochloric acid or HCl, sulfuric acid and phosphoric acid.
• organic acids which may be present may, in principle, be all organic acids which are soluble in the biocidal agent.
• Preferred organic acids are formic acid, acetic acid, citric acid, propionic acid or benzoic acid. Particularly preferred is formic acid.
• the content of acids can be varied within a wide range. In general, it is 0.01 to 2 wt .-%, preferably 0.03 to 1, 5 wt .-% and most preferably 0.05 to 1 wt .-% based on the total biocidal agent.
• biocidal agents described above may additionally contain other active ingredients and adjuvants. They can be present for example as a solution, emulsion or suspension.
• organic solvents may or may not be included.
• Organic solvents are, for example, aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, such as For example, petroleum fractions (white spirit, Shellsol D60 Fa.
• monohydric alcohols such as ethanol, isopropanol and butanol
• polyhydric alcohols such as glycerol, pentaerythritol, polyvinyl alcohol (eg Mowiol ® the company Kuraray)
• glycols such as ethylene glycol and propylene glycol
• oligoglycols and polyglycols ethers of oligoglycols such as, dipropylene glycol monomethyl ether (such as Dowanol ® TPM of Messrs. Dow)
• ethers and esters of alcohols such as (Texanol ® from.
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone strongly polar aprotic solvents, such as dimethylformamide and D imethylsulfoxid, and, for example vollveretherte glycols, oligoglycols and polyglycols such as ethylene glycol dibutyl ether, etherified polyols, esterified polyols, esters of mono- and polybasic carboxylic acids such as diisobutyl adipate, diisobutyl maleate (eg Rhodiasolv DIB ®) ,
• biocidal compositions 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, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids and mineral and vegetable oils or not.
• adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids and mineral and vegetable oils or not.
• biocidal agents of the present invention may contain, as further ingredients, dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes.
• dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes.
• the biocidal compositions of the invention may contain other stabilizers, such as chelating or organic epoxides. In many cases, synergistic effects are observed here.
• biocidal compositions according to the invention can be increased if they contain, where appropriate, further active compounds selected from the group of further antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients.
• Particularly favorable mixing partners are, for example, the following compounds, which may or may not in each case be contained individually: 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, (+)
• Pyridines and pyrimidines such as: ancymidol, buthiobate, fenarimol, mepanipyrine, nuarimol, pyroxyfur, triamirole;
• Succinate dehydrogenase inhibitors such as:
• Formaldehyde and formaldehyde-releasing compounds such as:
• Isothiazolinones such as:
• Pyridines such as: 1-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.
• Oxides such as: Oxides of the metals tin, copper and zinc, e.g. Tributyltin oxide, CU2O, CuO, ZnO; Oxidizing agents such as:
• Cufraneb Ferban, potassium N-hydroxymethyl-N'-methyl-dithiobarbamate, maleic or K-dimethyldithiocarbamate, macozeb, maneb, metam, metiram, thiram, zineb, ziram;
• 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, Buto-carboxy, Butoxycarboxime,
• Fenamiphos fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fensulfothion, fenthione, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flupyrazofos, fluffine, flumethrin flufenprox , Fluvalinate, Fonophos, Formethanates, Formothion, Fosmethilan Fosthiazat, Fubfenprox, Furathiocarb,
• Halofenocide HCH (CAS RN: 58-89-9), heptenophos, hexaflumuron, hexythiazox, hydramethylnone, hydroprene, imidacloprid, imiprothrin, indoxycarb, iprinomectin, Iprobenfos, isazophos, isoamidophos, isofenphos, isoprocarb, isoprothiolanes, isoxathione, ivermectin,
• 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, Pyralidyl, Pyrimidifen, Pyri-Prodi, Pyrithiobac-Sodium
• Molluscicides Fentin acetate, Metaldehyde, Methiocarb, Niclosamide; Herbicides and algicides:
• Haloxyfop hexazinone, imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, imazethapyr, loxynil, isopropalin, imazosulfuron, imazomox, isoxaflutole, imazapic,
• 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,
• the biocidal agents are particularly suitable for biocidal finishing of technical materials such as in particular paints such as paints, varnishes, primers, impregnations, glazes.
• paints such as paints, varnishes, primers, impregnations, glazes.
• alkyd resin-containing binder formulations especially if they contain transition metal driers and / or transition metal compounds as pigments, the stabilizing effect of the nitrogen-containing polymers on the iodine-containing compounds having a biocidal effect is particularly advantageous.
• the invention therefore furthermore relates to binder formulations comprising a) at least one binder, b) at least one iodine-containing compound having a biocidal effect and c) at least one nitrogen-containing polymer, wherein the ranges and preferred ranges mentioned above for the individual components apply in the same way.
• Preferred binders are oxidatively drying binders, such as, for example, alkyd resin-containing binders or binders coalescing through coalescing agents, in particular polymer latices.
• 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, ricinoleic oil, tall oil, castor oil, coconut oil, peanut oil, their fatty acids and synthetic monocarboxylic acids.
• 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, preferably 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 according to the invention preferably contain from 1 to 80% by weight, preferably from 2 to 70% by weight and more preferably from 3 to 60% by weight of binder, preferably alkyd resin.
• the binder formulation according to the invention preferably also contains at least one transition metal dryer.
