DK162146B - PESTICID AGENT FOR TREATMENT OF TREES - Google Patents
PESTICID AGENT FOR TREATMENT OF TREES Download PDFInfo
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- DK162146B DK162146B DK320683A DK320683A DK162146B DK 162146 B DK162146 B DK 162146B DK 320683 A DK320683 A DK 320683A DK 320683 A DK320683 A DK 320683A DK 162146 B DK162146 B DK 162146B
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- 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
- A01N25/02—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 liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/38—Aromatic compounds
- B27K3/40—Aromatic compounds halogenated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/50—Mixtures of different organic impregnating agents
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Agronomy & Crop Science (AREA)
- Dispersion Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (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)
Description
DK 162146 BDK 162146 B
Den foreliggende opfindelse angår et pesticidt middel til behandling af træ, f.eks. af bygningstømmer eller af træ til snedkerarbejde, indeholdende en i vand uopløselig pe-sticidbestanddel, en syntetisk harpiks, der kan fortyndes 5 med vand, en vandopløselig emulgator og en aminogruppe-holdig forbindelse. Opfindelsen angår især sådanne midler, der foreligger på koncentreret form, og som kan fortyndes med vand, før de tages i brug, såvel som sådanne midler, der er fortyndet med vand, og er klar til anven-10 delse.The present invention relates to a pesticidal agent for treating wood, e.g. of building timber or wood for carpentry, containing a water-insoluble pesticide component, a synthetic resin which can be diluted with water, a water-soluble emulsifier and an amino group-containing compound. In particular, the invention relates to such agents which are in concentrated form and which can be diluted with water before they are put into use, as well as such agents which are diluted with water and are ready for use.
Fra US patentskrift nr. 3 281 318 kender man pesticide midler af denne art, som består af vandige emulsioner af blandinger af en polychlorphenol, en voksart, en fedtsy-15 re, en ikke-ionisk emulgator og en alkanolamin. Den ikke-ioniske emulgator har i disse kendte pesticide midler til funktion at forstærke emulsionens homogenitet, og alka-nolaminen, som fortrinsvis er ethanolamin, har til opgave at lette dispergeringen af fedtsyren og af polychlorphe-20 nolen. Disse kendte pesticide midler udviser grundet til stedeværelsen af en voksart, der har til opgave at fungere som fikseringsmiddel for polychlorphenolen, den ulempe, at de kun med vanskelighed lader sig bruge til imprægnering i tilstrækkelig dybde af de behandlede emner 25 af træ, og den beskyttelse, som de sikrer, er af kort varighed. Disse pesticide midlers stabilitet er i øvrigt usikker.U.S. Patent No. 3,281,318 discloses pesticidal agents of this kind, which consist of aqueous emulsions of mixtures of a polychlorophenol, a wax, a fatty acid, a nonionic emulsifier, and an alkanolamine. The nonionic emulsifier has in these known pesticidal agents to enhance the homogeneity of the emulsion, and the alkanolamine, which is preferably ethanolamine, is intended to facilitate the dispersion of the fatty acid and of the polychlorophenol. These known pesticidal agents, due to the presence of a wax species which has the function of acting as a fixing agent for the polychlorophenol, exhibit the disadvantage that they can only be used with difficulty to impregnate in sufficient depth of the treated articles 25 of wood, and the protection which they ensure is of short duration. The stability of these pesticides is otherwise uncertain.
Man har til afhjælpning af disse ulemper i tysk patent-30 fremlæggelsesskrift nr. DE-A 3 004 319 foreslået pesticide midler i vandige emulsioner, hvori man for at sikre fikseringen af de aktive bestanddele til træet anvender en syntetisk harpiks, der lader sig fortynde med vand, sammen med en amin, idet den anvendte emulgator ligeledes 35 er ikke-ionisk.In order to alleviate these drawbacks, German Patent Publication No. DE-A-3 004 319 has proposed pesticidal agents in aqueous emulsions, in order to ensure the fixation of the active ingredients to the wood, a synthetic resin which can be diluted with water, together with an amine, the emulsifier used being also non-ionic.
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Den foreliggende opfindelse har til formål at tilvejebringe pesticide midler af denne art. Det har overraskende vist sig, at der ved anvendelse af en speciel anionisk emulgator og en speciel aminogruppeholdig forbindelse op-5 nås midler, som efter fortynding med vand fremtræder som en faktisk opløsning, idet de især er i besiddelse af transparens, som er forsynet med en fremragende stabilitet, og som har en høj penetrationsevne ind i træet.The present invention has for its object to provide pesticidal agents of this kind. Surprisingly, it has been found that by using a special anionic emulsifier and a special amino group-containing compound, agents are obtained which, after dilution with water, appear as an actual solution, having in particular the transparency provided with excellent stability and having a high penetration ability into the wood.
10 Med henblik herpå angår opfindelsen pesticide midler til behandling af træ bestående af et i vand uopløseligt pe-sticidemiddel, en syntetisk harpiks, der lader sig fortynde med vand, en vandopløselig emulgator og en aminogruppeholdig forbindelse, hvilket middel er ejendommeligt 15 ved det i krav l's kendetegnende del anførte.For this purpose, the invention relates to pesticidal agents for treating wood consisting of a water-insoluble pesticide, a water-soluble synthetic resin, a water-soluble emulsifier, and an amino group-containing compound, the agent of which is claimed. l's characteristic part stated.
