EP0863248A2 - Agent contre les organismes attaquant la kératine - Google Patents

Agent contre les organismes attaquant la kératine Download PDF

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Publication number
EP0863248A2
EP0863248A2 EP98103117A EP98103117A EP0863248A2 EP 0863248 A2 EP0863248 A2 EP 0863248A2 EP 98103117 A EP98103117 A EP 98103117A EP 98103117 A EP98103117 A EP 98103117A EP 0863248 A2 EP0863248 A2 EP 0863248A2
Authority
EP
European Patent Office
Prior art keywords
substrates
neem
ppm
pests
azadirachtin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98103117A
Other languages
German (de)
English (en)
Other versions
EP0863248A3 (fr
Inventor
Ingomar Dr. Krehan
Gabriele Koppe-Jans
Johannes Haas
Heinz Dr. Kölbl
Heinrich F. Dr. Moeschler
Klaus Dr. Naumann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19754572A external-priority patent/DE19754572A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0863248A2 publication Critical patent/EP0863248A2/fr
Publication of EP0863248A3 publication Critical patent/EP0863248A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/006Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with wool-protecting agents; with anti-moth agents
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/10Animal fibres
    • D06M2101/12Keratin fibres or silk

Definitions

  • the invention relates to an aqueous textile protection agent for controlling textile pests, especially of keratin-digesting pests and for finishing endangered textiles and substrates, which contains extracts of Fruits of the neem tree is labeled, and a method of equipment of keratinous substrates with these agents.
  • Keratin-containing substrates in the sense of the present invention are, for example Wool, silk, (rough) leather, furs, feathers, animal hair (e.g. as upholstery material), Horn (for example for the production of buttons, clips, etc.) and for yarns and Textiles whose combinations and blends with other natural or synthetic fibers, such as wool / polyacrylonitrile, wool / cotton, Wool / polyester etc.
  • Keratin pests are keratin-digesting insects, especially their larvae. Examples of this are pests from the order of the Tineidae (real moths), such as Tineola bisselliella (clothes moth), Tinea pellionella (fur moth) and Hofmannophila pseudospretella (seed moth), and pests from the series Beetles, such as the larvae of two genera of Dermestidae (bacon beetles), such as Anthrenus verbasci (cotton herb beetle), Anthrenus pimpinellae (Bibernell flower beetle), Anthrenus scrophulariae (common carpet beetle), Anthrenus fasciatus (banded carpet beetle), attagenus pellio (spotted fur beetle), Attagenus piceus (dark fur beetle) and Anthrenocerus australis.
  • Tineidae real moths
  • Tineola bisselliella
  • Keratin pests are Niptus hololeucus (brass beetle), Gibbium psylloides (Globular beetle) and Lepisnia saccharina (silverfish), some of which are not only Eat keratin.
  • neem tree (Azadirachta indica, Indian lilac) and its preparations, such as neem extract, neem oil or neem bark, are the subject of numerous descriptions (summary in Schmutterer, "The Neem Tree", Verlag Chemie-Verlagsgesellschaft Weinheim, New York, Cambridge, Tokyo, 1995).
  • the preparations of the neem tree are characterized by a content of azadirachtin; it has the formula Azadirachtin is the analytical lead substance; however, it is always associated with modified azadirachtins, which are designated with the capital letters A to K, and also with other substances, such as limonoids.
  • Neem supplements have a bioactive effect.
  • a toothpaste for preventing paradontosis contains active ingredients from the bark of the neem tree. It has also been described to use neem preparations as insecticides in the agricultural sector (Schmutterer, "The Neem Tree"), for example to protect ornamental plants in the field and in the greenhouse against the whitefly, mealybugs, trips, caterpillars and black mosquitoes. Neem oil has also been propagated as a moth repellent (preparation TN-MP 100 from Terra Nostra). However, a processing temperature of below 50-60 ° C is necessary so that finishing of textiles before a subsequent dyeing process at cooking temperature is impossible.
  • the protective effect is also short-lived and must be refreshed, for example, after each wet cleaning by renewed treatment. This short effect was confirmed by our own tests. Furthermore, oil as a natural substance is not immune to fungal attack and freedom from fungal toxins (aflatoxins). It therefore seemed hopeless to permanently equip keratin-containing substrates with neem preparations against pests.
  • extracts of the fruits of the neem tree show an excellent and long-lasting antioxidant action against textile pests, in particular against keratin-digesting insects, when they are used with industry-standard formulation auxiliaries in an aqueous formulation for the treatment of keratin-containing substrates of the above-mentioned alt, in particular keratin-containing substrates Textiles.