• transition metal dryers are understood as meaning, in particular, transition metal compounds which enable or accelerate the drying and curing of binders containing alkyd resin.
• the salts of transition metals of groups Vb, VIb, VIIb, VIII and Ib of the Periodic Table are preferred.
• 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 white spirit at 20 ° C in an amount greater than 10 g / l.
• it is the salts of carboxylic acids which have a good compatibility with the alkyd resins 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 the binder , preferably alkyd resin.
• the binder formulations in a preferred embodiment contain at least one polar organic solvent, preferably a polar protic organic solvent.
• polar protic organic solution such as dipropylene glycol monomethyl ether (for example Dowanol DPM from Dow Chemical) and furthermore alternatively, preferably in addition to polar aprotic organic solvents such as dimethylformamide and dimethyl sulfoxide, as well as e.g. etherified glycols, oligoglycols and polyglycols, etherified polyols and disperse polyols, esters of in and polyvalent carboxylic acids, e.g. Diisobutyl adipate, diisobutyl maleate (e.g., Rhodiasolv DIB).
• polar protic organic solution such as dipropylene glycol monomethyl ether (for example Dowanol DPM from Dow Chemical) and furthermore alternatively, preferably in addition to polar aprotic organic solvents such as dimethylformamide and dimethyl
• the binder formulation may or may not independently contain fillers, anti-skinning agents, rheology additives, such as anti-settling agents and thixotropic agents, other antimicrobial compounds, fungicides, bactericides, herbicides, insecticides, or other active ingredients, and for the antimicrobial compounds, fungicides, Bactericides, herbicides, insecticides or other active ingredients, the information given above for the biocidal agent apply here in the same way.
• the binder formulation may or may not independently contain solvents, process additives, plasticizers, heat stabilizers, and corrosion inhibitors.
• the biocidal agents or binder formulations according to the invention may also contain one or more adjuvants from the series of antioxidants, radical scavengers, UV stabilizers, chelators and UV absorbers. In some cases, synergistic effects are observed. Examples which may be mentioned as UV stabilizers: hindered phenols, such as
• Esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,
• Diethylene glycol triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate or
• Esters of ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono- or polyhydric alcohols e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
• Thiodiethylenglycol diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate or di-hydroxyethyl-oxalklarediamid.
• Phosphites and phosphonates such as, tri (nonylphenyl) phosphites, tris (2,4-di-tert-butylphenyl) phosphites, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphites, bis (2,6-di-tert-butyl) 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'-diylbisphosphonites, 2,2'-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphites, dioctadec
• N- (2-naphthyl) -N-phenylamines, 2,2,4-trimethyl-1,2-dihydroquinoline polymer (CAS No: 26780-96-1), N-2-propyl-N'-phenyl-p phenylenediamines, N- (1-naphthyl) -N-phenylamines, (Benzeneamines, N-phenyl-, reaction products with 2,4,4-trimethylpentenes) (CAS No. 68411-46-1), 4- (1 -Methyl-1-phenylethyl) -N- [4- (1-methyl-1-phenylethyl) phenyl] aniline.
• Thioethers and thioesters such as, distearyl-3,3-thiodipropionate, dilauryl 3,3'-thiodipropionate, ditetradecyl thiodipropionate, di-n-octadecyl disulfide.
• UV absorbers like,
• binder formulations according to the invention are particularly suitable for use as paints, in particular for use as paint, varnish, primer, impregnation or glaze.
• paints in particular for use as paint, varnish, primer, impregnation or glaze.
• the aforementioned uses are also the subject of the invention.
• the binder formulations according to the invention containing transition metal driers themselves do not show any prolongation of the drying time as compared to binder formulations in which the iodine-containing compounds, such as, in particular IPBC, are not stabilized, as frequently observed with the addition of stabilizers.
• the invention further relates to the use of the biocidal compositions of the invention for the protection of industrial materials against destruction or infestation by microorganisms.
• the biocidal agents according to the invention are suitable for the biocidal finishing of technical materials.
• Technical materials as used herein mean non-living materials prepared for use in the art.
• the technical materials are adhesives, glues, paper and cardboard, textiles, leather, wood, wood-based materials, paints and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms.
• microorganisms that can cause degradation or a change in the technical materials
• 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.
• 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 also includes the technical materials containing at least one iodine-containing compound having a biocidal effect and a nitrogen-containing polymer.
• Example 4 Binding Medium Formulations
• the compounds or agents obtained according to Examples 1, 2 and 3 were incorporated in a typical alkyd resin-containing paint system (Alkydlasur A / Table 1) in the presence of a transition metal drier (Co) and a metal oxide pigment (iron oxide).
• a typical alkyd resin-containing paint system Alkydlasur A / Table 1
• a transition metal drier Co
• a metal oxide pigment iron oxide
• IPBC an additional IPBC concentrate from Table 2 is added.
• IPBC is incorporated directly (unstabilized IPBC) or a concentrate from Table 3 (stabilized IPBC according to EP 2236033).
• the composition of the finished glazes is shown in Table 4. In all examples, the IPBC concentration in the glazes is 0.7%.
• IPBC 1 corresponds in each case to 0.7% by weight IPBC, based on the glaze.
• Table 5 Stability of the IPBC in alkyd stains A (-1) to (-V) at 40 ° C
• A-IV1) 100 96 52 0

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