EP0011789A1 - Process for treating wool - Google Patents

Process for treating wool Download PDF

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Publication number
EP0011789A1
EP0011789A1 EP79104557A EP79104557A EP0011789A1 EP 0011789 A1 EP0011789 A1 EP 0011789A1 EP 79104557 A EP79104557 A EP 79104557A EP 79104557 A EP79104557 A EP 79104557A EP 0011789 A1 EP0011789 A1 EP 0011789A1
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Prior art keywords
fluoro
ester
wool
phenoxy
benzyl
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EP79104557A
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German (de)
French (fr)
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EP0011789B1 (en
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Rainer Dr. Fuchs
Arnold Fuss
Johannes Haas
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Bayer AG
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Bayer AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/006—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with wool-protecting agents; with anti-moth agents

Definitions

  • the invention relates to agents which contain fluorine-substituted 3-vinyl-2,2-dimethyl-cycloprcpancarboxylic acid (3-phenoxy-benzyl) ester derivatives and are suitable for protecting wool against infestation and damage caused by pest digestion by keratin, and methods for treatment of wool with these means.
  • fluorine substituted cyclopropanecarboxylic acid phenoxybenzyl esters e.g. 3- (2,2-Dichlorcvinvl) -2, 2-dimethyl-cyclepropancarbonklare- (4-fluoro-3-phenoxy-benzyl) -ester, have strong insecticidal and acariside properties (cf. ) 264 and 2 730 515).
  • Formula (I) includes all stereoisomers, optical isomers and mixtures thereof.
  • the cyclopropanecarboxylic acid phenoxybenzyl esters of the formula (I) on the one hand have a considerably higher activity against keratin pests than the compounds of analogous constitution and the same direction of action known from the prior art, and on the other hand their protective action remains practically undiminished even after repeated washing or chemical cleaning.
  • the alkyl radicals preferably have 1 to 4 carbon atoms.
  • Halogen is preferably chlorine or bromine in the case of R 1 and R 2 and preferably fluorine or chlorine in the case of R 4 .
  • the application can be practically in all processing states and all usual in the textile industry N rust revitalizen made on wool, wool textiles and wool-containing textiles.
  • the wool preservative can, for example, be added to the dye bath before the usual dyeing process, but it can also be applied when washing wool.
  • the treatment is preferably carried out in an aqueous medium.
  • Woolen yarn is brought into a treatment bath at 40 ° C in a liquor ratio of 1:10, that per liter of water contains. The mixture is then heated to boiling temperature and the coloring is completed in the usual way. A yellow-colored wool is obtained which has good protection against moth and beetle damage and is also resistant to repeated washes.
  • Carpet yarn which consists of a wool-polyamide mixture in a ratio of 80:20, is brought into a treatment bath at 40 ° C in a liquor ratio of 1:25, that per liter of water contains. The mixture is then heated to the boil and the staining is finished in the usual way.
  • the yellow-colored wool portion of the carpet yarn treated in this way has good protection against moth and beetle damage, which is resistant to repeated washes.
  • a wool-polyester blend (ratio 45:55) is placed at 40 ° C in a liquor ratio 1:25 in a treatment bath, per liter of water contains. The mixture is then heated to boiling temperature and the coloring is completed in the usual way.
  • the wool portion of the tone-on-tone dyed fabric has good protection against moth and beetle damage, which is also resistant to repeated washes.
  • the dye specifications relate to Color Index (1971) Vol. 1 and 2.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

1. Process for treating wool for protection against infestation by keratin pests and against damage caused by being eaten by these pests, characterised in that the wool is treated with a fluorine-substituted 3-vinyl-2,2-dimethyl-cyclopropanecarboxylic acid 3-phenoxybenzyl ester.

