AU5835994A - Compositions for cleaning soiled animals and method therefor - Google Patents

Compositions for cleaning soiled animals and method therefor Download PDF

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Publication number
AU5835994A
AU5835994A AU58359/94A AU5835994A AU5835994A AU 5835994 A AU5835994 A AU 5835994A AU 58359/94 A AU58359/94 A AU 58359/94A AU 5835994 A AU5835994 A AU 5835994A AU 5835994 A AU5835994 A AU 5835994A
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AU
Australia
Prior art keywords
agent
animal
softening
washing
detaching
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Abandoned
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AU58359/94A
Inventor
Anne Basseres
Gerard Holtzinger
Nadine Medevielle
Bruno Verschuere
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Societe National Elf Aquitaine
Laboratoires de Biologie Vegetale Yves Rocher SA
Original Assignee
Societe National Elf Aquitaine
Laboratoires de Biologie Vegetale Yves Rocher SA
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Priority claimed from FR9300168A external-priority patent/FR2700342B1/en
Application filed by Societe National Elf Aquitaine, Laboratoires de Biologie Vegetale Yves Rocher SA filed Critical Societe National Elf Aquitaine
Publication of AU5835994A publication Critical patent/AU5835994A/en
Abandoned legal-status Critical Current

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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
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3734Cyclic silicones
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126Acylisethionates
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D3/16Organic compounds
    • C11D3/162Organic compounds containing Si
    • 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
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2093Esters; Carbonates
    • 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
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/80Derivatives of lignin containing no sulfo- or sulfate groups
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Peptides Or Proteins (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

A washing agent comprising: (a) 1-10 % washing and foaming agent; (b) 5-50 % wetting agent; (c) 0-25 % water-miscible solvent; and (d) the balance consisting of water and optional additives. The use of said agent for cleaning animals soiled by chemical compounds, especially hydrocarbons, is also disclosed.

Description

Translation of text of PCT application as published 1 COMPOSITIONS FOR CLEANING SOILED ANIMALS AND METHOD THEREFOR 5 The present invention relates to compositions for cleaning soiled animals. In particular, it relates to compositions for cleaning the coat, plumage, and so on of creatures that have become soiled by chemical products, notably by hydrocarbons. The present invention also 10 provides a method for using these compositions. Currently, hydrocarbons are notably transported by sea, in appropriate tankers. Transport costs combined with journey length have lead to the use of high-capacity tankers with a capacity in excess of 100,000 metric tons, 15 or even in excess of 300,000 metric tons. The term supertankers is currently used to describe such vessels. Unfortunately, such vessels have limited maneuverability due to their large size. Additionally, during storms and when subject to breakdown of rudder gear, engine and so 20 on, they are difficult to tow. It is sometimes impossible to take such ships in tow when meteorological conditions are particularly unfavorable. If the oil tanker, or supertanker is close to the coast, there is a risk of the ship coming ashore. Collision with rocks 25 causes damage to the hull or even a complete breaking up of the ship, leaving it in several parts. Hydrocarbons spread over the sand along the coast. This phenomenon, which is a major catastrophe, is known as a "black tide". Well known examples are those of the Amoco Cadiz and, 30 more recently, the Exxon Valdez. Black tides cause a heavy toll in flora and fauna. Thus, the black tide that the Exxon Valdiz produced in 1989 was reported to have killed thousands of marine mammals and more than 250 000 seabirds. Seabirds and 35 marine mammals are a particular target in an ecosystem destroyed by a black tide. Hydrocarbons, in particular crude oil, get attached to their plumage and coat, paralyzing them when the oil covers them practically 2 completely. Above all, the oil halts the natural mechanisms needed for the well-being of the animals occurring at the interface constituted by the coat or plumage. In the particular case of birds, under the 5 influence of hydrocarbons, the feathers become matted destroying the microstructures that capture air, used for insulation and needed for the well-being of the birds. Over a period of several hours and days, an inability to keep heat in leads to hypothermia, malnutrition and 10 dehydration. Moreover, hydrocarbon absorption at the birds' dermis leads to poisoning. Additionally, in an attempt to get rid naturally of the oils and