DK154534B - FUNGICID MIXING OF A QUATERNARY AMMONIUM COMPOUND AND A GUANIDINE COMPONENT, AND USE OF IT - Google Patents
FUNGICID MIXING OF A QUATERNARY AMMONIUM COMPOUND AND A GUANIDINE COMPONENT, AND USE OF IT Download PDFInfo
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- DK154534B DK154534B DK206478A DK206478A DK154534B DK 154534 B DK154534 B DK 154534B DK 206478 A DK206478 A DK 206478A DK 206478 A DK206478 A DK 206478A DK 154534 B DK154534 B DK 154534B
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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
- 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
- A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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Description
DK 154534 BDK 154534 B
Den foreliggende opfindelse angår et fungicidt middel, samt anvendelsen deraf til beskyttelse af tra eller trabaserede materialer.The present invention relates to a fungicidal agent, and to its use for the protection of wood or wood based materials.
5 Det fungicide middel ifølge opfindelsen er ejendommeligt ved, at det som aktiv komponent indeholder en blanding af en fungicid kvateriiær ammoniumforbindelse og mindst en guanideret •alifatisk diamin. øg/eller polyamin eller et syreadditionssalt deraf-med formlen 10The fungicidal agent of the invention is characterized in that it contains as an active component a mixture of a fungicidal quaternary ammonium compound and at least one guanidated aliphatic diamine. increasing / or polyamine or an acid addition salt thereof of formula 10
XX
X - HNR1 - (NR2)n - NH-X, hvori X er hydrogen eller en carboxamidingruppe, eventuelt , _ substitueret med alkylgrupper med 1-4 carbonatomer, idet 1 o mindst én X er en carboxamidingruppe, R1 og R2 uafhangig af hinanden er alifatiske grupper med 3-14 carbonatomer, og n = 0-6, hvorhos vagtforholdet af de aktive stoffer ligger i intervallet fra 1:2 til 20:1.X - HNR1 - (NR2) n - NH-X wherein X is hydrogen or a carboxamide group, optionally, substituted with alkyl groups of 1-4 carbon atoms, wherein at least one X is a carboxamide group, R1 and R2 are independently of one another aliphatic groups having 3-14 carbon atoms, and n = 0-6, where the active ratio of the active substances ranges from 1: 2 to 20: 1.
2020
De angivne fungicide midlers komponenter er tidligere hver for sig blevet anvendt som fungicider. Således er det f.eks. kendt fra DE patentskrift nr. 2.132.701 at anvende en kombination af thiourinstof og kvaternare ammoniumforbindelser som beskyttel-25 se mod blåpletinfektioner hos tra. Desuden er kvaternare ammoniumforbindelser, såsom alkylbenzyldimethylammoniumchlorid blevet anvendt til beskyttelse af tra f.eks. til beskyttelse mod hvidbakteriose. Guaniderede alifatiske diaminer og poly-aminer er overvejende blevet anvendt i gartneri og landbrug 30 til bekampelse af jord- og frøbårne svampe.The components of the fungicides mentioned have previously been used separately as fungicides. Thus, e.g. known from DE Patent Specification No. 2,132,701 to use a combination of thiourea and quaternary ammonium compounds as protection against blue-platelet infections in tra. In addition, quaternary ammonium compounds such as alkylbenzyldimethylammonium chloride have been used to protect tra for protection against white bacteria. Guanidated aliphatic diamines and polyamines have been predominantly used in horticulture and agriculture 30 to control soil and seed borne fungi.
Det har nu vist sig, at blandinger af kvaternare ammoniumforbindelser og guaniderede aminer ikke blot giver en additiv virkning, men også en synergistisk virkning. Blandinger ifølge 35 opfindelsen af aktive „komponenter giver en uventet forlængelse og også en udvidelse af den fungicide virkning, som ikke kan tilskrives en additiv virkning.It has now been found that mixtures of quaternary ammonium compounds and guanidated amines not only give an additive effect but also a synergistic effect. Mixtures according to the invention of active components provide an unexpected extension and also an extension of the fungicidal effect which cannot be attributed to an additive effect.
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De kvaternære ammoniumforbindelser, der er nyttige i midlerne ifølge opfindelsen, kan illustreres ved hjælp af den almene formelThe quaternary ammonium compounds useful in the compositions of the invention can be illustrated by the general formula
RR
5 , Ϊ-© i i fa5, Ϊ- © i i fa
R - N - RR - N - R
I I II JI I II J
RR
hvori mindst én af grupperne R har en højere carbonkæde, d.v.s.wherein at least one of the groups R has a higher carbon chain, i.e.