Description

Die Erfindung betrifft Mittel, die flucrsubstituierte 3-Vinyl-2,2-dimethyl-cycloprcpancarbonsäure-(3-phencxy- benzyl)-ester-Derivate enthalten und zum Schutz ven Wolle gegen Befall und Fraßschäden durch keratinverdauende Schädlinge geeignet sind, sowie Verfahren zur Behandlung von Wolle mit diesen Mitteln.The invention relates to agents which contain fluorine-substituted 3-vinyl-2,2-dimethyl-cycloprcpancarboxylic acid (3-phenoxy-benzyl) ester derivatives and are suitable for protecting wool against infestation and damage caused by pest digestion by keratin, and methods for treatment of wool with these means.

Es ist bekannt, daß fluersubstituierte Cyclopropancarbonsäurephenoxybenzylester, z.B. 3-(2,2-Dichlorcvinvl)-2, 2-dimethyl-cyclepropancarbonsäure-(4-fluoro-3-phenoxy- benzyl)-ester, starke insektizide und akariside Eigenschaften aufweisen (vgl. Deutsche Offenlegungssehriften 2 709 264 und 2 730 515S) 264 und 2 730 515).It is known that fluorine substituted cyclopropanecarboxylic acid phenoxybenzyl esters, e.g. 3- (2,2-Dichlorcvinvl) -2, 2-dimethyl-cyclepropancarbonsäure- (4-fluoro-3-phenoxy-benzyl) -ester, have strong insecticidal and acariside properties (cf. ) 264 and 2 730 515).

Weiter ist bereits bekannt, daß bestimmte Cyclopropan-carbonsäure-phenexybenzylester, z.B. 3-(2,2-Dichlere- vinyl)-2,2-dimethyl-cyclopropancarbonsäure-(3-phenoxy- benzyl)-ester ("Permethrin"), (vgl. Pestic., Sci. 1977, 8, 279-283) und z.B. 3-(2,2-Dimethylvinyl)-2,2-dimethyl- cyclopropancarbonsäure-(3-phenoxybenzyl)-ester (vgl. JP-058341) zur Bekämpfung von Textilschädlingen verwendet werden können.Furthermore, it is already known that certain cyclopropane-carboxylic acid phenoxybenzyl esters, for example 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylic acid (3-phenoxy- benzyl) ester ("permethrin"), (see Pestic., Sci. 1977, 8, 279-283) and, for example, 3- (2,2-dimethylvinyl) -2,2-dimethylcyclopropanecarboxylic acid (3-phenoxybenzyl ) esters (cf. JP-058341) can be used to control textile pests.

Die Wirkung von Permethrin gegen Textilschädlinge ist jedoch insbesondere bei niedrigen Aufwandmengen nicht zufriedenstellend und wird zudem durch Waschen oder chemische Reinigung der Textilien vermindert.However, the effect of permethrin against textile pests is unsatisfactory, especially when applied in small amounts, and is also reduced by washing or dry cleaning the textiles.

Es wurde nun gefunden, daß fluorierte 2-Vinyl-2,2-dimethyl-cyclopropancarbonsäure-(3-phenoxyphenyl)-esterDerivate, insbesondere solche der Formel

Figure imgb0001
in welcher

  • R1 für Wasserstoff, Alkyl oder Halogen,
  • R 2 für Alkyl, Halogen oder für gegebenenfalls durch Halogen substituiertes Phenyl,
  • R 3 für Wasserstoff, Cyano oder Äthinyl oder
  • R 4 für Wasserstoff oder Halogen stehen,
  • sehr gut zur Behandlung von Wolle, Wolltextilien und wollhaltigen Textilien als Fraßschutz gegen Keratinschädlinge geeignet sind.
It has now been found that fluorinated 2-vinyl-2,2-dimethyl-cyclopropanecarboxylic acid (3-phenoxyphenyl) ester derivatives, in particular those of the formula
Figure imgb0001
 in which
  • R 1 represents hydrogen, alkyl or halogen,
  • R 2 represents alkyl, halogen or phenyl which is optionally substituted by halogen,
  • R 3 is hydrogen, cyano or ethynyl or
  • R 4 represents hydrogen or halogen,
  • are very well suited for the treatment of wool, wool textiles and textiles containing wool as protection against keratin pests.

