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AU736807B2 - Cleaning compositions - Google Patents

Cleaning compositions Download PDF

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Publication number
AU736807B2
AU736807B2 AU52742/98A AU5274298A AU736807B2 AU 736807 B2 AU736807 B2 AU 736807B2 AU 52742/98 A AU52742/98 A AU 52742/98A AU 5274298 A AU5274298 A AU 5274298A AU 736807 B2 AU736807 B2 AU 736807B2
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AU
Australia
Prior art keywords
cleaning
cleaning composition
aqueous
ethyl
insects
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.)
Ceased
Application number
AU52742/98A
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AU5274298A (en
Inventor
Mohammad Jalalian
Roland Martin
Maria Elisabeth Prenzel
Francesco Rosell I Oller
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Merck Patent GmbH
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Merck Patent GmbH
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Publication date
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Publication of AU736807B2 publication Critical patent/AU736807B2/en
Anticipated expiration legal-status Critical
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

1 Cleaning compositions The invention relates to all types of cleaning compositions which comprise the insect repellent ethyl 3-(Nbutylacetamino)propionate and are therefore used for cleaning and for simultaneously repelling non-bloodsucking insects from the surfaces and rooms to be cleaned.
In many respects, insects are a nuisance or even a threat to humans. In addition to the damage caused by some species of insects (for example the destruction of entire harvests), both humans and also many animals are troubled in one way or another, bitten and otherwise plagued by a wide range of insects. This can lead to infections and the transmission of dangerous diseases.
Insecticides are the main weapon in the fight against insects, but their use and toxicity profiles are not always without problems. These toxins often have undesirable effects on humans and animals, so that 20 their use is limited or even banned.
However, measures such as the use of insecticides are not absolutely necessary to prevent the immediate nuisance. Some insects, such as, for example, cockroaches, in any case cannot be eradicated 25 completely, and efforts are therefore increasingly directed more at repelling these insects than at destroying them.
Furthermore, protection of the environment is nowadays very much in the foreground, and preventive 30 measures are therefore preferably taken.
Insect repellents are therefore now preferred to insecticides in combating insects, since the former are directed merely towards stopping insects from remaining and nesting on certain surfaces or in rooms.
Chemicals for repelling or destroying, for example, cockroaches, flies, mosquitoes or ants have been on the market for a long time, but many are 0 dangerous to humans and animals or have a very
RA/
2 unpleasant smell, so their adverse properties severely limit their use.
In view of the relatively small number of insect repellents which are not only effective but also acceptable from the toxicological aspect, great efforts to provide suitable products continue to be made in this field.
The substance ethyl 3-(N-butylacetamino)propionate is a proven insect repellent which has been known for a long time and is also employed as such in cosmetics formulations. It can be obtained commercially, for example from Merck KGaA, Darmstadt.
This substance, with its outstanding properties in respect of skin and mucosa tolerance without toxic, allergizing or sensitizing properties, has hitherto been used in cosmetics formulations in order to protect humans directly from attack by, for example, mosquitoes or flies.
This substance furthermore has a high chemical 20 stability, i.e. it cannot be hydrolysed, cannot be photooxidized, cannot be oxidized and has a high heat stability.
Surprisingly, it has now been found that ethyl 3-(N- 25 butylacetamino) propionate can also be incorporated into formulations of cleaning compositions of all types, and can therefore be used to drive off and keep away non-bloodsucking insects permanently from the surfaces cleaned with them, which can be hard or soft in nature.
It is known from the literature (US-A-3,018,217), for example, to incorporate an insect repellent into a polishing composition for domestic floors, dibutyl succinate having been employed as the repellent. EP 0 525 893 also describes compositions for cleaning comprising various insect repellents, such as, 3 for example, N, N-diethyl-m-toluamide (DEET) However, nowhere are cleaning compositions which comprise the abovementivned _ethyl -bu..tylaetamino) propionate described.
In contrast to the prior art, the invention employs an insect repellent which has hitherto been used directly on humans, and the cleaning compositions according to the invention can thus be regarded as toxicologically acceptable and are therefore highly superior to the compositions known to date.