Den omtalte pesticid-aktive bestanddel kan i midlet ifølge opfindelsen være et hvilket som helst i vand uopløseligt pesticidmiddel, således som det almindeligvis anven-20 des i pesticide præparater til behandling af træ. Det kan være et fungicid, der er uopløseligt i vand, eller et insekticid, der er uopløseligt i vand. De pesticide midler ifølge opfindelsen kan efter behov indeholde flere i vand uopløselige fungicider eller flere i vand uopløselige in-25 sekticider eller en blanding af et eller flere i vand uopløselige fungicider og et eller flere i vand uopløselige insekticider.The aforementioned pesticide active ingredient may in the composition of the invention be any water-insoluble pesticide agent, as is commonly used in pesticidal wood treatment compositions. It can be a water-insoluble fungicide or an insoluble water-insecticide. The pesticidal compositions of the invention may contain, as needed, more water-insoluble fungicides or more water-insoluble insecticides or a mixture of one or more water-insoluble fungicides and one or more water-insoluble insecticides.
Som eksempler på i vand uopløselige insekticider, der la-30 der sig anvende i det pesticide middel ifølge opfindelsen, kan nævnes pyrethrum, pyrethroiderne (såsom pyre-thrin, allethrin, cyclethrin, furethrin, tetramethrin, decamethrin og bioresmethrin), carbamater med insekticid virkning (såsom propoxur), estere af phosphoniumsyre, 35 phosphorsyre, thiophosphorsyre, dithiophosphorsyre eller thionophosphorsyre, chlorerede carbonhydrider, såsom me-thoxychlor, lindan, chlordan, heptachlor, aldrin og di- 3Examples of water-insoluble insecticides used in the pesticidal composition of the invention include pyrethrum, pyrethroids (such as pyrethrin, allethrin, cyclethrin, furethrin, tetramethrin, decamethrin and bioresmethrin), insecticidal carbamates. (such as propoxur), esters of phosphonic acid, phosphoric acid, thiophosphoric acid, dithiophosphoric acid or thionophosphoric acid, chlorinated hydrocarbons such as methoxychlor, lindane, chlorine, heptachlor, aldrin and di-3
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eldrin.eldrin.
Som eksempler på 1 vand uopløselige fungicider, der lader sig anvende i det omhandlede pesticide middel, kan nævnes 5 organiske forbindelser af tetravalent tin (såsom tribu-tyltinbenzoat, tris(tributyl-tin)phosphat og oxidet af bis(tributyltin), 1-trityl-l,2,4-triazolforbindelserne med den almene formel: 10 N i / o-j-oExamples of 1 water-insoluble fungicides which can be used in the present pesticide include 5 organic compounds of tetravalent tin (such as tributyltin benzoate, tris (tributyltin) phosphate and the oxide of bis (tributyltin), 1-trityl The 1,2,4-triazole compounds of the general formula: 10 N in / o
Rn 20 hvori R betegner et fluoratom, et chloratom eller et bromatom, en trifluormethylgruppe, en nitrogruppe eller cyangruppe, eller en alkylgruppe indeholdende op til 4 25 carbonatomer, og hvori n angiver et af tallene 1 eller 2, såvel som organiske eller uorganiske syreadditionssalte deraf (f.eks. trifluormethyl-triphenyl-methyltriazol), hexachlorbenzen, pentachlorbenzen, chelater med fungicid virkning af tris-(N-cyclohexyldiazeniumdioxid)-metal, 30 især sådanne, hvori aluminium indgår, og som man finder i et produkt, som kendes under betegnelsen "Xyligen Al" (BASF), N,N-dimethyl-N'-phenyl-N'-(fluordichlormethyl- thio)-sulfamid, Ν,Ν-dimethyl-N'-p-tolyl-N'-(dichlorfluor-methylthio)-sulfamid, chlorerede naphthalener, kobber- og 35 zinknaphtenater, mercaptobenzothiazolforbindelserne og salte deraf, 8-hydroxyquinolin og salte deraf, organo-bor-estere, kvaternære ammoniumforbindelser som derivater 4Rn 20 wherein R represents a fluorine atom, a chlorine atom or a bromine atom, a trifluoromethyl group, a nitro group or cyano group, or an alkyl group containing up to 4 25 carbon atoms and wherein n represents one of the numbers 1 or 2, as well as organic or inorganic acid addition salts thereof (e.g., trifluoromethyl-triphenylmethyl triazole), hexachlorobenzene, pentachlorobenzene, chelates with fungicidal action of tris (N-cyclohexyldiazenium dioxide) metal, especially those containing aluminum and found in a product known under designation "Xyligen A1" (BASF), N, N-dimethyl-N'-phenyl-N '- (fluorodichloromethylthio) sulfamide, Ν, Ν-dimethyl-N'-p-tolyl-N' - (dichlorofluorobenzyl) methylthio) sulfamide, chlorinated naphthalenes, copper and zinc naphthenates, the mercaptobenzothiazole compounds and their salts, 8-hydroxyquinoline and their salts, organo boro esters, quaternary ammonium compounds as derivatives 4
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deraf, kondensationsforbindelser afledt af diphenylaminer og acetone, N-cyclohexyl, N-methoxy, 2,5-dimethylfuran-3-carboxamid, som man finder i det produkt, der kendes under betegnelsen "Xyligen B" (BASF), N-(trichlormethyl-5 thio)-phthalimid, 5-ethoxy-3-trichlormethyl-l,2,4-thia-diazol, 2-(3-thiazolyl)-benzimidazol, 5-n-butyl-2-dime-thylamino-4-hydroxy-6-methyl-pyrimidin, ortho-phenylphe-nol og paraphenylphenol.thereof, condensation compounds derived from diphenylamines and acetone, N-cyclohexyl, N-methoxy, 2,5-dimethylfuran-3-carboxamide found in the product known as "Xyligen B" (BASF), N- (trichloromethyl) 5-thio) -phthalimide, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2- (3-thiazolyl) -benzimidazole, 5-n-butyl-2-dimethylamino-4-hydroxy -6-methyl-pyrimidine, ortho-phenylphenol and paraphenylphenol.