  • neem extracts are their toxicological harmlessness when they have an effect comparable to other pesticides.
  • the LD 50 value in rats and when administered orally reaches the astonishingly high value of> 5,000 mg / kg body weight; irritation to skin and eyes was not observed.
  • the LD 50 rate was still> 1,000 mg / kg body weight, whereby teratogenicity, mutagenicity and genotoxicity could not be determined.
  • the ecotoxicological behavior is therefore significantly cheaper than comparable protective agents.
  • the invention accordingly relates to agents for controlling textile pests, especially of keratin-digesting pests and those at risk of equipping Textiles and substrates containing extracts of the fruits of the neem tree a content of azadirachtins, surfactants and optionally auxiliary formers in the form of an aqueous formulation.
  • the invention further relates to a method for finishing keratin-containing Substrates for protection against infestation and damage caused by textile pests, the is characterized in that an agent containing extracts of the fruits of the neem tree containing azadirachtins, surfactants and, if necessary further forming aids in the form of an aqueous formulation with the help Application methods known per se in such an amount on the substrates brings that after application the substrates 100 to 30,000 ppm neem extract, calculated as azadirachtin and based on the weight of the substrates.
  • Extracts of the fruits of the neem tree are all that contain azadirachtins have, preferably extracts of the fruit kernel.
  • the neem extract is e.g. from the fruit kernels of the neem fruit by extraction with alcohols, such as Methanol or ethanol, with glycols, glycol ethers or hydrocarbons, such as for example petroleum ether, ligroin, kerosene, hexane, octane, cyclohexane, toluene, Xylene and others won.
  • Substrates containing keratin are those mentioned above, in particular wool, silk and their above-mentioned mixtures with other natural or synthetic fibers, as well as furs.
  • Keratin pests are the above, among which are exemplary in particular the clothes moth, the carpet beetle and the fur beetle are to be mentioned.
  • neem extracts contain 0.1 to 35% by weight, preferably 0.2 to 33% by weight, Azadirachtine.
  • Neem extracts are for example under the following names commercially available: Margosan-O® with 0.2% by weight azadirachtin (Grace Sierra), Azatin EC® with 2.9% by weight Azadirachtin (from Agridyne), Azal® with 30.7% by weight Azadirachtin (from Trifolio-M) and Azal F® with 5.6% by weight azadirachtin (from Trifolio-M).
  • Suitable surfactants for the agents according to the invention are anionic, cationic, nonionic and ampholytic surfactants.
  • Suitable anionic surfactants are those which contain a long-chain aliphatic or alkylaromatic radical of 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms and a carboxyl-sulfonic acid or phosphonic acid group, preferably a sulfonic acid group, and which as Cation one from the group of H + , Li + , Na + , K + , NH 4 + , HOCH 2 CH 2 NH 3 + , (HOCH 2 CH 2 ) 2 NH 2 + or (HOCH 2 CH 2 ) 3 NH + exhibit.
  • Suitable cationic surfactants are those which have a long-chain organic radical of the type mentioned for the anionic surfactants and an amino group, an amino group substituted with C 1 -C 4 -alkyl or an alnino group quaternized with C 1 -C 4 -alkyl, the thereof Counter cation OH - , Cl - , Br - , 1/2 SO 4 - , 1/3 PO 4 --- , acetate, formate or propionate.
  • Nonionic surfactants are those with an aliphatic, aromatic, araliphatic or alkylaromatic radical with a total of 10 to 20 carbon atoms, which has a hydroxyl, carboxyl, carboxamide or amino group with a mobile H atom and with ethylene oxide or propylene oxide in the Was condensed to form a polyether; the ethylene oxide or propylene oxide groups are present in a number of 4 to 60, preferably 6 to 30.
  • Ampholytic surfactants are those that carry a positive and a negative (partial) charge within the same molecule. Such surfactants are, for example, betaines or sulfobetaines, which have a long-chain residue in the sense of the length described for the other surfactants. All of these surfactants are well known to those skilled in the art and are widely used as emulsifiers, dispersants and wetting agents.
  • Preferred surfactants are the anionic, the nonionic and mixtures thereof.
  • Forming aids that can continue to be used are, for example Solvent / water mixtures, complexing agents, defoamers, acids and bases.
  • the inventive Means other known compounds effective against textile pests from the groups mentioned at the beginning.
  • the agents according to the invention are produced by combining the used extract of the fruits of the neem tree, the surfactant and water and optionally the other forming aids in any order.
  • the homogenization is done by simple stirring, shaking or other Mixing.