10 en lige eller forgrenet, substitueret eller usubstitueret ali-fatisk gruppe med 6-24 carbonatomer. Som et eksempel på en inaktiv substituent i den højere alifatiske gruppe kan nævnes en ethergruppe. De kvaternære ammoniumforbindelser indeholder en eller to højere grupper, medens de andre substituenter R uaf-15 hængig af hinanden er alkyl- eller hydroxyalkylgrupper med 1-4 carbonatomer eller benzylgrupper. To af de andre substituenter kan også danne en piperidin- eller morfoli ngruppe med nitrogenatomet. Anionen er fortrinsvis chlorid, men kan naturligvis erstattes med andre ioner, såsom bromid, ethylsulfation etc.10 is a straight or branched, substituted or unsubstituted aliphatic group having 6-24 carbon atoms. As an example of an inactive substituent in the higher aliphatic group, there may be mentioned an ether group. The quaternary ammonium compounds contain one or two higher groups, while the other substituents R are independently alkyl or hydroxyalkyl groups having 1-4 carbon atoms or benzyl groups. Two of the other substituents may also form a piperidine or morpholine group with the nitrogen atom. The anion is preferably chloride, but can of course be replaced by other ions such as bromide, ethyl sulfation, etc.
20 Den kvaternære ammoniumforbindelse indeholder passende en eller to alkylgrupper med 6-24 carbonatomer og fortrinsvis 8-14 carbonatomer. Som eksempel på egnede fungicide kvaternære ammoniumforbindelser til anvendelse i de foreliggende midler kan nævnes didecyldimethylammoniumchlorid, cetyltrimethylammo-25 niumchlorid, alkylbenzyldimethylammoniumchlorid og andre kvaternære ammoniumforbindelser, hvori kædelængdefordelingen af den højere alkylgruppe eller de højere alkylgrupper svarer til hvad, der kendes i naturligt forekommende stoffer, såsom i kokossyre, cetyldimethylethylammoniumethylsulfat etc.Suitably, the quaternary ammonium compound contains one or two alkyl groups having 6-24 carbon atoms and preferably 8-14 carbon atoms. Examples of suitable fungicidal quaternary ammonium compounds for use in the present agents may be mentioned didecyldimethylammonium chloride, cetyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride and other quaternary ammonium compounds wherein the chain length distribution of the higher alkyl group or the higher alkyl group, in coconut acid, cetyl dimethylethylammonium ethyl sulfate etc.
3030
De foreliggende midlers guadini nkomponent er mindst én guani-deret alifatisk diamin eller mindst én guanideret alifatisk polyamin, hvormed menes triaminer, tetraaminer og højere oli-gomere, eller en blanding af guaniderede aminer og polyaminer.The guadiene component of the present agents is at least one guanidated aliphatic diamine or at least one guanidated aliphatic polyamine by which are meant triamines, tetraamines and higher oligomers, or a mixture of guanidated amines and polyamines.
35 På grund af guanidingruppernes basestyrke indgår de guaniderede aminer almindeligvis som syreadditionsal te, f.eks. chlori-der, sulfater, nitrater, acetater, formiater, stearater, ole-ater etc.Because of the base strength of the guanidine groups, the guanidated amines are commonly used as acid additional teas, e.g. chlorides, sulfates, nitrates, acetates, formates, stearates, olefins, etc.
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Guanidinkomponenten kan illustreres ved hjælp af den almene formelThe guanidine component can be illustrated by the general formula
XX
1 I 2 . X - HNR - (NR) - HH - X (I) 5 n nvori X er hydrogen eller en carboxamidingruppe, d.v.s. gruppen1 I 2. X - HNR - (NR) - HH - X (I) wherein X is hydrogen or a carboxamide group, i.e. group
NHNH
10 .10.
Mindst én af grupperne X er carboxamidin. I carboxamidingrup-15 pen kan en eller flere af hydrogenatomerne være erstattet med alkylgrupper med 1-4 carbonatomer. X er fortrinsvis som en carboxamidingruppe usubstitueret. Ri og R2 er uafhængigt af hinanden alifatiske grupper med 3-14 carbonatomer, hensigtsmæssigt alkylengrupper med 6-12 carbonatomer, såsom hexylen-, 20 heptylen-, octylen-, nonylen-, decylen-, dodecylengrupper eller cykloalkylengrupper, såsom cyklopentylen-, cyklohexylen-, cykloheptylen-, eller cyklooctylengrupper. Alkylengrupperne indeholder bedst 6-9 carbonatomer. I formlen er n = 0-6, fortrinsvis 0-4. Grupperne R2 behøver ikke nødvendigvis at være 25 ens, når n>l.At least one of the groups X is carboxamidine. In the carboxamide group, one or more of the hydrogen atoms may be replaced by alkyl groups of 1-4 carbon atoms. X is preferably unsubstituted as a carboxamide group. R 1 and R 2 are independently aliphatic groups of 3-14 carbon atoms, suitably alkylene groups of 6-12 carbon atoms such as hexylene, heptylene, octylene, nonylene, decylene, dodecylene groups or cycloalkylene groups such as cyclopentylene, cyclohexylene groups. , cycloheptylene, or cyclooctylene groups. The alkylene groups best contain 6-9 carbon atoms. In the formula, n = 0-6, preferably 0-4. The groups R2 need not necessarily be equal when n> l.