Die Formel (I) schließt alle Stereoisomeren, optischen Isomeren und deren Mischungen ein.Formula (I) includes all stereoisomers, optical isomers and mixtures thereof.

Überraschenderweise zeigen die Cyclopropancarbonsäurephenoxybenzylester der Formel (I) einerseits eine erheblich höhere Wirkung gegen Keratinschädlinge als die aus dem Stand der Technik bekannte Verbindungen analoger Konstitution und gleicher Wirkungsrichtung, und andererseits bleibt ihre Schutzwirkung auch bei wiederholtem Waschen oder Chemischreinigen praktisch unvermindert erhalten.Surprisingly, the cyclopropanecarboxylic acid phenoxybenzyl esters of the formula (I) on the one hand have a considerably higher activity against keratin pests than the compounds of analogous constitution and the same direction of action known from the prior art, and on the other hand their protective action remains practically undiminished even after repeated washing or chemical cleaning.

In Formel (I) haben die Alkylreste vorzugsweise 1 bis 4 Kohlenstoffatome. Halogen'steht im Fall von R1 und R 2 bevorzugt für Chlor oder Brom und im Fall von R4 bevorzugt für Fluor oder Chlor.In formula (I) the alkyl radicals preferably have 1 to 4 carbon atoms. Halogen is preferably chlorine or bromine in the case of R 1 and R 2 and preferably fluorine or chlorine in the case of R 4 .

Besonders hervorzuheben sind Verbindungen der Formel (I) in der

  • R1 und R2 gleich sind und für Methyl, Chlor oder Brom stehen,
  • R 3 für Wasserstoff, Cyano oder Äthinyl und
  • R 4 für Wasserstoff oder Fluor stehen.
Particularly noteworthy are compounds of formula (I) in the
  • R 1 and R 2 are the same and represent methyl, chlorine or bromine,
  • R 3 is hydrogen, cyano or ethynyl and
  • R 4 represents hydrogen or fluorine.

Die Verbindungen der Formel (I) sind bereits bekannt (vgl. DE-OS 2.709 264 und deutsche Anmeldungen P 27 30 515 und P 27 39 854). Die Verbindungen können nach den dort beschriebenen Verfahren hergestellt werden. Als Beispiele für besonders bevorzugte Verbindungen seien genannt:

  • 3-(2-Methyl-propen(1)yl)-2,2-dimethyl-cyclopropancarbonsäure(4-fluoro-3-phenoxy-benzyl)-ester und -(4-fluoro-3-phenoxy-α -cyano-benzyl)-ester,
  • 3-(2,2-Dichloro-vinyl)-2,2-dimethyl-cyclopropancarbonsäure-(4-fluoro-3-phenoxy-benzyl)-ester, -(4-fluoro-3-phenoxy- α-cyano-benzyl)-ester und -(4-fluoro-3-phenoxy-α-äthinyl-benzyl)-ester sowie
  • 3-(2,2-Dibromo-vinyl)-2,2-dimethyl-cyclopropancarbonsäure-(4-fluoro-3-phenoxy-benzyl)-ester, -(4-fluoro-3-phenoxy-α-cyano-benzyl)-ester und -(4-fluoro-3-phenoxy-α-äthinyl-benzyl)-ester.
The compounds of formula (I) are already known (see. DE-OS No. 2. 709 264 and German Applications P 27 30 515 and P 27 39 854). The compounds can be prepared by the processes described there. Examples of particularly preferred compounds are:
  • 3- (2-methyl-propen (1) yl) -2,2-dimethyl-cyclopropanecarboxylic acid (4-fluoro-3-phenoxy-benzyl) ester and - (4-fluoro-3-phenoxy-α-cyano-benzyl ) -ester,
  • 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylic acid- (4-fluoro-3-phenoxy-benzyl) ester, - (4-fluoro-3-phenoxy-α-cyano-benzyl) esters and - (4-fluoro-3-phenoxy-α-äthinyl-benzyl) esters and
  • 3- (2,2-dibromo-vinyl) -2,2-dimethyl-cyclopropanecarboxylic acid- (4-fluoro-3-phenoxy-benzyl) ester, - (4-fluoro-3-phenoxy-α-cyano-benzyl) esters and - (4-fluoro-3-phenoxy-α-aethyl-benzyl) esters.