  • neem extract in such an amount that it becomes a content on azadirachtins from 100 to 30,000 ppm, preferably 250 to 10,000 ppm, particularly preferably 500 to 7,500 ppm, calculated.
  • the amount of surfactant is 0.05-3% by weight, based on the total amount of the formulation.
  • the amount of other forming aids are 0.1-5% by weight if they are used.
  • the rest, 100% by weight, is water.
  • the agents according to the invention are adjusted to a pH of 3-9, preferably 4-8.
  • Acids and bases which can be used for this purpose are, for example, HCl, H 2 SO 4 , H 3 PO 4 , formic acid, acetic acid, propionic acid, NaOH, KOH and NH 3 .
  • the use of the agents according to the invention in processes for the treatment of substrates containing keratin to protect against infestation and damage caused by Keratin-digesting pests can be found in practically all processing states and all wet application and spray processes customary in the textile industry and related areas, possibly simultaneously with other finishing processes on the substrates mentioned.
  • the agent according to the invention can For example, be added to the dye bath before the usual dyeing process can also be applied when washing the substrates mentioned.
  • the Treatment is carried out in an aqueous medium.
  • the process according to the invention is used in the process for the treatment of substrates containing keratin Agents placed on the substrates in an amount such that the substrates after application 100 to 30,000 ppm, preferably 250 to 20,000 ppm, particularly preferably 500 to 15,000 ppm, neem extract, calculated as azadirachtin and based on the weight of the substrates.
  • the necessary for this Amount of agent according to the invention in the form of an aqueous formulation results from a simple calculation of the content of the invention By means of azadirachtin on the one hand and the percentage absorption of the active ingredient on the other hand from the liquor to the treated substrate.
  • the invention Process for treating substrates containing keratin is carried out at pH in the range from 3 to 9, preferably from 4 to 8. You can do this at Exhaust process up to a temperature just below the boiling point, for example about 98 ° C, as well as in the continuous process at a temperature of 40 to 85 ° C can be worked. Other methods are the spraying method and the Foam application.
  • neem extract 10 g were at room temperature in 70 ml of diethylene glycol monobutyl ether registered and solved. Then 20 g of a nonionic Emulsifier (styrene-phenol adduct with approx. 16 equivalents of ethylene oxide per phenolic OH group) added. Then it was filtered through a 5 ⁇ m filter small amounts of insoluble residues from the neem extract remove. The solution obtained was stable in storage and formed on entry into Water stable emulsions.
  • a nonionic Emulsifier styrene-phenol adduct with approx. 16 equivalents of ethylene oxide per phenolic OH group
  • An aqueous finishing liquor contained 2 g / l Na di (3-ethylhexyl) phosphate as Wetting agents and graded amounts of the emulsions from example 1 or example 2, so that on neem extract 0.01 or 0.025 or 0.05 or 0.1 or 0.5 or 1% by weight, based on the total weight of the equipment fleet, was present.
  • White wool fabric was used treated until complete wetting with the equipment fleet, on one Foulard squeezed to 100% liquor intake and air dried.
  • Example 4 feeding control samples and test samples for moth larvae
  • the control of larval feeding activity in control examinations without the invention Treatment is the standard for evaluating the effect of an invention Treatment.
  • three control samples are set up.
  • the Control samples consist of white, untreated wool fabric and become Cut lobes of 4 x 4 cm each.
  • a flap was placed in each lid and at a laboratory temperature of 23 up to 25 ° C and 50 to 65% rel. Humidity stored.
  • pro Shell 25 clothing moth larvae (medium stage, i.e. 15 larvae) with a body weight of 15 ⁇ 2 mg). After a week it was made an evaluation using the method described below.
  • Test samples The same white woolen fabric as in the feeding controls was treated in the manner described with the agent according to the invention, cut into sample lobes of the size mentioned and placed in three petri dishes with an unperforated lid and populated with the same number of larvae under the same laboratory conditions. After another week, the same method was used for the evaluation.
  • Milling control sample and test samples The experiments were carried out similarly to Example 4, with the difference that 20 larvae of the carpet beetle (medium stage, ie 15 larvae with a body weight of 18 ⁇ 1 mg) were prepared per dish and lobule. After two weeks, the evaluation was carried out using the same method.
  • Feed control and test sample The procedure was similar to that in Example 4, but with 20 larvae of the fur beetle (medium stage, ie 15 larvae with a body weight of 55 ⁇ 3 mg). After two weeks, the evaluation was carried out again.

