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
  • 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
  • A01N47/18—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, directly attached to a heterocyclic or cycloaliphatic ring
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
  • Y10T428/249925—Fiber-containing wood product [e.g., hardboard, lumber, or wood board, etc.]

Definitions

• the present invention relates to multi-phase aqueous suspension emulsions and their use for the treatment of wood against attack by wood-damaging fungi.
• fenpropimorph (4- [3- ⁇ 4-tert-butylphenyl ⁇ -2-methylpropyl] -2, 6-cis-dimethylmorpholine) is generally known (cf. DE-A 26 56 747).
• WO-A 95/16349 discloses fungicidal mixtures and compositions for plant protection containing them which contain fenpropimorph and a triazole compound as active substances.
• Synergistic mixtures of triazole compounds are also common in wood preservation [propiconazole + tebuconazole: EP-A 393 746].
• DE-A 43 40 853 teaches a synergistic mixture for use in wood protection which, in addition to a copper compound and an alkanolamine, contains a triazole compound and a further fungicide, for example fenpropimorph.
• WO 97/39865 describes synergistic mixtures of fenpropimorph and various triazoles for use in wood protection. The combination of such mixtures with benzimidazoles or these releasing precursors is not described.
• EP 707 445 describes suspoemulsions based on the triazole epoxiconazole for crop protection.
• the solvents used there are not very suitable for use in wooden contactors, since they evaporate relatively quickly due to their high vapor pressure, which leads to destabilization. tion of the oil phase or breakage of the emulsion.
• m closed halls there is the problem of odor pollution when it is considered to be used as a wood treatment agent.
• the treatment systems in Pflan ⁇ zenschutz and wood preservatives are very different from each other and in that, as a rule in aqueous crop protection tank mix spray to brew only one Emulsionstabilitat of m usually needed a few hours and additionally then this Tankmixe be applied even dysentery factory supports can.
• aqueous treatment systems for weeks and months len be stable.
• the emulsions, suspoemulsions or microemulsions used up by the wood are replenished by treatment concentrates newly added with water, without the stability of a plunge pool mixture being adversely affected.
• aqueous emulsions in contrast to plant protection in wood protection completely different quality criteria, so that only partially formulated technical problem solving according to the prior art from plant protection m the wood protection can be transferred.
• BCM carbendazim
• fungicides fungicides
• wood preservatives have been widely described in the literature.
• the problem for BCM is that practically no water-insoluble solvents are known which are able to dissolve BCM at high concentrations and thus stabilize with surfactants as an emulsion or microemulsion.
• Water-soluble solvents caused the BCM to precipitate out or crystallize out again after the strong dilution.
• BCM is used.
• CA 97: 51133 describes phosphoric acid salts from BCM.
• BCM salts of this type are, however, completely unsuitable for use in high dilution, especially when using weakly basic tap water, since deprotomerization, crystal formation or precipitation of BCM occurred very quickly, which is then roughly particulate in the range >> 10 mm, is practically no longer effective and sediments very quickly.
• JP 03251507 Another possibility is offered by suppressing de sedimentation or the crystal growth of BCM using xanthan. However, this generally leads to very high xanthan fractions of approx. 0.2% based on the application concentration or the tank or. Plunge pool mix.
• the xanthans like the active ingredients, had to be used in the 100 g range of the finished formulation. This is not technically possible, since an excess of 0.2% xanthan gum in the suspoemulsion concentrate sets an extremely high viscosity and such formulations are no longer flowable and tend to provide gel-like or already solid products that procedurally completely unsuitable.
• the present invention was therefore based on the object of developing active substance-based, highly concentrated and liquid formulations with carbendazim and active substances from the class of the morpholes, nurses and / or cycloams or triazoles, which, as suspension emulsions for application in wood protection, have good storage stability of the suspoemulsion and have good long-term stability of the aqueous application agent. Furthermore, easily evaporable, odor-polluting, health-endangering and especially chlorine-containing solvents should be avoided. In addition, it should be possible to formulate the active ingredients at a high concentration.