Von Interesse sind ferner:

  • 3-(2-Methyl-propen(1)yl)-2,2-dimethyl-cyclopropancarbonsäure-(4-fluoro-3-(4-fluoro-phenoxy)-α-cyano-benzyl)-ester,
  • 3-(2,2-Dichloro-vinyl)-2,2-dimethyl-cyclopropancarbonsäure-(4-fluoro-3-(3-fluoro-phenoxy)-benzyl-ester, -(4-fluoro-3-(3-fluoro-phenoxy)- α-cyano-benzyl)-ester, -(4-fluoro-3-(4-fluoro-phenoxy)-benzyl)-ester und -(4-fluoro-3-(4-fluoro-phenoxy)-α -cyano-benzyl)-ester, 3-(2,2-Dibromo-vinyl)-2,2-dimethyl-cyclopropancarbonsäure-(4-fluoro-3-(3-fluoro-phenoxy)-benzyl)-ester, (4-fluoro-3-(3-fluoro-phenoxy)-α-cyano-benzyl)-ester und -(4-fluoro-3-(4-fluoro-phenoxy)- α-cyano-benzyl)-ester sowie 3-(2-Chloro-2-(4-chloro-phenyl)-vinyl)-2,2-dimethyl-cyclopropancarbonsäure-(4-fluoro-3-phenoxy-d-cyano-benzyl)-ester.
Also of interest are:
  • 3- (2-methyl-propen (1) yl) -2,2-dimethyl-cyclopropanecarboxylic acid- (4-fluoro-3- (4-fluoro-phenoxy) -α-cyano-benzyl) ester,
  • 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylic acid- (4-fluoro-3- (3-fluoro-phenoxy) -benzyl ester, - (4-fluoro-3- (3- fluoro-phenoxy) - α-cyano-benzyl) esters, - (4-fluoro-3- (4-fluoro-phenoxy) benzyl) ester and - (4-fluoro-3- (4-fluoro-phenoxy) -α-cyano-benzyl) ester, 3- (2nd , 2-dibromo-vinyl) -2,2-dimethyl-cyclopropanecarboxylic acid- (4-fluoro-3- (3-fluoro-phenoxy) -benzyl) ester, (4-fluoro-3- (3-fluoro-phenoxy) -α-cyano-benzyl) esters and - (4-fluoro-3- (4-fluoro-phenoxy) - α-cyano-benzyl) esters and 3- (2-chloro-2- (4-chloro-phenyl ) -Vinyl) -2,2-dimethyl-cyclopropanecarboxylic acid- (4-fluoro-3-phenoxy-d-cyano-benzyl) ester.

Zu den Keratinschädlingen gehören

  • aus der Ordnung der Tineidae (echte Motten)
  • z.B. Tineola bisselliella (Kleidermotte), Tinea pellionella (Pelzmotte) und Hofmannophila pseudopretella (Samenmotte)

und aus der Reihe der Käfer die Larven zweier Gattungen der Dermestidae (Speckkäfer),
  • z.B. Anthrenus verbasci (Wollkraut-Blütenkäfer), Anthrenus pimpinellae (Bibernell-Blütenkäfer)i -Anthrenus scrophilariae (Gemeiner Teppichkäfer), Anthrenus fasciatus (Bebänderter Teppichkäfer), Attagenus Pellio (Gefleckter Pelzkäfer) und Attagenus piceus (Dunkler Pelzkäfer).
Keratin pests include
  • from the order of the Tineidae (real moths)
  • e.g. Tineola bisselliella (clothes moth), Tinea pellionella (fur moth) and Hofmannophila pseudopretella (seed moth)

and from the row of beetles the larvae of two genera of the Dermestidae (bacon beetles),
  • e.g. Anthrenus verbasci (cotton herb beetle), Anthrenus pimpinellae (Bibernell flower beetle) i -Anthrenus scrophilariae (common carpet beetle), Anthrenus fasciatus (banded carpet beetle), Attagenus Pellio (spotted fur beetle) and Attagenus piceus (dark fur beetle).