10 Man vælger det pesticidt aktive middel i de pågældende pesticide midler blandt chlorerede phenoler i en særlig fordelagtig udførelsesform for opfindelsen. De foretrukne chlorerede phenoler er polychlorphenoler, tetrachlorphe-nol, og pentachlorphenol har vist sig at være særligt 15 fordelagtig.The pesticide active agent of the pesticidal agents concerned is selected from chlorinated phenols in a particularly advantageous embodiment of the invention. The preferred chlorinated phenols are polychlorophenols, tetrachlorophenol, and pentachlorophenol have been found to be particularly advantageous.
Den syntetiske harpiks, der lader sig fortynde med vand, og som er til stede i det pesticide middel ifølge opfindelsen, er fortrinsvis en alkydharpiks, som er opløselig 20 i vand takket være dannelsen af et salt med en amino-gruppeholdig forbindelse, eller en med acryl modificeret alkydharpiks, såsom den, der kendes under handelsmærket Hydrorob (Robbe).The water-dilutable synthetic resin present in the pesticidal agent of the invention is preferably an alkyd resin which is soluble in water thanks to the formation of a salt having an amino group-containing compound or a acrylic modified alkyd resin, such as that known by the trademark Hydrorob (Robbe).
25 Emulgatoren i de omhandlede forbindelser en anionisk emulgator og valgt blandt ammonium- og alkalimetalalkyl-benzensulfonater med den almene formel: R - S03 - M 30 hvori M betegner aminogruppen eller en alkalimetalgruppe, f.eks. natrium, og hvori R betegner en alkylbenzengruppe.The emulsifier of the present compounds is an anionic emulsifier and selected from ammonium and alkali metal alkylbenzenesulfonates of the general formula: R - SO3 - M 30 wherein M represents the amino group or an alkali metal group, e.g. sodium and wherein R represents an alkylbenzene group.
Alkylbenzensulfonaterne kan være ligekædede alkylbenzen-35 sulfonater eller forgrenede alkylbenzensulfonater; man foretrækker de ligekædede alkylbenzensulfonater, der i almindelighed betegnes "LAS". Særligt fordelagtige lige-The alkylbenzenesulfonates may be straight-chain alkylbenzene sulfonates or branched alkylbenzenesulfonates; preferred are the straight-chain alkylbenzene sulfonates, commonly referred to as "LAS". Particularly advantageous equal-
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kædede alkylbenzensulfonater er sådanne, hvis alkylkæde indeholder fra 8 til 18 carbonatomer, især fra 12 til 14 carbonatomer; dodecylbenzensulfonaterne, især natriumsaltet af dodecylbenzensulfonat, egner sig særdeles godt.chain alkylbenzene sulfonates are those whose alkyl chain contains from 8 to 18 carbon atoms, especially from 12 to 14 carbon atoms; the dodecylbenzenesulfonates, especially the sodium salt of dodecylbenzenesulfonate, are particularly suitable.
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Det anioniske overfladeaktive middel kan i de omhandlede midler anvendes, således som det foreligger, eller i form af en dispersion eller en opløsning i et organisk opløsningsmiddel eller i vand, dersom man ønsker at formindske 10 viskositeten deraf. Man opnår i almindelighed for opfindelsens rammer emulgerede produkter, som indeholder 30 til 80 vægtdele ammonium- eller alkalimetal-alkylbenzen-sulfonater indeholdende 10-14 carbonatomer i alkylkæden, samt 20 til 70 vægtdele af et eller flere organiske op-15 løsningsmidler og/eller vand. De bedste resultater opnås sædvanligvis med sådanne emulgerende produkter, som indeholder fra 40 til 60 vægtdele alkylbenzensulfonat(er) og fr§. 30 til 50 vægtdele organisk(e) opløsningsmiddel (ler) og/eller vand.The anionic surfactant can be used in the present compositions, as is present, or in the form of a dispersion or solution in an organic solvent or in water, if it is desired to decrease its viscosity. In general, emulsified products containing 30 to 80 parts by weight of ammonium or alkali metal alkyl benzene sulfonates containing 10-14 carbon atoms in the alkyl chain are obtained, and 20 to 70 parts by weight of one or more organic solvents and / or water. . The best results are usually obtained with such emulsifying products which contain from 40 to 60 parts by weight of alkyl benzene sulfonate (s) and sections. 30 to 50 parts by weight of organic solvent (s) and / or water.
2020
De alkanolaminer, som indgår i det omhandlede pesticide middel, kan være konventionelle produkter, hvori alkanol-gruppen består af 2-4 carbonatomer, og som opnås ved omsætning mellem ammoniak og ethylenoxid, propylenoxid el-25 ler butenoxid, såsom monoethanolamin, diethanolamin, tri-ethanolamin, monoisopropanolamin, diisopropanolamin, tri-isopropanolamin, mono-sek-butanol, di-sek.-butanolamin og tri-sek.-butanolamin. Man foretrækker dog sådanne alkanolaminer, hvor alkanolgruppen består af 2 til 4 carbon-30 atomer, og som er substitueret med mindst én alkylgruppe eller phenylgruppe fortrinsvis bestående af 1 til 8 carbonatomer, især til sådanne alkanolaminer, der er substitueret med to alkylgrupper, som fortrinsvis indeholder 1-4 carbonatomer. Eksempler på sådanne alkanolaminer er på 35 den ene side methylethanolamin, butylethanolamin, phenyl-ethylethanolamin, methyldiethanolamin, ethyldiethanolamin og phenyldiethanolamin, og på den anden side dimethyl-The alkanolamines included in the subject pesticide may be conventional products wherein the alkanol group consists of 2-4 carbon atoms and is obtained by reaction between ammonia and ethylene oxide, propylene oxide or butene oxide such as monoethanolamine, diethanolamine, tri -ethanolamine, monoisopropanolamine, diisopropanolamine, tri-isopropanolamine, mono-sec-butanol, di-sec-butanolamine and tri-sec-butanolamine. However, such alkanolamines are preferred where the alkanol group consists of 2 to 4 carbon atoms and is substituted by at least one alkyl group or phenyl group preferably consisting of 1 to 8 carbon atoms, especially to such alkanolamines substituted by two alkyl groups, preferably contains 1-4 carbon atoms. Examples of such alkanolamines are, on the one hand, methylethanolamine, butylethanolamine, phenylethylethanolamine, methyldiethanolamine, ethyl diethanolamine and phenyldiethanolamine, on the other
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6 ethanolamin, diethylethanolamin, diisopropylethanolamin, dibutylethanolamin og dimethylisopropanolamin. Man har opnået de bedste resultater med alkanolaminer, hvis størkningspunkt er lavere end -25 °C, fortrinsvis lavere 5 end -50 °C, og i særdeleshed med diethylethanolamin.6 ethanolamine, diethylethanolamine, diisopropylethanolamine, dibutylethanolamine and dimethylisopropanolamine. The best results have been obtained with alkanolamines whose solidification point is lower than -25 ° C, preferably lower than -50 ° C, and especially with diethylethanolamine.