• the systems according to the invention should make it possible to demonstrate economically and ecologically improved processes for wood protection.
• this object is achieved by multiphase aqueous suspension emulsions containing essential components
• fungicidal active ingredient from the class of the benzimidazoles or the precursors of the formulas 1.1 releasing them. up to 1.4 as microsuspended solid particles,
• fungicidal active ingredient selected from compounds of the formulas II.1. to II.5 and
• n a value from 0 to 3
• R 1 is hydrogen, -CC 8 alkyl, C 6 -C 4 -aryl, C 6 -C 4 -aryl- C: -C 8 alkyl-, halogen, -C-C 6 alkoxy.
• connections 1.1 to 1.4 are known per se:
• compound I is the active ingredient which is commercially available under the common name carbendazim.
• the proportion of the compounds of Fortmel I is in the range from 1 20 to 50, preferably from 5 to 30 and in particular from 10 to 20% by weight, based on the total weight of the multiphase suspension emulsion.
• Component b (emulsion) generally makes up 5 to 60, preferably 10 to 50 and particularly preferably 20 to 40,% by weight of the multiphase suspension emulsion.
• the proportion of morpholine derivatives in emulsion b) is generally in the range from 20 to 90, preferably in the range from 40 to 45,% by weight, based on the total weight of component b.
• III.1 common name: bromuconazole, Proc. Br. Crop Prot. Conf. - Pests Dis., 5-6, 439 (1990);
• III.2 common name: cyproconazole, US-A 4,664,696;
• III. common name: Fiuqumconazol Proc. Br. Crop Prot. Conf. - Pest Dis. , 5-3, 411 (1992);
• III 9 common name: hexaconazole, CAS RN [79983-71-4]; III 10 common name: Metconazole, Proc. Br. Crop Prot. Conf. -Pests Dis., 5-4, 419 (1992);
• III 13 common name: tebuconazole, US-A 4,723,984; III 14 common name: tetraconazole, Proc. Br. Crop Prot. Conf. - Pest Dis. , 1, 49 (1988);
• III 17 common name: Myclobutani l, CAS RN [88671 - 89 - 0]
• Propiconazole, penconazole, cyproconazole, hexaconazole, tebuconazole and mixtures thereof are used with particular advantage as the triazole compound.
• the proportion of the azole active ingredients III in the emulsion b) is generally in the range from 0 to 60, preferably from 10 to 40 and particularly preferably from 20 to 35% by weight.
• aromatic esters of the formula IV are known derivatives of benzoic acid, the preparation of which is known per se to the person skilled in the art and is described in the literature.
• the benzyl esters of benzoic acid are preferred.
• the proportion of the compounds IV in the emulsion b) is generally in the range from 0 to 55, preferably from 10 to 50 and particularly preferably from 25 to 35% by weight.
• the multiphase suspension emulsions according to the invention can be used in emulsion b as mixtures of active ingredients II with aromatic esters of formula IV, mixtures of active ingredients II and active ingredients of formula III (preferred) or mixtures of compounds of formula II, compounds of formula III and
• wood secondary products such as
• the compounds II and the azole compounds III are generally in the form of the free base.
• Typical pH values strength by weight of a 1% Wass I Q ring Struktursbruhe be in the range of 6.5 to 9, preference, in the range 7 to 8
• the components of emulsion b) should preferably have an oil phase density in the range from 0.95 to 1.05, preferably from 0.975
• a mixing ratio in the range of 1.5 has been used to set a suitable density : 1 to 5: 1, in particular from 2: 1 to 4: 1 as suitable and advantageous.
• An component composed of fen propimorph and propiconazole is particularly preferably used as component b.
• the aromatic esters of the formula IV can also be improved according to the invention to adjust the oil phase density of the emulsion containing the active compounds of the formula II. Triazoles are therefore not absolutely necessary to achieve the desired effect.
• 45 is usually 30 to 200 g / 1, preferably in the range from 50 to 150 g / 1, based on the overall formulation.