Die Anwendung kann praktisch in allen Bearbeitungszuständen und allen in der Textilindustrie üblichen Naßprozessen an Wolle, Wolltextilien und wollhaltigen Textilien erfolgen. Das Wollschutzmittel kann beispielsweise dem Färbebad vor dem üblichen Färbeprozeß zugesetzt werden, es kann aber auch beim Waschen von Wolle appliziert werden. Bevorzugt wird die Behandlung in wäßrigem Medium durchgeführt.The application can be practically in all processing states and all usual in the textile industry N aßprozessen made on wool, wool textiles and wool-containing textiles. The wool preservative can, for example, be added to the dye bath before the usual dyeing process, but it can also be applied when washing wool. The treatment is preferably carried out in an aqueous medium.

Beispiel 1example 1

1000 kg Rohwolle werden nach dem Kontinue-Waschprozeß pro Stunde in einem Leviathan gewaschen und mottenecht ausgerüstet. Dazu wird im letzten Bottich des Leviathans die Flotte mit verdünnter Essigsäure auf einen pH-Wert unterhalb 7 eingestellt und mit 0,02 g/1 der Verbindung der DE-OS 2 709 264, Beispiel 6, versetzt. Die Behandlung erfolgt bei 40-45°C,After the continuous washing process, 1000 kg of raw wool are washed in a Leviathan per hour and mothproof. For this purpose, the liquor is adjusted to a pH below 7 in the last vat of leviathan with dilute acetic acid and 0.02 g / 1 of the compound of DE-OS 2 709 264, example 6, is added. The treatment takes place at 40-45 ° C,

Zur Aufrechterhaltung der Wirkstoffkonzentration im Behandlungsbad erfolgt ein Nachsatz von 0,02 % Wirkstoff, bezogen auf Warengewicht. Dieser Nachsatz wird als wäßrige Lösung während der gesamten Behandlungszeit dem Bad kontinuierlich zugegeben. Die so behandelte Rohwolle besitzt einen guten Schutz gegen Motten - und Käferfraß, der auch gegen wiederholte Wäschen beständig ist. Die Wolle kann so ohne Beeinträchtigung ihrer technologischen Eigenschaften allen in der Textilindustrie üblichen Weiterverarbeitungsprozessen zugeführt werden.To maintain the concentration of active substance in the treatment bath, an addition of 0.02% of active substance, based on the weight of the goods, is carried out. This additive is continuously added to the bath as an aqueous solution during the entire treatment time. The raw wool treated in this way has good protection against moth and beetle damage, which is also resistant to repeated washes. The wool can thus be fed to all of the further processing processes customary in the textile industry without impairing its technological properties.

Beispiel 2Example 2

Wollgarn wird bei 40°C im Flottenverhältnis 1:10 in ein Behandlungsbad gebracht, das pro Liter Wasser

Figure imgb0002
enthält. Anschließend wird auf Siedetemperatur erhitzt und die Färbung auf übliche Weise fertiggestellt. Es wird eine gelbgefärbte Wolle erhalten, die einen guten Schutz gegen Motten- und Käferfraß besitzt, der auch gegen wiederholte Wäschen beständig ist.Woolen yarn is brought into a treatment bath at 40 ° C in a liquor ratio of 1:10, that per liter of water
Figure imgb0002
 contains. The mixture is then heated to boiling temperature and the coloring is completed in the usual way. A yellow-colored wool is obtained which has good protection against moth and beetle damage and is also resistant to repeated washes.