hydrocarbons with which they are soiled, animals have a tendency to clean themselves. During this operation, they ingest 15 hydrocarbons which also results in poisoning. This shock to their metabolism, both at their coat or plumage as well as at alimentary level, leads to the birds dying. It is obvious that rapid cleaning in order to eliminate the hydrocarbons is extremely important in the animals' 20 rehabilitation, although this is only a first step. The different steps in such cleaning are the following: the animal is caught, transported to the place of treatment, clinically observed with, if necessary, administration of first aid. Subsequent steps concern 25 feeding, anti-stress treatment and then the actual cleaning performed by washing in successive baths of appropriate products. This is followed by rinsing, drying and release as quickly as possible. Throughout these steps, the animal is observed in order to decide 30 whether treatment should be continued or whether to administer euthanasia where the state of the animal is considered to be too critical. Great efforts have been made in recent years to provide compositions enabling animals, and particularly 35 birds, to be washed and cleaned effectively, and inoffensively. Several products have been proposed, such as, for example, conventional detergents such as Teepol (sold in France by Temama France, Puteaux, France), PCL 3 (Registered trademark), sawdust, corn starch, mineral oils, organic solvents, storage tank cleaning agents, and others. J. Haggin in "Science and Technology" reports the use of shampoos and washing-up detergents. These 5 products are described as having a good foaming ability, but poor suitability in the elimination of oils or hydrocarbons. Promising results obtained in the laboratory have in fact not been able to be reproduced under natural outdoor conditions. B. Jenssen and M. 10 Ekker in the magazine Marine Pollution Bulletin, vol. 20, page 509-512, 1989 describe the action and properties of four cleaning agents consisting of conventional detergents. The products that were tested were Zalo (A/S DeNoFa og Lilleborg Fabriker, Oslo, Norway); Taski-Profi 15 (Sutler A.G. Minchweilen, Switzerland); and OB-5 and OB-7 (Bentelsen, Blommenhalen, Norway) . Out of these, the authors report that Taski-Profi is the most effective, for a cleaning period of 10 to 13 minutes. Recently, several authors have studied the effect of a powerful 20 detergent, Teepol, and unfortunately came to the conclusion that although it is powerful, it is also extremely aggressive to the animal, such as a bird, and to the person performing cleaning. The problems listed above are encountered in 25 situations other than so called black tides. Similar problems occur when hydrocarbons of all natures are accidentally spilled, or are voluntarily dumped which happens when tankers clean their tanks at sea, in a process usually called degassing. Moreover, aquatic 30 media of all natures are concerned, rivers and streams, canals and so on being involved just as much as the marine environment. Moreover, oils and hydrocarbons are not the only compounds which create problems with pollution and damage to the natural environment. All 35 spillage of toxic chemical products poses comparable problems. Thus, the problems encountered at the time of black tides are met up with each time a chemical agent having a degree of toxicity vis-a-vis certain animal 4 species is spilled. Solutions provided here thus apply to all these cases. There is thus a need for a washing agent which is effective, quick to act, non-toxic and, obviously, 5 inexpensive. These aims, as well as further aims, are satisfied by this invention. Thus, the invention provides a washing agent comprising, by weight based on the total weight of said washing agent: 10 (a) 1 to 10% of a foaming and detergent agent; (b) 5 to 50% of a wetting agent; (c) 0 to 25% of a water-miscible solvent; (d) the balance consisting of water and optionally additives. 15 The foaming and detergent agent employed consists of detergents or surfactants conventionally employed for this purpose. The foaming and detergent agent is in fact what is also called, in the trade, a "shampoo" and in the present specification, the following terms: foaming and 20 detergent agent, shampoo and shampoo base all signify the same thing. Conventional shampoo bases are described in "Encyclopedia of Shampoo Ingredients" by Anthony Hunting, Micelle Press Inc. This shampoo base is thus constituted by conventional 25 surfactants. In the framework of the present invention, a foaming and detergent agent comprised, by weight of: (a) 60 to 95% of an anionic surfactant; and (b) 40 to 5% of an amphoteric surfactant,are 30 preferred. Any conventional anionic surfactant known to those skilled in the art can be used for the anionic surfactant. Examples from the following families can be cited: alkali metal or alkaline-earth or ammonium alkyl 35 (ether) sulfates in which the alkyl is long-chain fatty alkyl, such as for example ammonium and magnesium lauryl (ether) sulfates; sulfosuccinates; betaines; imidazoles.