• the preparation of the multiphase aqueous suspension emulsions according to the invention can be carried out in a manner known per se, e.g. carried out according to the method described in EP-A 707,445, so that further details are unnecessary here.
• the azole component III can also be present as a suspension concentrate portion (SC portion) in a mixture with a compound of the formula I, in particular when the melting point of the azole is above 100 ° C. and at the same time its Lichity active ingredients of formula II or compounds of formula IV less than 10g / l, in particular less than 2 g / 1.
• SC portion suspension concentrate portion
• An example of such an azole component, which advantageously as a mixture with e.g. Carbendazim can be formulated is Epoxi conazol.
• the multiphase aqueous suspension emulsions according to the invention can also be added
• Alkali, alkaline earth or ammonium salts of aromatic sulfonic acids e.g. Lignm-, Phenol-, Naphthalin- and Dibutylnaphthalmsulfonsaure, as well as from
• alkylaryl polyether alcohols alkylaryl polyether alcohols, isotridecyl alcohol, ethoxylated castor oil, ethoxylated t ⁇ arylphenols, salts of phosphated triarylphenol ethoxylates, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfate leaching or methyl cellulose or mixtures thereof.
• surface-active substances are also used, their proportion is generally in the range from 0.5 to 25% by weight, based on the total weight of the suspension emulsion according to the invention.
• Non-ionic, cationic and anionic emulsifiers can be used as emulsifiers. Quaternary ammonium compounds and alkoxylated, especially ethoxylated: fet talc alcohols, oxo alcohols and oils (ricmusol, fish oil) are preferred.
• fatty amines have been found as an emulsifier, which are alkoxylated with from 2 to 25 moles of ethylene oxide, such as Ethomen ® C 15, Ethomen® T23 or S20 Ethomen® (Akzo Chemicals GmbH, Duren 52355, Germany).
• the abovementioned losungs--containing formulations or emulsion concentrates can with white ⁇ more advanced drugs combined, which are incorporated in the latter case with suitable additional emulsifiers.
• Suitable mixing partners are e.g. the following connections:
• Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet;
• Benzimidazoles such as Carbendazim, Benomyl, Fube ⁇ dazole, Thiabendazole or their salts;
• Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate
• quaternary ammonium compounds such as benzyldimethyletradecylamomum chloride, benzyldimethyldodecylammonium chloride, didecyl dimethylammonium chloride;
• Iodine derivatives such as di-odmethyl-p-tolysulfone, 3-iodo-2-propmyl alcohol, 4-chlorophenyl-3-] odpropargyl formal, 3-bromo-2, 3-d ⁇ -; iodine-2-propenylethyl carbonate, 2,3, 3rd -T ⁇ jodallylalkohol, 3-bromo-2, 3-d ⁇ -] od-2-propenyl alcohol, 3-iodo-2-propmyl-n-butyl carbamate, 3-iodo-2-propionyl-n-hexyl carbamate, 3-iodo 2-prop ⁇ - nyl-cyclohexyl carbamate, 3-iodo-2-propmyl-phenyl carbamate, 0-1- (6-iodo-3-oxo-hex-5-myl) butyl carbamate, 0-1- (6-iodo-3 -oxo-
• Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol; Bromine derivatives such as 2-bromo-2-mtro-i, 3-propanediol, 2-bromo-2-bromomethyl-glutardinol;
• Isothiazole mones such as N-methyl-isothiazolm-3-one, 5-chloro-N-methyl-isothiazolm-3-one, 4,5-di-chloro-N-octyl-isothioazo lm-3-one, N-octyl-isothiazolm-3-one;
• Benzisothiazolmone such as 4, 5-T ⁇ methyl ⁇ soth ⁇ azol-3-one
• Metal soaps such as tin, copper, zinc naphthenate, octate, 2-ethylhexanoate, oleate, phosphate, benzoate.