Når guanidinkomponenten er en guanideret alifatisk diamin, har den passende den almene formelWhen the guanidine component is a guanidated aliphatic diamine, it suitably has the general formula
NR NRNR NO
30 il , II30 µl, II
(R) N-C-NH-R -NH-C-N(R) (II) 2 2.(R) N-C-NH-R -NH-C-N (R) (II) 2 2.
hvori R fortrinsvis er hydrogen, men også kan være en lavere alkylgruppe med 1-4 carbonatomer, og R* er en alkylengruppe 35 med 3-14 carbonatomer, hensigtsmæssigt 6-12 carbonatomer.wherein R is preferably hydrogen but may also be a lower alkyl group of 1-4 carbon atoms and R * is an alkylene group 35 of 3-14 carbon atoms, preferably 6-12 carbon atoms.
Guaniderede alifatiske polyaminer er forbindelser med den almene formelGuanidated aliphatic polyamines are compounds of the general formula
DK 154534BDK 154534B
44
XX
1 I 2 X - HNR - (NR ) -NH - X (III) n hvor X er hydrogen eller en carboxamidingruppe, eventuelt sub-5 stitueret med alkylgrupper med 1-4 carbonatomer, R* og R2 uafhængigt af hinanden er alifatiske grupper med 3-14 carbonatomer, hensigtsmæssigt 6-12 carbonatomer, og n = 1-6, fortrinsvis 1-4. Grupperne R2 behøver ikke nødvendigvis at være ens, når n>l.1 In 2 X - HNR - (NR) -NH - X (III) n where X is hydrogen or a carboxamide group, optionally substituted with alkyl groups of 1-4 carbon atoms, R * and R 2 are independently aliphatic groups having 3-14 carbon atoms, conveniently 6-12 carbon atoms, and n = 1-6, preferably 1-4. The groups R2 need not necessarily be equal when n> l.
1010
Som et eksempel på en egnet guanideret alifatisk polyamin kan nævnes triaminen med formlen X - HNRl - NHR2 - NH ” X' 15 hvori X er carboxamidingrupper, og R* og R2 har de ovenfor anførte betydninger.As an example of a suitable guanidated aliphatic polyamine, mention may be made of the triamine of formula X - HNR1 - NHR2 - NH4 X 'wherein X is carboxamide groups and R * and R 2 have the meanings set forth above.
Når guanidinkomponenten er en guanideret alifatisk polyamin, 2o er den fortrinsvis sammensat af en blanding af derivater med den ovennævnte formel (III) med en guanideringsgrad, som overstiger 30% og fortrinsvis overstiger 70%. Som nævnt indgår guanidinkomponenten almindeligvis som et syreadditionssalt.When the guanidine component is a guanidated aliphatic polyamine, it is preferably composed of a mixture of derivatives of the above formula (III) having a degree of guanidation exceeding 30% and preferably exceeding 70%. As mentioned, the guanidine component is generally included as an acid addition salt.
25 En guanideringsgrad på over 30% for en blanding af derivater med formlen (III) betyder, at det samlede antal carboxamidingrupper i blandingen overstiger 30% af det samlede antal N-atomer baseret på blandingen af derivater med formlen (III). I de foreliggende blandinger af kvaternære ammoniumforbindelser 30 og guanidinkomponenter er sidstnævnte passende blandinger af guaniderede alifatiske diaminer og guaniderede alifatiske po-lyami ner.A degree of guanidation greater than 30% for a mixture of derivatives of formula (III) means that the total number of carboxamide groups in the mixture exceeds 30% of the total number of N atoms based on the mixture of derivatives of formula (III). In the present mixtures of quaternary ammonium compounds 30 and guanidine components, the latter are suitable mixtures of guanidated aliphatic diamines and guanidated aliphatic polymers.
Guanidinkomponenten har herved en guanideringsgrad, som over-35 stiger 45%, hensigtsmæssigt overstiger 70% og fortrinsvis en guanideringsgrad i intervallet 70-95%. Komponenten består fortrinsvis af 15-30 vægt% diamin, 20-50 vægt% triamin, 30-60 vægt% tetraamin og højere oligomere og har en guanideringsgrad i intervallet fra 70-95%.The guanidine component hereby has a degree of guanidation exceeding 45%, suitably exceeding 70% and preferably a degree of guanidation in the range 70-95%. The component preferably consists of 15-30% by weight diamine, 20-50% by weight triamine, 30-60% by weight tetraamine and higher oligomers and has a degree of guanidation in the range of 70-95%.
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Særligt gode resultater er blevet opnået med midler, hvori gu-anidinderivaterne med ovennævnte formler har alkylengrupper med otte carbonatomer.Particularly good results have been obtained by means wherein the guanidine derivatives of the above formulas have alkylene groups of eight carbon atoms.