The term "non-bloodsucking insect" is used here in the broadest sense and is intended to include, for example.
common cockroaches (German cockroaches and also American roaches), flies, ants, lice, bugs and even spiders.
Thus, in accordance with the present invention there is provided a method for cleaning an object or surface, whilst simultaneously repelling therefrom non-blood sucking insects, wherein there is applied to such object or surface a toxicologically acceptable cleaning composition based on aqueous or aqueous-alcoholic solutions or in the form of a detergent, wax, gel, shampoo, spray, solid product, emulsion, cream or dispersion, the said composition comprising an active amount, sufficient to repel insects upon treatment with the cleaning 25 composition of the non-blood sucking insect repellent ethyl 3- (N-butylacetamino)propionate.
The cleaning compositions according to the invention preferably comprise 0.1 to 20% by weight of ethyl 3- (N-butylacetamino) propionate, particularly preferably 0.1 to 10% by weight, especially preferably 0.1 to 6% by weight.
The insect repellent of the present invention can be incorporated into all types of cleaning 4 compositions, preferably into domestic cleaners. If appropriate, these domestic cleaners can additionally comprise, as well as the ethyl 3-(N-butylacetamino)propionate according to the invention, one or more insect repellents in each case in an amount of 0.1 to by weight. These can be both synthetic substances, such as, for example, diethyltoluamide, 2-ethyl- 1,3-hexanediol, dimethyl phthalate or dibutyl succinate, and also essential oils which are naturally occurring or identical to those in nature and act as insect repellents, such as, for example, menthol oil, citronella oil or lemon oil.
The insect repellent is preferably incorporated into solutions (aqueous or aqueous-alcoholic) or dispersions (or dispersed in a pulverulent carrier), into cleaning agent compositions such as detergents, floor or wall cleaners (tile cleaners), window cleaners, upholstery or carpet cleaners, also in shampoo form, into solid or liquid soaps, into wax, 20 into creams or into sprays.
It can be incorporated into any other suitable .formulation in which it could be of benefit. For example into insecticides or antibacterial compositions, furniture polishes or floor waxes or else 25 into compositions for cleaning certain hand tools which are used, for example, for animal husbandry or in horticulture.
The use of the cleaning compositions according to the invention causes non-bloodsucking insects to avoid 30 contact with the cleaned surface after the hard or soft surfaces have been cleaned, since a film of this cleaning composition comprising the insect repellent has been formed as a result of the cleaning process.
The non-bloodsucking insects are additionally kept away from the area of the cleaned surface by the smell of this composition.
Thus, for example, ants, common cockroaches and other non-bloodsucking insects can be stopped from Spenetrating into 5 storage rooms by cleaning shelves, walls and the floor with a cleaning composition according to the invention.
Cleaning upholstery or carpets with suitable shampoos can also stop the non-bloodsucking insects from nesting there and laying their eggs therein.
Detergents can furthermore prevent insects from entering linen cupboards and therefore into clothes.
From the above description, it is obvious that a wide range of compositions are possible for the cleaning agent according to the invention, and the cleaning compositions can be used for many different purposes.
However, the invention is preferably used in the field of domestic cleaners.
Such cleaners are composed of a large number of components.
For example, they comprise organic (soaps) or preferably synthetically organic surface-active, washactive substances (surfactants), which can be anionic, amphoteric, ampholytic, zwitterionic, nonionic or cationic in nature, or else a mixture thereof. The anionic detergent bases are by far the most important here. Many such detergents are described in "Surface Active Agents and Detergent", Volume II, by Schwartz, 25 Perry and Berch (1958 Interscience Publishers, Inc.).
However, the expert can also read about the most common surfactants in all the major reference works of chemistry (for example R6mpp, Beilstein and the like).
The cleaners furthermore comprise builders and, 30 if appropriate, bleaching agents, fragrances and auxiliaries.
Any detergent suitable for this purpose can be used as an anionic surfactant. Anion-based surfactants usually include, for example, fatty alcohol sulfates, paraffinsulfonates, fatty acid condensation products and alkylbenzenesulfonates and -phosphonates, and also alkyl sulfates and phosphates. The anionic surfactants are preferably sodium salts, but potassium, ammonium 6 and triethanolammonium salts are also often employed in some liquid compositions. The alkyl radicals are preferably straight-chain and preferably have 12 to 16 carbon atoms.