Beispiel 3Example 3

Teppichgarn, das aus einer Wolle-Polyamid-Mischung im Verhältnis 80:20 besteht, wird bei 40°C im Flottenverhältnis 1:25 in ein Behandlungsbad gebracht, das pro Liter Wasser

Figure imgb0003
enthält. Anschließend wird auf Siederemperatur erhiazt und die Färbung auf übliche Weise fertiggeszellt. Der gelbgefärbte Wollanteil des so behandelten Tsppichgarnes besitzt einen guten Schutz gegen Motten- und Käferfraß, der gegen wiederholte Wäschen beständig ist.Carpet yarn, which consists of a wool-polyamide mixture in a ratio of 80:20, is brought into a treatment bath at 40 ° C in a liquor ratio of 1:25, that per liter of water
Figure imgb0003
 contains. The mixture is then heated to the boil and the staining is finished in the usual way. The yellow-colored wool portion of the carpet yarn treated in this way has good protection against moth and beetle damage, which is resistant to repeated washes.

Beispiel 4Example 4

Ein Wolle-Polyester-Mischgewebe (Verhältnis 45:55) wird bei 40°C im Flottenverhältnis 1:25 in ein Behandlungsbad gebracht, das pro Liter Wasser

Figure imgb0004
enthält. Anschließend wird auf Siedetemperatur erhitzt und die Färbung in üblicher Weise fertiggestellt. Der Wollanteil des Ton-in-Ton gefärbten Gewebes besitzt einen guten Schutz gegen Motten- und Käferfraß, der auch gegen wiederholte Wäschen beständig ist. Die Farbstoffangaben beziehen sich auf Colour-Index (1971) Band 1 und 2.A wool-polyester blend (ratio 45:55) is placed at 40 ° C in a liquor ratio 1:25 in a treatment bath, per liter of water
Figure imgb0004
 contains. The mixture is then heated to boiling temperature and the coloring is completed in the usual way. The wool portion of the tone-on-tone dyed fabric has good protection against moth and beetle damage, which is also resistant to repeated washes. The dye specifications relate to Color Index (1971) Vol. 1 and 2.

Claims (6)

1. Mittel zum Schutz von Wolle gegen Befall und Fraßschäden durch Keratinschädlinge, gekennzeichnet durch einen Gehalt an einem fluorsubstituierten 3-Vinyl-2,2-dimethyl-cyclopropan-carbonsäure-(3-phenoxybenzyl)-ester.1. Agent for protecting wool against infestation and damage caused by keratin pests, characterized by a content of a fluorine-substituted 3-vinyl-2,2-dimethyl-cyclopropane-carboxylic acid (3-phenoxybenzyl) ester. 2. Mittel nach Anspruch 1, gekennzeichnet durch einen Gehalt an einem Ester der Formel
Figure imgb0005
in welcher R1 für Wasserstoff, Alkyl oder Halogen, R 2 für Alkyl, Halogen oder für gegebenenfalls durch Halogen substituiertes Phenyl, R 3 für Wasserstoff, Cyano oder Äthinyl und R 4 für Wasserstoff oder Halogen stehen. 2. Composition according to claim 1, characterized by a content of an ester of the formula
Figure imgb0005
 in which R 1 represents hydrogen, alkyl or halogen, R 2 represents alkyl, halogen or phenyl which is optionally substituted by halogen, R 3 is hydrogen, cyano or ethynyl and R 4 represents hydrogen or halogen. 3. Mittel Anspruch 2, gekennzeichnet durch eine Gehalt an einem Ester der Formel des Anspruchs 2, in der R1 und R gleich sind und für Methyl, Chlor oder Brom stehen, R 3 für Wasserstoff, Cyano oder Äthinyl und R4 für Wasserstoff oder Fluor stehen. 3. Means claim 2, characterized by a content of an ester of the formula of claim 2, in which R 1 and R are the same and represent methyl, chlorine or bromine, R 3 is hydrogen, cyano or ethynyl and R 4 represents hydrogen or fluorine. 4. Verfahren zur Behandlung von Wolle zum Schutz gegen Befall und Fraßschäden durch Keratinschädlinge, dadurch gekennzeichnet, daß man die Wolle mit einem fluorsubstituierten 3-Vinyl-2,2-dimethyl-cyclopropan-carbonsäure-(3-phenoxybenzyl)-ester behandelt.4. Process for the treatment of wool to protect against infestation and damage caused by keratin pests, characterized in that the wool is treated with a fluorine-substituted 3-vinyl-2,2-dimethyl-cyclopropane-carboxylic acid (3-phenoxybenzyl) ester. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man die Wolle mit einem Ester des Anspruchs 2 behandelt.5. The method according to claim 4, characterized in that the wool is treated with an ester of claim 2. 6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man die Behandlung in wäßrigem Medium vornimmt.6. The method according to claim 4, characterized in that one carries out the treatment in an aqueous medium.
EP79104557A 1978-12-01 1979-11-19 Process for treating wool Expired EP0011789B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2852028 1978-12-01
DE19782852028 DE2852028A1 (en) 1978-12-01 1978-12-01 AGENT AGAINST KERATIN PEDES AND METHOD FOR TREATING WOOL WITH THESE AGENTS