5 Blandinger af guaniderede alifatiske polyaminer, som indeholder uregelmæssigt guaniderede nitrogenatomer, er blevet udviklet fornylig. Da der ikke kræves nogen specifik guanidering, kan blandingerne fremstilles på simpel måde ud fra f.eks. en teknisk blanding af aminer, som guanideres med cyanamider, u-10 rinstof- eller thiourinstofderivater til den ønskede guanide-ringsgrad. Disse blandinger kan naturligvis også indeholde guaniderede diaminer.5 Mixtures of guanidated aliphatic polyamines containing irregularly guanidated nitrogen atoms have been developed recently. Since no specific guanidation is required, the mixtures can be prepared in a simple manner from e.g. a technical mixture of amines which are guanidated with cyanamides, urea or thiourea derivatives to the desired degree of guanidation. Of course, these mixtures may also contain guanidated diamines.
I midlerne ifølge opfindelsen ligger vægtforholdet af kvater-15 nær ammoniumforbindelse til guanidinkomponent i intervallet fra 1:2 til 20:1, fortrinsvis i intervallet fra 2:1 til 10:1. Midlerne kan fremstilles ved simpel blanding af de to aktive komponenter, fortrinsvis i vandige opløsninger, selv om polære opløsningsmidler også kan anvendes.In the compositions of the invention, the weight ratio of quaternary near ammonium compound to guanidine component is in the range of 1: 2 to 20: 1, preferably in the range of 2: 1 to 10: 1. The agents can be prepared by simply mixing the two active components, preferably in aqueous solutions, although polar solvents may also be used.
2020
Midlerne kan anvendes til landbrugs- og gartner i formål, men anvendes fortrinsvis til forskellige industrielle formål.The funds can be used for agricultural and horticultural purposes, but are preferably used for various industrial purposes.
Midlerne er særligt egnede som træbeskyttelsesmidler til byg-25 ge- og konstruktionsmaterialer. Det har vist sig, at midlerne giver en fremragende beskyttelse mod trænedbrydende svampe, såsom skimmelsvampe, rød og blå svampe. En væsentligt forlænget virkning opnås ved anvendelse af kombinationen af aktive bestanddele i sammenligning med anvendelsen af hver af be-30 standdelene særskilt. Det har også vist sig, at beskyttelsen mod blå svampe er væsentligt forbedret med midlerne. Alle slags træ og træbaserede materialer, som er modtagelige for trænedbrydende svampe, kan beskyttes ved behandling med de foreliggende midler under anvendelse af almindelige fremgangsmå-35 der, såsom dypning, sprøjtning, pensling og imprægnering.The agents are particularly suitable as wood preservatives for building and construction materials. It has been found that the agents provide excellent protection against wood-breaking fungi, such as molds, reds and blue fungi. A substantially prolonged effect is obtained by using the combination of active ingredients in comparison with the use of each of the components separately. It has also been found that protection against blue fungi has significantly improved with the means. All types of wood and wood-based materials susceptible to wood-decomposing fungi can be protected by treatment with the present agents using common methods such as dipping, spraying, brushing and impregnation.
Opfindelsen angår også anvendelse af de fungicide midler ifølge opfindelsen til beskyttelse af træ eller træbaserede materialer.The invention also relates to the use of the fungicides of the invention for the protection of wood or wood-based materials.
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Midlernes to aktive komponenter er kationiske, og der opnås således en meget god retention til det negativt ladede cellulosemateriale. Yderligere stoffer til at lette midlernes retention til træ er således ikke nødvendig. De aktive komponen-5 ter er desuden opløselige i vand, således at hydrocarbonopløs-ningsmidlerne, der sædvanligvis anvendes i forbindelse med træbeskyttelsesmidler, og som af toksikologiske grunde er uønskede, ikke behøver at blive anvendt. Midlerne kan naturligvis alligevel indgå i alle sædvanlige præparattyper inklusive pul-10 verformede præparater. De foreliggende midler har en yderligere fordel i sammenligning med almindeligt anvendte stoffer til træbeskyttelse, såsom pentachlorphenoler og bifluorider, da komponenterne har ubetydelige damptryk og således ikke afgiver dampe, hvilket er en betydelig fordel af toksikologiske og 15 miljømæssige grunde.The two active components of the agents are cationic and thus a very good retention is obtained for the negatively charged cellulose material. Thus, additional substances for facilitating the retention of wood are not necessary. Furthermore, the active components are soluble in water, so that the hydrocarbon solvents usually used in conjunction with wood preservatives and which are undesirable for toxicological reasons need not be used. Of course, the agents can still be included in all usual types of compositions, including powdered preparations. The present agents have a further advantage over commonly used wood preservatives, such as pentachlorophenols and bifluorides, as the components have negligible vapor pressure and thus do not emit vapors, which is a significant benefit for toxicological and environmental reasons.
Koncentrationen af de aktive komponenter i flydende præparater til anvendelse som træbeskyttelsesmidler ligger almindeligvis i intervallet fra 0,1 til 10 vægt%. Koncentrationen er imid-20 lertid ikke kritisk, men afpasses under hensyntagen til den ønskede beskyttelsesgrad og trætypen.The concentration of the active components in liquid preparations for use as wood preservatives is generally in the range of 0.1 to 10% by weight. However, the concentration is not critical, but is adjusted taking into account the desired degree of protection and the type of tree.