Synergistic combinations, primarily with fatty alcohol polyglycol ethers, have proved suitable as the base for many compositions.
Suitable nonionic raw materials are condensation products of lipophilic components and lower alkylene oxides or polyalkyleneoxy units. The fatty alcohol polyglycol ethers mentioned, the alkylphenol polyglycol ethers or else fatty acid alkylamides, for example, are preferably employed.
Cationic surfactants can also be used, for example aliphatic quaternary ammonium salts.
The substances known as builders are also generally known and can be inorganic or organic in nature and water-soluble or insoluble. Substances such as polyphosphates, for example pentasodium triphosphate, carbonates or bicarbonates, for example sodium carbonate or sodium bicarbonate, zeolites, for example zeolite A, polycarboxylates, for example sodium salts of copolymers of acrylic acid and maleic acid, and also borates and silicates, for example laminar sodium silicate, are preferred.
Further auxiliaries or additives which can be added are fragrances and dyestuffs, bleaching agents or brighteners, antistatic agents, antibacterial agents, fungicides, foam-forming reagents and also anti-foaming substances, antioxidants and enzymes.
The abovementioned substances for composing cleaning compositions are intended to be examples and have no limiting character for the formulations according to the invention.
All the substances known in the prior art which are described for formulating such cleaning compositions can according to the invention [sic] be mixed according to the invention with ethyl 3-(N- 7butylacetamino)propionate.
The cleaning compositions according to the invention can be present in solid form, as a powder, as tablets, in block or piece form, as a paste, as a gel, in liquid form, as a wax, as a cream, as an emulsion, as a dispersion, as a foam or as a spray (aerosol form) or as other suitable forms appropriate for the particular use.
The quantitative composition of the individual components for the various formulation possibilities is well-known to the expert in this field and does not have to be listed here in more detail.
According to the invention, the content of ethyl 3-(N-butylacetamino)propionate in the particular formulations is 0.1 to 20% by weight, preferably 0.1 to by weight, especially preferably 0.1 to 6% by weight.
The cleaning compositions according to the invention are preferably present as an aqueous or aqueous-alcoholic solution, as a detergent, as a wax, as a gel, as an emulsion, as a cream, as a shampoo, as a spray, as a dispersion or as a solid product.
The methods for the preparation of such products are generally known to the expert in the field of preparation of soaps and detergents and do not have to be explained in more detail here.
To prepare an aqueous or aqueous-alcoholic solution, the insect repellent is preferably dissolved in a suitable solvent, such as water (which usually means demineralized water), lower alcohols, such as, for example, ethanol, or mixtures thereof. These mixtures can of course also additionally comprise other substances, such as, for example, esters, aldehydes, ketones, hydrocarbons and also halogenated hydrocarbons. Examples of the latter which may be mentioned are isobutane, dichlorodifluoromethane, monofluorotrichloromethane and other chlorinated and/or fluorinated methanes, ethanes or propanes. Such
J
8 substances include those liquefiable gases which remain in the liquid state in pressurized containers ready for use as sprays.
Particularly preferred cleaning compositions of this invention comprise, as a synthetic organic surfactant, an anionic or nonionic surfactant, or mixtures thereof, builders and/or fillers and the insect repellent.
These cleaning compositions or detergents can be present in particle form or in liquid form. The liquid form comprises the same individual components, but in addition a liquid medium, and if appropriate also emulsifying substances and other auxiliaries.
Preferred shampoos for cleaning upholstery or carpets also comprise water-soluble soaps and synthetic wash-active substances, builder salts, the insect repellents, and usually water as the liquid medium.
Such shampoos can also be formulated as a gel or in paste or powder form.
Solid products according to the invention in block, tablet or piece form (bars of soap), which can be used for cleaning laundry, carpets and/or hard surfaces, such as, for example, floors and walls, can also be prepared.
In all these formulations, the ratios of soaps or synthetic organic surfactants, builders and auxiliaries to insect repellent are similar and can be varied within wide ranges. Preferably, the formulations comprise 1 to 40% of surfactants or soaps, 10 to 90% of builders and fillers and 0.1 to 20% of ethyl 3-(Nbutylacetamino)propionate (figures in by weight).