Den relative mængde alkanolamin, som det er bekvemt at tage i arbejde, kan let bestemmes eksperimentelt, og den afhænger af forskellige faktorer, blandt hvilke især fi-10 gurerer arten af alkanolaminen, såvel som arten og den relative mængde af hver af bestanddelene i midlet, samt den ønskede koncentration for den vandige emulsion, som skal dannes. Som en almen regel har det vist sig ønskværdigt at indrettet vægtindholdet af alkanolaminen på en 15 sådan måde, at forholdet mellem vægten af alkanolamin og vægten af midlet med pesticid virkning er på mellem 0,1 og 2, fortrinsvis mellem 0,25 og 1,25, idet man har opnået de mest fordelagtige resultater med vægtforhold på mellem 0,5 og 1.The relative amount of alkanolamine conveniently employed can be readily determined experimentally, and it depends on various factors, among which, in particular, the nature of the alkanolamine, as well as the nature and relative amount of each of the ingredients in the agent, is determined. , as well as the desired concentration of the aqueous emulsion to be formed. As a general rule, it has been found desirable to arrange the weight content of the alkanolamine in such a way that the ratio of the weight of alkanolamine to the weight of the pesticidal action agent is between 0.1 and 2, preferably between 0.25 and 1. 25, having obtained the most advantageous results with a weight ratio of 0.5 to 1.
2020
Alt andet lige sikrer udvælgelsen af alkanolaminen blandt sådanne, som har et størkningspunkt lavere end -25 “C, opnåelsen af vandige emulsioner med meget stor stabilitet, som er i stand til at tåle betydelige temperaturva-25 riationer, især skiftevise perioder med frost og perioder med^optøning, uden at deres stabilitet, deres klarhed og deres penetrationsevne ind i træet lider derunder.All else being equal, the selection of the alkanolamine from those having a solidification point lower than -25 ° C ensures the achievement of very high stability aqueous emulsions capable of withstanding significant temperature variations, especially alternating periods of frost and periods. with ^ thawing, without affecting their stability, their clarity and their penetrating ability into the tree.
Man kan som en variation for at reducere kosten af mid-30 lerne, som svarer til den foretrukne udførelsesform for opfindelsen, uden at man skader egenskaberne af de dermed opnåede vandige emulsioner, substituere en del af alkanolaminen med lavt størkningspunkt med en ækvivalent mængde alkanolamin med et højere størkningspunkt. Ved 35 denne variant af opfindelsen er de relative mængder af alkanolaminer med lav og med høj størkningstemperatur, som skal anvendes, afhængig af det temperaturområde, somAs a variation to reduce the diet of the agents corresponding to the preferred embodiment of the invention without damaging the properties of the aqueous emulsions thus obtained, one can substitute a portion of the low solidification alkanolamine with an equivalent amount of alkanolamine with a higher solidification point. In this variant of the invention, the relative amounts of low and high solidification temperature alkanolamines to be used depend on the temperature range which
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7 man forudser, at de vandige emulsioner vil blive udsat for, idet den relative andel af alkanolamin med lav størkningstemperatur er desto større, jo større temperaturområdet er, og jo lavere temperaturen ved oplagringen, 5 håndteringen eller anvendelsen kan være. Det er i praksis ønskværdigt at anvende mindst 10 vægt-%, fortrinsvis mindst 20 vægt-%, alkanolamin med størkningspunkt lavere end -25 °C, fortrinsvis lavere end -50 °C. Det er i praksis ikke nødvendigt at overskride 75 vægt-%, og 10 hyppigst 50 % af en sådan alkanolamin.It is envisaged that the aqueous emulsions will be exposed, with the relative proportion of low solidification alkanolamine being larger, the greater the temperature range, and the lower the temperature at storage, handling or use. In practice, it is desirable to use at least 10% by weight, preferably at least 20% by weight, of alkanolamine having a solidification point lower than -25 ° C, preferably lower than -50 ° C. In practice, it is not necessary to exceed 75% by weight and 10 most frequently 50% of such an alkanolamine.
Den optimale mængde anionisk emulgator, der skal anvendes i de pesticide midler ifølge opfindelsen, kan ligeledes bestemmes eksperimentelt og den afhænger ligeledes af 15 forskellige faktorer, især af den valgte emulgator, såvel som arten og koncentrationen af de øvrige bestanddele.The optimum amount of anionic emulsifier to be used in the pesticidal compositions of the invention can also be determined experimentally and it also depends on 15 different factors, in particular the emulsifier chosen, as well as the nature and concentration of the other ingredients.