Midlerne ifølge opfindelsen har både en profylaktisk og retablerende virkning og kan, foruden den ovennævnte anvendelse, 25 også anvendes til desinfektion af trætørringsudstyr og af bygninger og andre konstruktioner, som er blevet angrebet af skimmel og råd. Til desinfektion af beskadigede bygninger kan midlerne i form af opløsninger eller dispersioner indføres i fundamenter, mellemrum, vægge og andre beskadigede steder.The agents of the invention have both a prophylactic and restorative effect and, in addition to the aforementioned application, can also be used to disinfect wood drying equipment and of buildings and other structures that have been attacked by mold and debris. For disinfecting damaged buildings, the means in the form of solutions or dispersions can be introduced into foundations, spaces, walls and other damaged places.
30 Midlet kan anvendes til behandling af fundamenter for at beskytte bindere, som anvendes deri, mod angreb af svampe eller svampevækst. De kan også anvendes til fibermaterialer, såsom papir og tekstiler, og kan herved indføres i forskellige trin af den respektive produktionsproces. De kan f.eks. tilsættes 35 til en pulpsuspension i forbindelse med papirfremstillingen.The agent can be used to treat foundations to protect binders used therein against fungal or fungal growth. They can also be used for fiber materials, such as paper and textiles, and can thereby be introduced in various stages of the respective production process. For example, they can 35 is added to a pulp suspension in connection with the papermaking.
Midlerne kan kombineres med fortyndingsmidler og additiver, der kendes per se, ligesom de kan indgå i præparater, som indeholder ellers kendte fungicide og pesticide stoffer.The agents can be combined with diluents and additives known per se, as well as they can be included in preparations containing otherwise known fungicides and pesticides.
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Opfindelsen beskrives yderligere i de følgende eksempler.The invention is further described in the following examples.
Eksempel 1, 5 Frisk udskårne skiveformede fyrreplader med en omtrentlig diameter på 5 cm og tykkelse på 1 cm blev dyppet i en standard sporeopløsning, hovedsagelig indeholdende sporer af Cladosporium Herbarum/ Pullularia Pullulans og Ceratosystis Coerulem. Pladerne fik derpå lov til at tørre i 1 minut. Der blev udtaget en referenceplade, og de andre pla-jO der blev i 30 sekunder neddyppet i behandlingsbade af vandige opløsninger af forskellige koncentrationer af kvaternære ammoniumforbindelser, guaniderede aminer og blandinger af disse ifølge opfindelsen. En referenceplade og to identisk behandlede plader blev derefter anbragt i plastposer, som blev lukket og lagret ved stuetemperatur. Visuel undersøgelse af angreb blev foretaget på forskellige tidspunkter efter infektionen, og angrebenes omfang blev bedømt efter en skala fra 0-4, hvor 0 betegner intet angreb, 1 en tendens til angreb, 2 angreb, 3 kraftigt angreb og 4 meget kraftigt angreb.EXAMPLES 1, 5 Freshly cut disc-shaped pine plates with an approximate diameter of 5 cm and thickness of 1 cm were dipped in a standard spore solution, mainly containing spores of Cladosporium Herbarum / Pullularia Pullulans and Ceratosystis Coerulem. The plates were then allowed to dry for 1 minute. A reference plate was taken, and the other plates were immersed for 30 seconds in treatment baths of aqueous solutions of various concentrations of quaternary ammonium compounds, guanidated amines and mixtures thereof according to the invention. A reference plate and two identically treated plates were then placed in plastic bags which were closed and stored at room temperature. Visual examination of attacks was performed at different times after infection and the extent of attacks was rated on a scale of 0-4, with 0 denoting no attack, 1 tendency to attack, 2 attacks, 3 vigorous attacks and 4 very vigorous attacks.
I den efterfølgende tabel er anvendt følgende betegnelser: 20 a) alkylbenzyldimethylammoniumchlorid, hvori antallet af carbonatomer i alkylgruppen hovedsagelig er 12-18.The following table uses the following terms: a) alkylbenzyl dimethylammonium chloride, wherein the number of carbon atoms in the alkyl group is mainly 12-18.
b) en guanidinkomponent omfattende 20% n-octylendiamin, 40% bis (8- 25 aminooctyl)-amin og 40% højere oligomere, idet blandingen har en samlet guanideringsgrad på 82%. Guanidinkomponenten indgik som acetat.b) a guanidine component comprising 20% n-octylenediamine, 40% bis (8- 25 aminooctyl) amine and 40% higher oligomers, the mixture having a total guanidation rate of 82%. The guanidine component was included as acetate.
I tabellen er anført vurderinger for hver koncentration af det pågældende aktive stof i sammenligning med den tilsvarende reference, 30 for hvilken vurderingen er givet efter skråstregen.The table lists assessments for each concentration of the active substance concerned in comparison with the corresponding reference 30 for which the assessment is given after the slash.