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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)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP98103117A 1997-03-06 1998-02-23 Agent contre les organismes attaquant la kératine Withdrawn EP0863248A3 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19709123 1997-03-06
DE19709123 1997-03-06
DE19754572A DE19754572A1 (de) 1997-03-06 1997-12-09 Mittel gegen Keratinschädlinge
DE19754572 1997-12-09

Publications (2)

Publication Number Publication Date
EP0863248A2 true EP0863248A2 (fr) 1998-09-09
EP0863248A3 EP0863248A3 (fr) 1999-03-17

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EP98103117A Withdrawn EP0863248A3 (fr) 1997-03-06 1998-02-23 Agent contre les organismes attaquant la kératine

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EP (1) EP0863248A3 (fr)
JP (1) JPH10251114A (fr)
AU (1) AU5634498A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2826380A1 (fr) * 2001-06-22 2002-12-27 Nathalie Chetboun Procede de traitement anti-acariens et anti-microbien des materiaux textiles par huile naturelle microencapsulee
WO2007079768A1 (fr) * 2005-12-22 2007-07-19 Rieke Hermann A Utilisation d'un complément alimentaire pour animaux

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5110591A (en) * 1990-03-01 1992-05-05 Ppg Industries, Inc. Neem oil emulsifier
DE4109473A1 (de) * 1991-03-22 1992-09-24 Kleeberg Hubertus Dr Verfahren zur herstellung eines lagerfaehigen azadirachtinreichen insektizids aus samenkernen des neem-baumes
US5372817A (en) * 1991-01-03 1994-12-13 W. R. Grace & Co.-Conn. Insecticidal compositions derived from neem oil and neem wax fractions
DE19532447A1 (de) * 1995-09-04 1997-03-06 Heinz Prof Dr Rembold Repellens zur Schädlingsbekämpfung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5110591A (en) * 1990-03-01 1992-05-05 Ppg Industries, Inc. Neem oil emulsifier
US5372817A (en) * 1991-01-03 1994-12-13 W. R. Grace & Co.-Conn. Insecticidal compositions derived from neem oil and neem wax fractions
DE4109473A1 (de) * 1991-03-22 1992-09-24 Kleeberg Hubertus Dr Verfahren zur herstellung eines lagerfaehigen azadirachtinreichen insektizids aus samenkernen des neem-baumes
DE19532447A1 (de) * 1995-09-04 1997-03-06 Heinz Prof Dr Rembold Repellens zur Schädlingsbekämpfung

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2826380A1 (fr) * 2001-06-22 2002-12-27 Nathalie Chetboun Procede de traitement anti-acariens et anti-microbien des materiaux textiles par huile naturelle microencapsulee
WO2003002807A3 (fr) * 2001-06-22 2004-02-19 Nathalie Chetboun Procede de traitement anti-acarien et anti-microbien de materiaux textiles
US9220275B2 (en) 2001-06-22 2015-12-29 Yereb Lab Ltd. Method for acaricidal and microbicidal treatment of textile materials
WO2007079768A1 (fr) * 2005-12-22 2007-07-19 Rieke Hermann A Utilisation d'un complément alimentaire pour animaux

Also Published As

Publication number Publication date
JPH10251114A (ja) 1998-09-22
EP0863248A3 (fr) 1999-03-17
AU5634498A (en) 1998-09-10

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