Det har i al almindelighed vist sig at være ønskværdigt at indrette indholdet af anionisk emulgator på en sådan måde, at forholdet mellem summen af vægtmængderne af 20 emulgator og af alkanolamin og summen af vægtmængderne af de øvrige bestanddele i midlet bortset fra vand, som normalt er uopløselige i vand, er på mellem 1 og 2, fortrinsvis mellem 1,25 og 1,50.In general, it has been found desirable to arrange the content of anionic emulsifier in such a way that the ratio between the sum of the weight amounts of 20 emulsifier and of alkanolamine and the sum of the weight amounts of the other constituents of the agent other than water which is normally insoluble in water is between 1 and 2, preferably between 1.25 and 1.50.
25 Det omhandlede pesticide middel kan udover pesticidet, der er uopløseligt i vand, indeholde den syntetiske harpiks, der kan fortyndes med vand, den anioniske emulgator og alkanolaminen samt andre bestanddele, især et blødgø-ringsmiddel og et såkaldt co-solvent.The present pesticidal agent may contain, in addition to the water-insoluble pesticide, the synthetic resin which can be diluted with water, the anionic emulsifier and the alkanolamine, and other ingredients, in particular a plasticizer and a so-called co-solvent.
3030
Man kan som blødgøringsmiddel anvende et hvilket som helst blødgøringsmiddel, der er flydende eller pastaag-tigt ved omgivelsernes temperatur. Eksempler på sådanne blødgøringsmidler er fedstyrephosphater og fedtsyreeste-35 re, såsom tributylphosphat, butylstearat, butyloleat, di-butylsebacat og dioctylphthalat. Disse blødgøringsmidler er fortrinsvis estere afledt af dicarboxylsyrer indehol- 8Any plasticizer that is liquid or paste-like at ambient temperature can be used as a plasticizer. Examples of such plasticizers are fatty acid phosphates and fatty acid esters such as tributyl phosphate, butyl stearate, butyl oleate, di-butyl sebacate and dioctyl phthalate. These plasticizers are preferably esters derived from dicarboxylic acids.
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dende 4 til 10 carbonatomer, såsom maleinsyre, adipinsyre og phthalsyre, samt af alkoholer indeholdende 2-8 carbon-atomer. Man har opnået de bedste resultater med phthala-ter af alkoholer indeholdende 3 til 6 carbonatomer, især 5 med dibutylphthalat.containing 4 to 10 carbon atoms, such as maleic, adipic and phthalic acids, as well as alcohols containing 2-8 carbon atoms. The best results have been obtained with phthalates of alcohols containing 3 to 6 carbon atoms, especially 5 with dibutyl phthalate.
Man kan som co-solvent anvende alle de co-solventer, der sædvanligvis anvendes ved vandopløselige alkydharpikser, især alkoholer, og fortrinsvis glycoler og glycolethere 10 indeholdende 2-8 carbonatomer. De bedste resultater er opnået med glycoler indeholdende 2 til 4 carbonatomer, især med ethylenglycol. Midler, der indeholder co-solvent, egner sig særligt godt til anvendelse ved vintertemperaturer. Det er ønskeværdigt, at vægten af co-sol-15 vent, som tages i arbejde, ikke overskrider 20 %, fortrinsvis 10 vægt-% af den syntetiske harpiks, som kan fortyndes med vand.As the co-solvent, all the co-solvents usually used in water-soluble alkyd resins, especially alcohols, and preferably glycols and glycol ethers containing 2-8 carbon atoms can be used. The best results are obtained with glycols containing 2 to 4 carbon atoms, especially with ethylene glycol. Co-solvent-containing agents are particularly suitable for use at winter temperatures. It is desirable that the weight of the co-sol vent taken into operation does not exceed 20%, preferably 10% by weight of the synthetic resin which can be diluted with water.
Det omhandlede pesticide middel kan eventuelt indeholde 20 en voksart; men det er i så tilfælde ønskværdigt, at denne voksart findes i en vægtmængde, som ikke overskrider 0,5 vægt-% af midlets samlede vægt. Det foretrækkes i almindelighed, at det omhandlede middel er fri for voks.The pesticide agent in question may optionally contain a wax species; but in that case it is desirable that this wax species be present in a weight amount not exceeding 0.5% by weight of the total weight of the agent. It is generally preferred that the agent in question be free of wax.
25 Det omhandlede middel foreligger i koncentreret form, som eventuelt kan indeholde en smule fortyndingsvand, hvilket er beregnet til at give midlet en tilstrækkelig god let-flydeenhed, således at det let kan overføres mellem oplagringsbeholdere, og for at lette håndteringen af det, 30 når der skal fremstilles pesticide midler, som er fortyndet med vand, og som er parat til at anvendes. Mængden af vand til fortynding er i princippet ikke kritisk, og den kan let bestemmes i hvert enkelt tilfælde, i afhængighed af bestanddelene i koncentratet og den ønskede letflyden-35 hed. Man opnår i praksis i almindelighed gode resultater med koncentrater indeholdende en mængde vand op til 50 vægt-% af den samlede vægt af koncentratet, idet man fo- 9The agent in question is in concentrated form which may optionally contain some dilution water, which is intended to provide the agent with a sufficiently good light flow unit so that it can be easily transferred between storage containers and to facilitate handling thereof when 30 pesticide diluted with water must be prepared and ready for use. The amount of water for dilution is in principle not critical and can be readily determined in each case, depending on the constituents of the concentrate and the desired ease of flow. In practice, good results are generally obtained with concentrates containing an amount of water up to 50% by weight of the total weight of the concentrate, since
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retrækker værdier større end 10 %, i almindelighed på mellem 25 og 30 %.retrieves values greater than 10%, generally between 25 and 30%.