Tid efter Aktivt stof, vægt% i behandlingsbad infektion, uger__a_ _b_ _a + b_ 1% 2% 4% 0,2% 0,4% 1% l%+0,2% 2%+0,2% 35 2 2/3 2/3 1,5/3 2/3 0/2,5 0/3 0/0 0/0 4 3/4 3/4 2,5/3,5 2,5/4 0,5/3 0/4 0/2,5 0/2,5 9 4/4 3/4 2/4 3/4 2/4 2/4 1/4 0,5/4 8Time after Active substance, weight% in treatment bath infection, weeks__a_ _b_ _a + b_ 1% 2% 4% 0.2% 0.4% 1% l% + 0.2% 2% + 0.2% 35 2 2 / 3 2/3 1.5 / 3 2/3 0 / 2.5 0/3 0/0 0/0 4 3/4 3/4 2.5 / 3.5 2.5 / 4 0.5 / 3 0/4 0 / 2.5 0 / 2.5 9 4/4 3/4 2/4 3/4 2/4 2/4 1/4 0.5 / 4 8
DK 154534 BDK 154534 B
Det fremgår helt klart af resultaterne, at de foreliggende midler giver en bedre og mere langvarig beskyttelse end komponenterne særskilt. 1% af den kvaternære ammoniumforbindelse giver således overhovedet ikke nogen beskyttelse efter 9 ugers forløb, dvs. hele pladen 5 er angrebet af svampe. På samme måde giver 0,2% af den anden komponent ikke nogen beskyttelse efter 9 ugers forløb. Kombinationen af disse aktive stoffer giver imidlertid kun et ganske svagt angreb efter 9 ugers forløb ved en dosis på 1,0% + 0,2%.It is clear from the results that the available funds provide better and longer lasting protection than the components separately. Thus, 1% of the quaternary ammonium compound does not provide any protection at all after 9 weeks, ie. the entire plate 5 is attacked by fungi. Similarly, 0.2% of the second component does not provide any protection after 9 weeks. However, the combination of these active substances gives only a very slight attack after 9 weeks at a dose of 1.0% + 0.2%.
jq Eksempel 2.and Example 2.
En tilsvarende behandling af fyrreplader som beskrevet i eksempel 1 blev foretaget, men med den forskel, at der til infektionen blev anvendt en opløsning af sporer fremstillet af svampe fra naturligt inficeret træ. Opløsningen indeholdt hovedsagelig sporer fra Penicil-15 lium, Trichoderma, Aspergillus og Pullularia Pullulans.A similar treatment of pine boards as described in Example 1 was performed, but with the difference that a solution of spores made from fungi from naturally infected wood was used for the infection. The solution mainly contained spores from Penicillium, Trichoderma, Aspergillus and Pullularia Pullulans.
Der blev afprøvet følgende aktive stoffer: a) didecyldimethylammoniumchlorid, 20 b) en guanidinkomponent svarende til det i eksempel 1 anførte.The following active substances were tested: a) didecyldimethylammonium chloride, b) a guanidine component similar to that of Example 1.
Resultaterne af de visuelle undersøgelser er anført i sammenligning med den tilsvarende reference.The results of the visual studies are given in comparison with the corresponding reference.
25 Tid efter Aktivt stof, vægt% i behandlingsbadet infektion, uger__a_ ___ a + b_ 1% 2% 4% 0,2% 0,4% 1% l%+0,2% 2%+0,2% 2 0/0 0,5/0,5 0/0 0/3 0/3 0/3 0/1,5 0/1 4 2/2 1,5/2,5 0/2,5 1/4 1,5/4 0,5/4 0/3 0/3 30 9 4/4 3/4 1,5/4 3/4 3/4 2/4 3/4 1,5/425 Time after Active substance, weight% in treatment bath infection, weeks__a_ ___ a + b_ 1% 2% 4% 0.2% 0.4% 1% l% + 0.2% 2% + 0.2% 2 0 / 0 0.5 / 0.5 0/0 0/3 0/3 0/3 0 / 1.5 0/1 4 2/2 1.5 / 2.5 0 / 2.5 1/4 1.5 / 4 0.5 / 4 0/3 0/3 30 9 4/4 3/4 1.5 / 4 3/4 3/4 2/4 3/4 1.5 / 4
Eksempel 3Example 3
Ved dette forsøg blev der undersøgt et middel som omfatter a) 35 alkylbenzyldimethylammoniumchlorid, hvori antallet af carbon-atomer i alkylgruppen er i alt væsentligt 12-18, og b) digua-nideret octylendiamin.In this experiment, an agent comprising a) 35 alkyl benzyl dimethyl ammonium chloride was investigated in which the number of carbon atoms in the alkyl group is substantially 12-18, and b) diguanidated octylenediamine.