Water, alcohols, auxiliaries and/or emulsifying substances are usually added for completion (to 100% by weight).
The various cleaning compositions described can be prepared by methods known to the expert. Such processes include spray drying, dry mixing, dissolving and/or dispersing and/or emulsifying, grinding or 17 1 i IN) 9alternatively pressing.
When the cleaning compositions according to the invention are applied by spraying, wiping, rubbing or other methods to the surfaces to be cleaned, the insect repellent which they comprise is deposited on these surfaces in a sufficiently high concentration or amount to act as a repellent against insects.
Particularly preferred cleaning compositions of this invention are those in liquid form.
The following formulations, which are used as general-purpose cleaners, are especially preferred embodiments according to the invention.
Amphoteric surfactants, for example those based on cocamidoalkylbetaine, alone or mixed with anionic, cationic and nonionic surfactants, are preferably employed in these general-purpose cleaners. Neutral formulations as well as alkaline or acidic compositions can be prepared with these.
Salt-free capryl iminodipropionate is preferably employed as a further amphoteric surfactant for use in highly alkaline or strongly acidic formulations.
Further particularly preferred surfactant groups are the amine oxides and the alkyl polyglucosides, which are particularly readily mixed with betaines and lauryl ether sulfates.
General-purpose cleaners can be employed universally, as the name implies. They are usually neutral to slightly alkaline formulations.
Formulations according to the invention of this type with antibacterial additives are also particularly preferred.
The cleaning compositions according to the invention have a particularly good action against ants and common cockroaches.
With the cleaning compositions of the present invention, the consumer thus has available essentially non-toxic and therefore highly environment-friendly but nevertheless highly active products.
10 By using the cleaning compositions according to the invention and the process according to the invention, it has been possible to demonstrate in practice that, for example, significantly fewer cockroaches were to be found behind cupboards or under refrigerators compared with beforehand.
If floors, walls, sinks, doors or cupboards in a house or flat are therefore treated regularly with the cleaning compositions according to the invention, the incidence of insects, in particular cockroaches or ants, is reduced practically to zero.
Without further embodiments, it is also assumed that an expert can use the above description in the broadest scope. The preferred embodiments are therefore to be interpreted merely as a descriptive and not in any way as a limiting disclosure.
The complete disclosure of all the Applications, Patents and publications mentioned above and below is introduced into this Application by reference.
20 The following examples are intended to illustrate the invention.
Example 1: General-purpose cleaner with a good cleaning and non-blood sucking insect repellent action Composition: Ethyl 3-(N-butylacetamino)propionate 3.000 (Art. No. 111887) Tego® Betaine F 50 7.500 Ammonyx LO 10.000 Texapon N 28 15.000 Trisodium citrate dihydrate (Art. No. 4.000 106446) Sodium carbonate (Art. No. 106392) 3.000 Ethanol 96% (Art. No. 100971) 3.000 Water, demineralized to 100.000 11 The sodium carbonate and trisodium citrate are dissolved in water. The other substituents are then added in the sequence shown while stirring.
Sources of supply: Merck KGaA, Darmstadt Th. Goldschmidt AG, Essen Henkel KGaA, DUsseldorf Example 2: Alkaline general-purpose cleaner Composition: Ethyl 3-(N-butylacetamino)propionate (Art. No. 111887) Tegotain® 485 Lutensol A 8 Trisodium citrate dihydrate (Art. No. 106446) Water, demineralized %3.000 3.000 10.000 9.000 3.000 to 100.000 The trisodium citrate is dissolved in water. The other constituents are then added in the sequence shown while stirring.
Sources of supply: Merck KGaA, Darmstadt Th. Goldschmidt AG, Essen BASF, Ludwigshafen 12 Example 3: Antibacterial general-purpose cleaner Ethyl 3-(N-butylacetamino)propionate (Art. No. 111887) Tego@ Betaine F 50 BTC 50 Trisodium citrate dihydrate (Art. No. 106446) Sodium carbonate (Art. No. 106392 Water, demineralized %3.000 3.000 5.000 5.000 4.000 3.000 to 100.000 9 .9 9 4*9 .9.
.9 9 S *99* 9
C
9 S 9 9 *5 9 9 9 9.
The sodium carbonate and trisodium citrate are dissolved in water. The other constituents are then added in the sequence shown while stirring. An antibacterially acting general-purpose cleaner with a non-blood sucking insect-repellent action is obtained.
Sources of supply: Merck KGaA, Darmstadt Th. Goldschmidt AG, Essen The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge in Australia.
Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers or steps but not the exclusion of any other integer or group of integers or steps.