Et foretrukket pesticidt middel, der har vist sig særligt 5 velegnet til dannelsen af vandige fortyndede pesticid-emulsioner, som er parat til anvendelse, og som har en høj stabilitet, er meget fine og har en høj grad af gennemskinnelighed, har følgende sammensætning: 10 5 til 20 vægtdele chloreret phenol, op til 4 vægtdele af en chloreret carbonhydrid med insekticid virkning, 5 til 20 vægtdele alkydharpiks, der er opløseligt i vand, 5 til 20 vægtdele blødgøringsmiddel, 15 5 til 20 vægtdele alkanolamin, 5 til 20 vægtdele ligekædet natriumalkylbenzensulfonat, hvori alkylkæden indeholder 10 til 14 carbonatomer, 5 til 20 vægtdele co-solvent, samt op til 50 vægtdele vand, 20 idet den eventuelle restmængde består af stoffer, der sædvanligvis er til stede i pesticide midler beregnet til behandling af træ. Sådanne midler kan f.eks. være anti-UV-midler, sikkativer eller pigmenter.A preferred pesticidal agent which has been found particularly suitable for the formation of aqueous diluted pesticide emulsions which are ready for use and which have a high stability, are very fine and have a high degree of translucency, has the following composition: 5 to 20 parts by weight of chlorinated phenol, up to 4 parts by weight of a chlorinated hydrocarbon with insecticidal effect, 5 to 20 parts by weight of water-soluble alkyd resin, 5 to 20 parts by weight of plasticizer, 15 to 20 parts by weight of alkanolamine, 5 to 20 parts by weight of straight-chain sodium alkylbenzene sulfonate wherein the alkyl chain contains 10 to 14 carbon atoms, 5 to 20 parts by weight of co-solvent, and up to 50 parts by weight of water, 20 with any residual amount consisting of substances usually present in pesticidal agents intended for the treatment of wood. Such agents may e.g. be anti-UV agents, sicatives or pigments.
25 Det pesticide middel fortyndes før brugen med vand til en fortyndingsgrad, der vælges i hvert enkelt tilfælde, og som afhænger af diverse faktorer, især af arten og de respektive koncentrationer af de deri indgående bestanddele. I almindelighed svarer den fortyndingsgrad, der egner 30 sig, til en vægtdel af bestanddelene udover vand pr. 2 til 6 vægtdele vand i midlet.The pesticidal agent is diluted before use with water to a degree of dilution selected in each case, which depends on various factors, in particular the nature and the respective concentrations of the constituents contained therein. In general, the degree of dilution suitable for 30 corresponds to one part by weight of the constituents in addition to water per minute. 2 to 6 parts by weight of water in the agent.
Det er til fremstilling af det omhandlede pesticide middel i almindelighed tilstrækkeligt at blande bestandelene 35 sammen. Det er i praksis bekvemt at gennemføre blandingen ved sådanne temperaturer og trykforhold, at man ikke risikerer en stivnen af blandingen af bestanddelene eller 10Generally, it is sufficient to mix the ingredients 35 together with the preparation of the present pesticidal agent. In practice, it is convenient to carry out the mixture at such temperatures and pressure conditions so as not to stiffen the mixture of the components or
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en fordampning af en eller flere af disse bestanddele.evaporation of one or more of these components.
Man kan f.eks. gennemføre blandingen ved en temperatur på mellem 15 og 55 °C, og ved tryk på mellem 0,535 og 1,135 bar, idet de foretrukne temperaturer befinder sig mellem 5 30 og 55 °C, og de foretrukne tryk befinder sig mellem 0,865 og 1,055 bar.One can, for example. carry out the mixture at a temperature of between 15 and 55 ° C, and at pressures of between 0.535 and 1.135 bar, with the preferred temperatures being between 5 and 55 ° C and the preferred pressures being between 0.865 and 1.055 bar.
Det omhandlede pesticide middel forekommes i form af en vandig emulsion med ekstrem høj finhedsgrad, det har et 10 udseende som en transparent og homogen opløsning. Det har stor stabilitet i lang til og stor modstandsdygtighed over for temperaturvariationer samt over for mekaniske påvirkninger, såsom stød, fald eller centrifugeringer, uden at stabiliteten berøres deraf.The present pesticidal agent is in the form of an aqueous emulsion of extremely high fineness, having a appearance as a transparent and homogeneous solution. It has great stability in long to and high resistance to temperature variations as well as to mechanical stresses, such as shocks, falls or centrifuges, without affecting stability.
15 I de efterfølgende eksempler beskrives koncentrater af midlet ifølge opfindelsen.In the following examples, concentrates of the agent according to the invention are described.
EKSEMPEL 1 20EXAMPLE 1 20
Man blander omhyggeligt ved en temperatur på ca. 40 °C pentachlorphenol, aldrin, diisobutylphthalat, ethylengly-col og det produkt, der er kendt under handelsnavnet "Uradil 30100" (Scado N.V.), hvilket er en alkydharpiks.Mix thoroughly at a temperature of approx. 40 ° C pentachlorophenol, aldrin, diisobutyl phthalate, ethylene glycol and the product known under the trade name "Uradil 30100" (Scado N.V.), which is an alkyd resin.
2525
Man tilsætter til den derved opnåede blanding successivt en blanding af diethylethanolamin og monoethanolamin, og derpå et emulgeringsprodukt indeholdende ca. 1 vægtdel vand, en vægtdel isobutanol og 2 vægtdele af en blanding 30 af natriumalkylbenzensulfonater med ligekædet alkylkæde og med den almene formel: 35 CnH2n+1--S0,Ne 11To the mixture thus obtained, a mixture of diethylethanolamine and monoethanolamine is successively added, and then an emulsifying product containing approx. 1 part by weight of water, one part by weight of isobutanol and 2 parts by weight of a mixture 30 of sodium alkylbenzenesulfonates of straight chain alkyl chain and of the general formula: 35 CnH2n + 1 - SO, Ne 11
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hvori: 10 s n * 14.wherein: 10 s n * 14.