DK 154534 BDK 154534 B
99
Fyrreplader med en tykkelse på ca. 1 cm og en diameter på ca. 6 cm blev neddyppet i en sporeopløsning indeholdende sporer af blå svampe. Pladerne fik derpå lov til at tørre i 5-10 sekunder og blev derefter neddyppet i vandige opløsninger af henholdsvis komponenterne a) og b)-5 og blandinger af disse komponenter. Pladerne blev neddyppet i opløsningerne i 5-10 sekunder og derefter tørret i ca. 20 sekunder. To identisk behandlede plader blev anbragt i plastposer sammen med en referenceplade, som udelukkende var blevet dyppet i sporeopløsningen. Poserne blev lukket og lagret ved stuetemperatur.Pine plates with a thickness of approx. 1 cm and a diameter of approx. 6 cm was immersed in a spore solution containing spores of blue fungi. The plates were then allowed to dry for 5-10 seconds and then immersed in aqueous solutions of components a) and b) -5 and mixtures of these components, respectively. The plates were immersed in the solutions for 5-10 seconds and then dried for approx. 20 seconds. Two identically treated plates were placed in plastic bags along with a reference plate which had been dipped exclusively in the spore solution. The bags were closed and stored at room temperature.
1010
Visuel undersøgelse af angreb i sammenligning med referencepladen blev foretaget på forskellige tidspunkter efter infektionen, og der blev givet karakterer efter en skala fra 0 til 4, hvor 0 betegner intet angreb, 1 en. tendens til angreb, 2 angreb, 3 kraftigt angreb og 4 meget kraftigt angreb. Resultaterne er vist i den efterfølgende tabel.Visual examination of attacks in comparison with the reference plate was done at different times after the infection, and scores were given on a scale of 0 to 4, with 0 denoting no attack, 1 a. tendency to attack, 2 attacks, 3 powerful attacks and 4 very powerful attacks. The results are shown in the following table.
Tid efter Aktiv stof, vægt% i behandlingsbadet infektion, dage a_ _b a + b 2Q 1% 2% 0,2% 0,4% 1% + 0,2% 2% + 0,4% 26 3 3 3 3 0 0 33 4 3,5 3 3 0,5 0Time after Active substance, weight% in treatment bath infection, days a_ _b a + b 2Q 1% 2% 0.2% 0.4% 1% + 0.2% 2% + 0.4% 26 3 3 3 3 0 0 33 4 3.5 3 3 0.5 0
Eksempel 4.Example 4
2525
Dette forsøg blev gennemført på samme måde som beskrevet i eksempel 3. De undersøgte aktive komponenter var a) didecyldimethylammonium= chlorid og b) acetat af bis(8-guanidinooctyl)amin.This experiment was carried out in the same manner as described in Example 3. The active components examined were a) didecyldimethylammonium = chloride and b) acetate of bis (8-guanidinooctyl) amine.
Tid efter infektion, Aktivt stof, vægt% i behandlingsbad 30 da?e a b a + b 1% 2% 0,2% 0,4% 1% + 0,2% 2% + 0,4% 26 3 3 3 1,5 0 0 33 3 3 3 2,5 0 0 35Time after infection, Active substance, weight% in treatment bath 30 da? Eaba + b 1% 2% 0.2% 0.4% 1% + 0.2% 2% + 0.4% 26 3 3 3 1.5 0 0 33 3 3 3 2.5 0 0 35
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7705398A SE425043B (en) | 1977-05-10 | 1977-05-10 | FUNGICID COMPOSITION, PREFERRED FOR USE AS A THREE PROTECTIVE, CONTAINING AT LEAST ONE QUARTER OF AMMONIUM SUBSTANCE IN MIXING WITH AN AMINE COMPONENT |
| SE7705398 | 1977-05-10 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK206478A DK206478A (en) | 1978-11-11 |
| DK154534B true DK154534B (en) | 1988-11-28 |
| DK154534C DK154534C (en) | 1989-04-17 |
Family
ID=20331269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK206478A DK154534C (en) | 1977-05-10 | 1978-05-10 | FUNGICID MIXING OF A QUATERNARY AMMONIUM COMPOUND AND A GUANIDINE COMPONENT, AND USE OF IT |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS53139721A (en) |
| AT (1) | AT383770B (en) |
| CA (1) | CA1101605A (en) |
| CH (1) | CH639823A5 (en) |
| CS (1) | CS201005B2 (en) |
| DD (1) | DD135852A5 (en) |
| DE (1) | DE2820409C2 (en) |
| DK (1) | DK154534C (en) |
| FI (1) | FI62203C (en) |
| FR (1) | FR2390100A1 (en) |
| GB (1) | GB1581205A (en) |
| NZ (1) | NZ187128A (en) |
| PL (1) | PL111204B1 (en) |