• Organozmn compounds e.g. Tributyl (TBT) compounds, dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide;
• TBT Tributyl
• dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide
• Benzothiazoles such as 2-mercaptobenzoth ⁇ azole
• Chmolme such as 8-hydroxychmolm and their Cu salts or Qui noxyfen
• Phosphoric acid esters such as azmphos-ethyl, azmphos-methyl,
• Pyrethroids such as Allethnn, Alphamethrm, Bioresmethrm, By fenthrm, Cycloproth, Cyfluth m, Decamethrm, Cyhalothrm, Cypermethrm, Deltamethrm, a-Cyno-3-phenyl-2-methyl-ben cyl-2, 2-dimethyl-3- (2- chloro-2-t ⁇ fluormethylvmyl) cyclopro pancarboxylat, Fenpropathrm, Fenfluthrm, Fenvalerate, Flucyythrmate, Flumethr n, Fluvalmate, Permethrm, Resemethrm and Tralomethrm;
• Nitroimme and nitromethylenes such as 1- ((6-chloro-3-py ⁇ d ⁇ - nyl) methyl) -4, 5-d ⁇ hydro-N-n ⁇ tro-lH- ⁇ m ⁇ dazol-2-amm (midaclo p ⁇ d), N- ((6- Chloro-3-pyridyl) methyl) -N '-cyano-N' -methyl acetamide;
• Suitable water-insoluble organic acids are e.g. aliphatic or aromatic mono- or polycarboxylic acids, e.g.
• an aliphatic unbranched monocarboxylic acid with 5 to 20 carbon atoms such as hexanoic acid, heptanoic acid, octanoic acid, nonane acid and decanoic acid
• an aliphatic branched monocarboxylic acid with 5 to 20 carbon atoms such as 2-ethylpentanoic acid, 2-ethylhexane acid, 2-ethylheptanoic acid, isooctanoic acid , Isononanoic acid and versatic acid, or neocarboxylic acid (more strongly branched monocarboxylic acid), or an aliphatic dicarboxylic acid with 5 to 20 carbon atoms such as sebacic acid and decanedicarboxylic acid, or an aromatic or aromatic / aliphatic carboxylic acid such as naphthenic acid and benzoic acid.
• Such acids are preferably used as anions of metal salts, in particular of alkali or alkaline earth metals, optionally as Cu salts, ammonium or organic ammonium salts derived from primary, secondary or tertiary amines or quaternary ammonium salts.
• aqueous multiphase suspension emulsions according to the invention or their aqueous dilutions may additionally contain binders, e.g. Oil-soluble or water-thinnable alkyd resins, acrylic dispersion, or in the case of primers, which are approx. 2 to 10% by weight
• binders e.g. Oil-soluble or water-thinnable alkyd resins, acrylic dispersion, or in the case of primers, which are approx. 2 to 10% by weight
• Solid resin or glazes Contain solid resin or glazes, which contain approx. 10 to 25% solid resin, also inorganic or organic pigment preparations.
• gene, water and ollosische dyes, "water repellants” such as metal stearates or waxes and / or other auxiliaries such as dryers, wetting agents and penetration aids are added.
• the application for protecting the wood can e.g. e after the wood is endangered:
• the concentration of the fungicidal mixture in the respective wood preservative mostly depends on the degree of danger to the wood to be treated by the fungi and also on the selected application method.
• undiluted concentrates e.g. plywood, chipboard, bagasse panels.
• the success of the treatment with the fungicidal mixtures or the ready-to-use wood preservatives, in particular with the suspension emulsions according to the invention, also generally depends on the application process.
• these When using dilute systems, these generally contain 0.1 to 3, preferably 0.3 to 1.5% of the suspension emulsion according to the invention, the remainder being water or a mixture of water / organic solvent; Water is preferred.
• the mixtures and wood preservatives used in accordance with the invention provide particularly effective protection against wood-coloring fungi, especially blue fungi and, in particular, Aureobasidium pullulans and Sclero phoma pityophila, which are paid for the Ascomycetes.