5 Efter fortynding med vand, hvorved man opnår tilstrækkelige gode flydeegenskaber, til at blandingen kan overhældes til oplagringsbeholdere, har det pågældende koncentrat følgende vægtmæssige sammensætning: 10 _5 After dilution with water to obtain sufficient good flow properties to allow the mixture to be poured into storage containers, the concentrate in question has the following weight composition:
Bestanddele Vægt-%Ingredients Weight%
Pentachlorphenol 14Pentachlorophenol 14
Aldrin 2 15 Harpiks "Uradil 30100" 13Aldrin 2 15 Resin "Uradil 30100" 13
Diisobutylphthalat 13Diisobutylphthalate 13
Ethylenglycol 1Ethylene glycol 1
Diethylethanolamin 4Diethylethanolamine 4
Monoethanolamin 10 20 Emulgator 10Monoethanolamine 10 Emulsifier 10
Vand 33Water 33
Man dispergerer dette koncentrat i vand i en mængde på 1 25 vægtdel koncentrat og 4 vægtdele vand, således at man opnår en fortyndet pesticidblanding, som er klar til anvendelse ved behandlingen af træstykker, især af konstruktionsmaterialer, såsom bygningstømmer. Sådanne midler har vist sig at bestå af vandige emulsioner med ekstremt høj 30 finhedsgrad, hvor de enkelte kugler udviste en middeldiameter mindre end 0,05 μπι i overensstemmelse med definitionen i den franske norm AFN0R T730409. Af denne grund havde de et udseende som transparente vandige opløsninger. Når de blev underkastet et centrifugeringsforsøg 2 35 svarende til centrifugalkraft på 98100 m/sek igennem en time, undergik de ikke nogen ændring.This concentrate is dispersed in water in an amount of 1 25 parts by weight of concentrate and 4 parts by weight of water, so as to obtain a dilute pesticide mixture which is ready for use in the treatment of pieces of wood, especially of structural materials such as building timber. Such agents have been found to consist of aqueous emulsions of extremely high degree of fineness, with the individual spheres having a mean diameter less than 0.05 μπι in accordance with the definition in French standard AFN0R T730409. For this reason, they had the appearance of transparent aqueous solutions. When subjected to a centrifugation experiment 2 corresponding to centrifugal force of 98100 m / sec for one hour, they did not undergo any change.
1212
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EKSEMPEL 2EXAMPLE 2
Man blander omhyggeligt ved temperatur på ca. 40 "C deca-methrin, et fungicid kendt under betegnelsen "Xyligen B" 5 (BASF), som i hovedsagen består af N-cyclohexyl, N-me-thoxy, 2,5-dimethyl-furan-3-carboxamid, samt det produkt, der kendes under handelsbetegnelsen "Hydrorob 2428" (Robbe), som er en acrylmodificeret alkydharpiks. Man tilsætter først til den derved opnåede blanding en blan-10 ding af diethanolamin og monoethanolamin, og derpå det samme emulgatorprodukt, som blev anvendt i eksempel 1.Mix thoroughly at a temperature of approx. 40 "C deca-methrin, a fungicide known under the designation" Xyligen B "5 (BASF), which mainly consists of N-cyclohexyl, N-methoxy, 2,5-dimethyl-furan-3-carboxamide, and the a product known by trade name "Hydrorob 2428" (Robbe), which is an acrylic modified alkyd resin, first adding to the mixture thus obtained a mixture of diethanolamine and monoethanolamine, and then the same emulsifier product used in Example 1 .
Efter fortynding med vand udviste koncentratet følgende vægtmæssige sammensætning: 15After dilution with water, the concentrate showed the following weight composition: 15
Bestanddele Vægt-%Ingredients Weight%
Decamethrin 0,2 20 Fungicid "Xyligen B" 0,6Decamethrin 0.2 Fungicide "Xyligen B" 0.6
Harpiks "Hydrorob 2428" 12,0Resin "Hydrorob 2428" 12.0
Diethanolamin 1,0Diethanolamine 1.0
Monoethanolamin 1,0Monoethanolamine 1.0
Emulgator 10,0 25 Vand 69,8Emulsifier 10.0 25 Water 69.8
Dette koncentrat blev dispergeret i vand i en mængde på en vægtdel koncentrat og fire vægtdele vand på en sådan 30 måde, at man opnåede et fortyndet pesticidmiddel, der var klar til anvendelse til behandling af træstykker, især konstruktionsmaterialer, såsom bygningstømmer. Disse midler viste sig ligeledes at bestå af vandige emulsioner med ekstrem høj finhedsgrad, hvor de enkelte kugler havde 35 en middeldiameter lavere end 0,05 um i overensstemmelse med definitionen i den franske norm AFNOR T73-409. Af denne grund udviste de et udseende som transparente van- 13This concentrate was dispersed in water in an amount of one part by weight of concentrate and four parts by weight of water in such a way as to obtain a dilute pesticide ready for use in treating wood pieces, especially structural materials such as building timber. These agents were also found to consist of aqueous emulsions of extremely high fineness, with the individual spheres having a mean diameter lower than 0.05 µm in accordance with the definition in French standard AFNOR T73-409. For this reason, they showed an appearance as transparent water 13
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dige opløsninger. Underkastet et centrifugeringsforsøg 2 svarende til en centrifugalkraft på 98100 m/sek igennem en time, undergik de ikke nogen ændringer.solid solutions. Undergoing a spin 2 experiment corresponding to a centrifugal force of 98100 m / sec for one hour, they did not undergo any changes.
5 EKSEMPEL 3 (sammenligningseksempel)EXAMPLE 3 (Comparative Example)
Vandige pesticidmidler i emulsionsform af den type, som er blevet beskrevet i US patentskrift nr. 3 281 318 som ovenfor nævnt, viste sig til sammenligning, når de blev 10 underkastet det samme centrifugeringsforsøg, at adskilles i to oven på hinanden liggende faser efter 15 minutters centrifugering.Aqueous emulsion pesticide agents of the type described in U.S. Patent No. 3,281,318 as mentioned above, when compared to the same centrifugation test, were found to be separated in two successive phases after 15 minutes. centrifugation.