| SE (1) | SE425043B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2483177A1 (en) * | 1980-05-29 | 1981-12-04 | Salkin Nicolas | NOVEL DISINFECTANT COMPOSITION COMPRISING A QUATERNARY AMMONIUM AND A HEXAMETHYLENE BIGUANIDE HYDROCHLORIDE OLIGOMER |
| JPS6028906A (en) * | 1983-07-26 | 1985-02-14 | Dainippon Ink & Chem Inc | Agricultural and horticultural fungicide |
| DK158570C (en) * | 1984-07-04 | 1990-11-12 | Gori As | FUNGICID AGENT FOR THE PROTECTION OF FRESH-CUTTED TREES AGAINST BLAST BINDING AND MOLD Fungi |
| JPS6157305A (en) * | 1984-08-29 | 1986-03-24 | 株式会社ザイエンス | Rotproof composition |
| DE3531356A1 (en) * | 1985-09-03 | 1987-03-12 | Hoechst Ag | MICROBICIDAL AGENTS BASED ON ALKYL-DI-GUANIDINIUM SALTS |
| DE4035772A1 (en) * | 1990-11-08 | 1992-05-14 | Bruno Wixforth | New fungicidal wood-dye - contg. water-insol. prod. of reaction of humic acid(s) with organic fungicide |
| CN1282698C (en) * | 2002-03-15 | 2006-11-01 | 上海塑杰科技有限公司 | Functional agglomerates of polyolefin as well as its preparing method and application |
| JP5101828B2 (en) * | 2006-03-22 | 2012-12-19 | 日本曹達株式会社 | Antifungal composition for wood and antifungal method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1184035B (en) * | 1962-10-17 | 1964-12-23 | Hoechst Ag | Disinfecting mild detergents |
| DE1249577B (en) * | 1964-06-18 | 1967-09-07 | Telefunken Patentverwertungsgesellschaft M.B.H., Ulm/Donau | Method and device for recognizing the position of a flat object with respect to a feature applied to it |
| GB1274668A (en) * | 1968-06-10 | 1972-05-17 | Ici Ltd | Pesticidal compositions comprising aminoguanidines |
| SE370003B (en) * | 1971-05-18 | 1974-09-30 | Kema Nord Ab | |
| AT318152B (en) * | 1972-07-31 | 1974-09-25 | Hurka Wilhelm | Disinfectants |
| DE2330481A1 (en) * | 1973-06-15 | 1975-01-09 | Benckiser Gmbh Joh A | DISH AND RINSE AGENT FOR DISHES AND THE LIKE |
| SE417569B (en) * | 1975-10-22 | 1981-03-30 | Kemanobel Ab | Certain stated mixtures of guanidated aliphatic polyamines, or their acid addition salts, for use as pesticides and antimicrobial agents |
-
1977
- 1977-05-10 SE SE7705398A patent/SE425043B/en not_active IP Right Cessation
-
1978
- 1978-04-27 AT AT306478A patent/AT383770B/en not_active IP Right Cessation
- 1978-05-01 NZ NZ18712878A patent/NZ187128A/en unknown
- 1978-05-04 CS CS285778A patent/CS201005B2/en unknown
- 1978-05-06 PL PL20664678A patent/PL111204B1/en unknown
- 1978-05-08 FI FI781435A patent/FI62203C/en not_active IP Right Cessation
- 1978-05-09 DD DD20527878A patent/DD135852A5/en unknown
- 1978-05-09 CA CA302,900A patent/CA1101605A/en not_active Expired
- 1978-05-09 FR FR7813616A patent/FR2390100A1/en active Granted
- 1978-05-10 DK DK206478A patent/DK154534C/en not_active IP Right Cessation
- 1978-05-10 JP JP5456278A patent/JPS53139721A/en active Granted
- 1978-05-10 GB GB1883078A patent/GB1581205A/en not_active Expired
- 1978-05-10 CH CH510078A patent/CH639823A5/en not_active IP Right Cessation
- 1978-05-10 DE DE19782820409 patent/DE2820409C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| SE425043B (en) | 1982-08-30 |
| DE2820409C2 (en) | 1981-12-03 |
| PL111204B1 (en) | 1980-08-30 |
| DD135852A5 (en) | 1979-06-06 |
| FR2390100B1 (en) | 1981-01-23 |
| FI62203B (en) | 1982-08-31 |
| SE7705398L (en) | 1978-11-11 |
| FI781435A (en) | 1978-11-11 |
| JPS614367B2 (en) | 1986-02-08 |
| FI62203C (en) | 1982-12-10 |
| CS201005B2 (en) | 1980-10-31 |
| AT383770B (en) | 1987-08-25 |
| GB1581205A (en) | 1980-12-10 |
| DK206478A (en) | 1978-11-11 |
| DK154534C (en) | 1989-04-17 |
| CA1101605A (en) | 1981-05-26 |
| NZ187128A (en) | 1980-03-05 |
| FR2390100A1 (en) | 1978-12-08 |
| CH639823A5 (en) | 1983-12-15 |
| JPS53139721A (en) | 1978-12-06 |
| PL206646A1 (en) | 1979-05-21 |
| ATA306478A (en) | 1987-01-15 |
| DE2820409A1 (en) | 1978-12-14 |
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Legal Events
| Date | Code | Title | Description |
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| PUP | Patent expired |