• Basidiomycetes e.g. Serpula lacrymans, Coniophora quina
• mold eg Aspergillus m ger
• mold rot eg Chaetomium globosum
• suspoemulsions according to the invention with the recipes according to Tables 1a, 1b and 2 and application agents can be prepared in a manner analogous to that described in EP 707 445.
• This document also contains information regarding the properties of EC and SC formulations.
• the multiphase systems described in EP 707 445 are generally also, like the formulations of the present invention, suspension emulsions which consist of a water phase, an oil phase (also called an EC phase) and an SC phase.
• suspension emulsions according to the invention according to Tables 1a, 1b and 2 below were prepared by introducing an oil phase of the composition given in the table into a suspension concentrate of the active ingredient carbendazim (1.2) with vigorous stirring or dispersing or shearing and thus suspoemulsifying
• BCM carbendazim
• BCM-Stamm-SC carbendazim suspension
• 500 g of BCM (calc. 100% active ingredient) are stirred into 500 ml of distilled or deionized water and 20 g of Pluronic PE 10500 and 20 g of Wettol Dl 1 1 metered.
• Pluronic PE 10500 and 20 g of Wettol Dl 1 1 metered.
• the mixture was then milled in a ball mill with cooling to 10 ° C. until a particle size of 80% ⁇ 2 microns had been established.
• This BCM stock suspension was then proportionately according to u. G. Recipes used for all suspo emulsions.
• the finished formulations according to Table la were 0.7 and 2.8% with tap water ad. Diluted 150 ml and homogenized for 5 minutes with a magnetic stirrer. Subsequently, calibrated 100 ml pointed cylinders were filled completely and air-free with the diluted suspo emulsions, closed with a stopper and set up with the calibrated tip upwards or upside down with the stopper down.
• the frame is read m mm, then shaken 30 times or largely rehomogenized and left to stand again.
• JU naten by determining the proportion of particles with a particle size of less than 2 microns gave la-1 a value of 46.5 and 51.1% (at 40 and 50 ° C); the corresponding values for la-2 were 36.5 and 35.1%.
• La each contain 1.8 g / 1 of the biocide Kathon TM MK, commercial product from Rohm and Haas (Philadelphia) and 2.5 g / 1 of the antifoam as further components Silicon SRE, commercial product from Wacker-Chemie.
• the desired densities were adjusted by 1.0 g ml by iteratively mixing FPM with the components 2-phenylphenol or dimethyl phthalate.
• test was carried out according to test series I.
• Table 2 contains information on auxiliaries and active substances g / 1 under 0.5% application concentration of the suspo emulsions and results on framing tests according to table 1. Furthermore, the storage stability of the suspo emulsions used is described in the form of particle sizes.
• All formulations according to Table 2 contain 0.2 g / 1 1, 2-propylene glycol, 0.01 g / 1 antifoaming agent Silicon SRE (product from Wacker-Chemie GmbH) and 0.01 g / 1 as further inert components of the Bioeids Kathon TM MK.
• the formulation 2c according to the invention gives a significant improvement in the framing behavior under use concentrations.
• the suspension emulsions according to the invention are generally used 0.1-3%, but preferably 0.3-1.5% in water as wood treatment agent.
• the optimal application rate of the suspo emulsions varies depending on the microbiological hazard potential of the wood. Regional quantities and qualities of existing microorganisms and pathogens require an adapted application rate depending on the treatment method and average temperature of the wood storage conditions.

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• Life Sciences & Earth Sciences (AREA)
• Dentistry (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Agronomy & Crop Science (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Chemical And Physical Treatments For Wood And The Like (AREA)

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• 1998
  • 1998-07-28 DE DE19834028A patent/DE19834028A1/de not_active Withdrawn
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  • 1999-07-14 WO PCT/EP1999/004968 patent/WO2000005955A1/de not_active Ceased
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  • 1999-07-14 AT AT99934692T patent/ATE238659T1/de active
  • 1999-07-14 ES ES99934692T patent/ES2199584T3/es not_active Expired - Lifetime
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