15 20 25 30 3515 20 25 30 35
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8212531A FR2530121A1 (en) | 1982-07-13 | 1982-07-13 | PESTICIDE COMPOSITIONS FOR TREATING WOOD |
| FR8212531 | 1982-07-13 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK320683D0 DK320683D0 (en) | 1983-07-12 |
| DK320683A DK320683A (en) | 1984-01-14 |
| DK162146B true DK162146B (en) | 1991-09-23 |
| DK162146C DK162146C (en) | 1992-02-24 |
Family
ID=9276063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK320683A DK162146C (en) | 1982-07-13 | 1983-07-12 | PESTICID AGENT FOR TREATMENT OF TREES |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0102093B1 (en) |
| JP (1) | JPS5976203A (en) |
| AR (1) | AR230923A1 (en) |
| AT (1) | ATE24683T1 (en) |
| AU (1) | AU562630B2 (en) |
| BR (1) | BR8303702A (en) |
| CA (1) | CA1203473A (en) |
| DE (1) | DE3368889D1 (en) |
| DK (1) | DK162146C (en) |
| ES (1) | ES524051A0 (en) |
| FI (1) | FI70770C (en) |
| FR (1) | FR2530121A1 (en) |
| MA (1) | MA19833A1 (en) |
| NO (1) | NO158713C (en) |
| OA (1) | OA07494A (en) |
| PT (1) | PT77009B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270602A (en) * | 1987-04-30 | 1988-11-08 | Nippon Seika Kk | Evaporating gel preparation of antibacterial and antifugal agents |
| DE4112652A1 (en) * | 1991-04-18 | 1992-10-22 | Wolman Gmbh Dr | WOOD PRESERVATIVES |
| DE10106230A1 (en) * | 2001-02-10 | 2002-08-14 | Creavis Tech & Innovation Gmbh | Process for the production of microbicidal surfaces by immobilization of amino alcohols |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3281318A (en) * | 1962-09-06 | 1966-10-25 | Chapman Chem Co | Wood treatment composition and method of formulating same |
| US3617314A (en) * | 1968-07-23 | 1971-11-02 | Monsanto Co | Wood treatment |
| BE756541A (en) * | 1969-09-24 | 1971-03-01 | Norddeutsche Affinerie | WOOD PRESERVATION AGENT |
| DE3004319A1 (en) * | 1980-02-06 | 1981-08-13 | Desowag-Bayer Holzschutz GmbH, 4000 Düsseldorf | WOOD PROTECTIVE CONCENTRATE AND PRODUCT MADE THEREOF FOR THE PRESERVATION OF WOOD AND WOOD MATERIALS |
| DE3014194A1 (en) * | 1980-04-14 | 1981-10-22 | Dr. Wolman Gmbh, 7573 Sinzheim | AQUEOUS WOOD PRESERVATIVE |
-
1982
- 1982-07-13 FR FR8212531A patent/FR2530121A1/en active Granted
-
1983
- 1983-06-29 AT AT83200962T patent/ATE24683T1/en not_active IP Right Cessation
- 1983-06-29 DE DE8383200962T patent/DE3368889D1/en not_active Expired
- 1983-06-29 EP EP83200962A patent/EP0102093B1/en not_active Expired
- 1983-07-01 MA MA20053A patent/MA19833A1/en unknown
- 1983-07-04 CA CA000431733A patent/CA1203473A/en not_active Expired
- 1983-07-07 FI FI832500A patent/FI70770C/en not_active IP Right Cessation
- 1983-07-08 AU AU16677/83A patent/AU562630B2/en not_active Ceased
- 1983-07-11 BR BR8303702A patent/BR8303702A/en not_active IP Right Cessation
- 1983-07-11 NO NO832514A patent/NO158713C/en unknown
- 1983-07-11 PT PT77009A patent/PT77009B/en not_active IP Right Cessation
- 1983-07-12 ES ES524051A patent/ES524051A0/en active Granted
- 1983-07-12 OA OA58061A patent/OA07494A/en unknown
- 1983-07-12 DK DK320683A patent/DK162146C/en not_active IP Right Cessation
- 1983-07-13 AR AR293596A patent/AR230923A1/en active
- 1983-07-13 JP JP58127518A patent/JPS5976203A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| PT77009B (en) | 1986-01-24 |
| NO832514L (en) | 1984-01-16 |
| FR2530121A1 (en) | 1984-01-20 |
| FI70770B (en) | 1986-07-18 |
| FI70770C (en) | 1986-10-27 |
| AR230923A1 (en) | 1984-08-31 |
| BR8303702A (en) | 1984-02-14 |
| FR2530121B1 (en) | 1984-12-28 |
| EP0102093A1 (en) | 1984-03-07 |
| NO158713C (en) | 1988-10-26 |
| DK162146C (en) | 1992-02-24 |
| DK320683A (en) | 1984-01-14 |
| ES8404148A1 (en) | 1984-04-16 |
| JPS5976203A (en) | 1984-05-01 |
| ES524051A0 (en) | 1984-04-16 |
| MA19833A1 (en) | 1984-04-01 |
| NO158713B (en) | 1988-07-18 |
| FI832500A0 (en) | 1983-07-07 |
| JPH0337485B2 (en) | 1991-06-05 |
| AU562630B2 (en) | 1987-06-18 |
| DE3368889D1 (en) | 1987-02-12 |
| EP0102093B1 (en) | 1987-01-07 |
| CA1203473A (en) | 1986-04-22 |
| OA07494A (en) | 1985-03-31 |
| PT77009A (en) | 1983-08-01 |
| AU1667783A (en) | 1984-01-19 |
| FI832500L (en) | 1984-01-14 |
| ATE24683T1 (en) | 1987-01-15 |
| DK320683D0 (en) | 1983-07-12 |
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