Claims (6)

1. A method for cleaning an object or surface, whilst simultaneously repelling therefrom non-blood sucking insects, wherein there is applied to such object or surface a toxicologically acceptable cleaning composition based on aqueous or aqueous-alcoholic solutions or in the form of a detergent, wax, gel, shampoo, spray, solid product, emulsion, cream or dispersion, the said composition comprising an active amount, sufficient to repel insects upon treatment with the cleaning composition of the non-blood sucking insect repellent ethyl 3-(N- butylacetamino)propionate.
2. A method according to claim 1 wherein the cleaning composition comprises 0.1 to by weight of ethyl 3-(N-butylacetamino)propionate and, if appropriate, one or more additional insect repellents in an amount of 0.1 to 20% by weight.
3. A method according to claim 1 or 2 wherein the cleaning composition further comprises one or more insect repellents from the group consisting of diethyltoluamide, 2-ethyl-1,3-hexanediol, dimethyl phthalate, dibuthyl [sic] succinate, and/or one or more essential oils which act as insect repellents.
4. A method according to any one of claims 1-3 wherein the cleaning composition further comprises one or more essential oils which act as insect repellents from the group consisting of citronella oil, menthol oil and lemon oil.
A method according to any one of claims 1-4 wherein the cleaning composition is based on an aqueous or aqueous-alcoholic solution or in the form of a detergent, wax, gel, shampoo, spray, solid product, emulsion, cream or dispersion.
6. A method for cleaning an object or surface whilst simultaneously repelling 25 therefrom non-blood sucking insects, substantially as hereinbefore described with reference to the Examples. DATED this 15th day of June, 2001 MERCK PATENT GMBH By its Patent Attorneys DAVIES COLLISON CAVE
AU52742/98A 1996-10-17 1997-10-08 Cleaning compositions Ceased AU736807B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19642957A DE19642957A1 (en) 1996-10-17 1996-10-17 cleaning supplies
DE19642957 1996-10-17
PCT/EP1997/005525 WO1998017772A1 (en) 1996-10-17 1997-10-08 Detergents