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EP0011789A1 true EP0011789A1 (en) 1980-06-11
EP0011789B1 EP0011789B1 (en) 1981-11-25

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4602912A (en) * 1984-06-27 1986-07-29 Ciba-Geiby Corporation Mothproofing and beetleproofing composition: 5-(pyridyloxy- or thiothenylcarbamoyl)barbituric acid
EP0883710A1 (en) * 1995-12-21 1998-12-16 Wool Research Organisation Of New Zealand (Inc.) A method for insect-resist treatment of carpet and textiles
US6290992B1 (en) 1996-02-13 2001-09-18 Shelby J. Magnuson-Hawkins Foam formulation for termite control and method of application therefor

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0170611B1 (en) * 1984-04-06 1988-10-12 Ciba-Geigy Ag Process for protecting keratinic material against deterioration by keratin devouring insects
DE3734341A1 (en) * 1987-10-10 1989-04-27 Bayer Ag AGENT AGAINST KERATIN PEDS AND METHOD FOR TREATING WOOL
EP2108733B1 (en) 2008-04-08 2013-03-06 THOR GmbH Insect repellent treated natural fibre materials, process and use

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2709264A1 (en) * 1977-03-03 1978-09-07 Bayer Ag SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES
DE2730515A1 (en) * 1977-07-06 1979-01-18 Bayer Ag SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2709264A1 (en) * 1977-03-03 1978-09-07 Bayer Ag SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES
DE2730515A1 (en) * 1977-07-06 1979-01-18 Bayer Ag SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE TEXTILE INSTITUTE, Band 70, Nr. 2, The Textile Institute, Manchester M35 DR, GB, R. MAYFIELD et al.: "A comparison of new synthetic pyrethroids for the industrial insectproofing of wool", Seiten 53-61. * Ganz * *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4602912A (en) * 1984-06-27 1986-07-29 Ciba-Geiby Corporation Mothproofing and beetleproofing composition: 5-(pyridyloxy- or thiothenylcarbamoyl)barbituric acid
EP0883710A1 (en) * 1995-12-21 1998-12-16 Wool Research Organisation Of New Zealand (Inc.) A method for insect-resist treatment of carpet and textiles
EP0883710A4 (en) * 1995-12-21 2000-11-29 Wool Res Organisation A method for insect-resist treatment of carpet and textiles
US6290992B1 (en) 1996-02-13 2001-09-18 Shelby J. Magnuson-Hawkins Foam formulation for termite control and method of application therefor

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AU5330079A (en) 1980-06-05
DE2852028A1 (en) 1980-06-12
NZ192259A (en) 1981-05-29
AU527269B2 (en) 1983-02-24
DE2961469D1 (en) 1982-01-28
EP0011789B1 (en) 1981-11-25
JPS616184B2 (en) 1986-02-24
JPS5580578A (en) 1980-06-17

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