5 Preferred anionic surfactants are ammonium lauryl sulfate and magnesium lauryl ether sulfate. The amphoteric surfactant employed can be any conventional amphoteric surfactant known to those skilled 5 in the art. Examples of these from the following families can be cited: the betaines, in particular the sulfo-betaines; the alkylamphodiacetates in which the alkyl is a long-chain fatty alkyl such as cocoamphodiacetate. Preferred amphoteric surfactants are 10 sulfo-betaine and cocoamphodiacetate. For the wetting agent, any conventional wetting agent known to those skilled in the art may be employed. A non-exhaustive list is for example provided in the Encyclopedia of Shampoo ingredients cited above. The 15 preferred wetting agent is an alkali metal or alkaline earth or ammonium dialkylsulfosuccinate, advantageously dioctylsodium sulfosuccinate, which will be abbreviated to DOSS below. The solvent may not be present in the washing agent. 20 It is however preferred to employ it to obtain a solvent action on the chemical compound requiring elimination. When employed, the solvent is selected as a function of the chemical compound to be eliminated and consists of any water-miscible solvent that is a solvent for the 25 chemical compound concerned. When it is required to eliminate hydrocarbons, the solvent is a solvent for fats, in particular oils and hydrocarbons. In one preferred embodiment of the invention, the solvent is a water-miscible solvent for fats. 30 The preferred solvents are alcohols, such as polypropylene and ethyleneglycol, ethyl alcohol, isopropyl alcohol, to mention but some. Preferably, the washing agent comprises, by weight based on the total weight of said washing agent: 35 (a) 2 to 5% of a foaming and detergent agent; (b) 15 to 20% of a wetting agent; (c) 10 to 20% of a water-miscible solvent; 6 (d) the balance consisting of water and optionally additives. In one embodiment the washing agent further comprises a conditioner, in an amount of from 0.1 to 5% by weight, 5 based on the total weight of the agent. The purpose of this conditioning agent, which has a film-forming effect, is to restore the natural hydrophobic nature of the feathers, hairs and so on of the creatures. Actually, it appears from the literature (Jenssen and Ekker, 1988) 10 that it is the physical structure of the feather which partially provides the feather with its hydrophobic nature. This hydrophobic effect is also obtained, for feathers as well as for hairs, with a naturally secreted product. Following cleaning with a detergent or 15 surfactant, secretion returns within days of cleaning, but at a slow rhythm. This rhythm of secretion is for example of the order of 50 mg/day, whereas the product of secretion is naturally present in an amount of several grams. One thus looks for a product having a cleaning 20 action which also re-establishes the hydrophobic character of the plumage or coat of the animal, in order to return the creature as quickly as possible to satisfactory conditions, the time factor being a key element. This aim is achieved by the embodiment of the 25 present invention mentioned above. The conditioning agent can be any conventional conditioning agent known to those skilled in the art. In the framework of this invention, a conditioning agent consisting, by weight of: 30 (a) 20 to 50% of a cationic polymer; and (b) 80 to 50% of a silicone, is preferred. The cationic polymer can be any conventionally employed cationic polymer, such as a quaternary ammonium polymer, and is preferably a quaternized guar gum. 35 The silicone employed can be any conventionally employed silicone; preferably, this is a silicone gum advantageously in solution in a cyclic silicone oil.
7 The washing agent may furthermore include all conventional additives. The following can be cited as typical examples: a pH regulating agent, a thickening agent, a preserving agent, a co-surfactant, a perfuming 5 agent, and so on. In particular, the washing agent can include a chelating or complexing compound. This chelating agent is advantageously present in an amount of 0.05 to 1% by weight, based on the weight of the washing agent. A 10 preferred chelating agent for this present invention consists of the tetra-sodium salt of ethylene diamino tetra-acetic acid (Na 4 EDTA). The washing agent is concentrated, which facilitates handling notably during transport to the place of use. 15 However, it is preferably used in diluted form. It is diluted with fresh water, or, failing this, with sea water. Thus, the present invention also provides aqueous compositions comprising, by weight based on the total 20 weight of the aqueous composition 0.1 to 20%, preferably 0.5 to 5%, of a washing agent according to the present invention. The present invention also relates to the application of the present washing agent to the cleaning of animals 25 and thus provides a method for cleaning animals, in particular birds. Thus, the present invention provides a method for cleaning soiled animals, said method comprising the steps of: 30 a) applying a washing agent according to this invention, optionally in an aqueous composition, to said animal; b) leaving said washing agent to act for 1 to 60 minutes; 35 c) optionally repeating steps a) and b); d) rinsing and optionally drying said animal. The washing agent can be applied in pure form, in which case it can be sprayed or applied by brush or 8 otherwise onto the body of the animal. Alternatively, it can be diluted in an aqueous composition such as described in this invention, after which the aqueous composition is applied to the animal. 5 Preferably, the washing agent is included in an aqueous composition of which the washing agent constitutes 0.1 to 20% by weight, preferably 0.5 to 5%. In one preferred embodiment, during step a) of the method, the composition is applied to the animal by 10 immersing the latter in the composition, taking care to keep its respiratory tract clear. Advantageously, the composition is left to act for preferably 5 to 20 minutes during step b). Preferably, mechanical action is applied to the 15 animal during step b). Such mechanical action can consist of pressure action on the plumage or coat, frequently manual. In the majority of cases, the pressure action is accompanied by massage action on the animal within the bath constituted by the composition, 20 administered by the personnel responsible for cleaning the animals. During step c), steps a) and b) are repeated 1 to 4 times, preferably twice. When several immersions are performed, the washing 25 agent concentration in the aqueous composition employed can be the same or different. When the concentrations vary, they preferably decrease during treatment. The cleaning method is not limited to hydrocarbons but similarly applies to all chemical compounds required 30 to be eliminated. The operating conditions are then adapted to the particular chemical compound. The operating conditions also comprise the use of appropriate temperatures. In effect, effectiveness can vary with temperature; generally, high temperatures give 35 good effectiveness. Account should be taken of the animal's physiology. Considering that hydrocarbons provoke hypothermia, the washing bath will advantageously be warm compared to the animal's body temperature.