Publications (2)

Publication Number Publication Date
AU5274298A AU5274298A (en) 1998-05-15
AU736807B2 true AU736807B2 (en) 2001-08-02

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ID=7809064

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AU52742/98A Ceased AU736807B2 (en) 1996-10-17 1997-10-08 Cleaning compositions

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EP (1) EP0934392B1 (en)
JP (1) JP4177459B2 (en)
KR (1) KR100497021B1 (en)
CN (1) CN1175095C (en)
AR (1) AR008495A1 (en)
AU (1) AU736807B2 (en)
BR (1) BR9712353A (en)
CA (1) CA2268920C (en)
CZ (1) CZ290022B6 (en)
DE (2) DE19642957A1 (en)
ES (1) ES2187759T3 (en)
ID (1) ID22707A (en)
PL (1) PL186314B1 (en)
TR (1) TR199900829T2 (en)
TW (1) TW415963B (en)
WO (1) WO1998017772A1 (en)
ZA (1) ZA979280B (en)

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US6646011B2 (en) * 1998-06-03 2003-11-11 Johnson & Johnson Consumer Companies, Inc. Insect repellant compositions
DE19909015C2 (en) * 1999-03-02 2001-11-29 Dirk Mundt Device for cleaning surfaces, in particular floors and wall surfaces
DE10034396A1 (en) * 2000-07-14 2002-01-31 Bayer Ag Creeping insect deterrent compositions
DE20115729U1 (en) 2001-09-25 2001-12-20 Stubna, Eduard, 80634 München Detergent with repetitive chemical substances
DE10351859A1 (en) * 2003-11-06 2005-06-09 Beiersdorf Ag Cosmetic and/or dermatological oil/water emulsions with viscosity within specified range, used as sprayable cosmetic preparation and textile impregnant, contain microcrystalline cellulose, xanthan gum and optionally repellent
DE102006045774A1 (en) * 2006-09-26 2008-04-03 Henkel Kgaa Textile treatment agents
DE102006045775A1 (en) * 2006-09-26 2008-04-03 Henkel Kgaa Surface treatment agent
KR101089418B1 (en) * 2008-08-14 2011-12-07 양원동 Scented cosmetics
KR101000557B1 (en) 2008-08-16 2010-12-14 양원동 Scented soap
KR101043182B1 (en) * 2008-08-21 2011-06-20 김미경 perfume
JP5897329B2 (en) * 2011-12-28 2016-03-30 住化エンバイロメンタルサイエンス株式会社 Cleaner for foamable glass
JP6095427B2 (en) * 2013-03-19 2017-03-15 大日本除蟲菊株式会社 Tick repellent efficacy enhancer and tick repellent method using tick repellent composition containing the same
MY199207A (en) * 2016-07-15 2023-10-19 Lec Kk Pest repellent composition, and method for repelling pests
JP7146484B2 (en) * 2018-06-27 2022-10-04 大日本除蟲菊株式会社 Spray agent for controlling pests on clothing, and method for controlling pests on clothing
KR102140537B1 (en) * 2018-11-01 2020-08-03 전남대학교산학협력단 Controlling composition for blight and controlling method for blight using the same

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CN1175095C (en) 2004-11-10
ID22707A (en) 1999-12-09
ES2187759T3 (en) 2003-06-16
ZA979280B (en) 1998-05-11
WO1998017772A1 (en) 1998-04-30
CN1234067A (en) 1999-11-03
DE59709030D1 (en) 2003-01-30
TR199900829T2 (en) 1999-06-21
EP0934392B1 (en) 2002-12-18
DE19642957A1 (en) 1998-04-23
PL186314B1 (en) 2003-12-31
KR20000049212A (en) 2000-07-25
EP0934392A1 (en) 1999-08-11
JP4177459B2 (en) 2008-11-05
JP2001502729A (en) 2001-02-27
CA2268920C (en) 2005-09-06
KR100497021B1 (en) 2005-06-23
BR9712353A (en) 1999-08-31
TW415963B (en) 2000-12-21
CZ128299A3 (en) 1999-08-11
CZ290022B6 (en) 2002-05-15
CA2268920A1 (en) 1998-04-30
AU5274298A (en) 1998-05-15
PL332822A1 (en) 1999-10-11
AR008495A1 (en) 2000-01-19

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