9 Account will also be taken of the fact that the cleaning operation is often performed manually and the human operators need to withstand the cleaning temperatures. Thus, cleaning temperatures are conventionally comprised 5 between 10 and 500C, with a preferred range of from 20 to 45 0 C. In the case of birds, taking account of their normal body temperature, the bath is advantageously at 404C. This invention also provides an alternative 10 embodiment of the cleaning process described above. It has surprisingly been found that it is possible to apply the products constituting the washing agent separately without this leading to a substantial reduction in effectiveness. 15 Thus, the present invention provides a method for cleaning soiled animals, said method comprising the steps of: a) applying a wetting agent to said animal; b) allowing said wetting agent to act for 1 to 60 20 minutes; c) applying a foaming and detergent agent to said animal; d) leaving said foaming and detergent agent to act for 1 to 60 minutes; 25 e) optionally repeating steps a) to d); f) rinsing and, optionally, drying said animal. The expression, "optionally repeating steps a) to d)" should be taken to mean that one can simply repeat steps a) and b), or c) and d) or a), b), c) and d), or any 30 combination thereof; application of wetting agent as the last step is not generally necessary. Preferably, the wetting agent and the shampoo base, in other words the foaming and detergent agent, are included in compositions, for example alcohol or aqueous 35 compositions. These agents or compositions, are preferably applied by immersing the animal in the composition. It is left to act, during steps b) and d), preferably for 5 to 20 10 minutes. Advantageously, during steps b) and d), the animal is subjected to mechanical action. Mechanical action is identical to that described above. Similarly, as stated above, this method is not limited to 5 hydrocarbons but applicable to any chemical contaminant. The present invention thus provides a washing agent and various methods for applying it. The washing agent according to the present invention is distinctly more effective than agents conventionally 10 employed, all the most so as it is non-toxic. However, where the animal is not treated rapidly after exposure to the black tide, the hydrocarbons have a tendency to age on the plumage or coat, and it then becomes difficult to eliminate them. This difficulty also arises with very 15 heavy, high-boiling point hydrocarbons. In this case, pre-treatment is necessary. J. Haggin, Science & Technology, suggests pre-treatment that takes the form of treatment designed to soften the hydrocarbons. To achieve this, the use of methyl oleate is proposed, by 20 way of a pre-treatment agent. The present invention, according to one of its aspects, thus discloses an effective softening and detaching agent. Thus, the present invention also provides a softening and detaching agent comprised, by 25 weight, based on the total weight of said agent: (a) 10 to 90% of a fatty acid ester; (b) 90 to 10% of a wetting agent. This softening and detaching agent is also called a pre-shampoo or pre-washing agent and these terms have the 30 same meaning in this specification. The fatty acid ester employed can be any conventional ester known to those skilled in the art. Examples which can be cited are: isopropyl myristate and palmitate, and ethylhexyl cocoate. Ethylhexyl cocoate is preferred for 35 the purposes of this invention. The wetting agent is any known agent as indicated above when discussing the washing agent. In this present invention, the preferred wetting agent is an alkaline or 11 alkaline earth metal or ammonium dialkylsulfosuccinate and is advantageously dioctylsodium sulfosuccinate (DOSS), like it is in the washing agent. Preferably, the softening and detaching agent 5 comprises: (a) 30 to 70% of a fatty acid ester; (b) 70 to 30% of a wetting agent. The softening agent in fact acts as would a detaching agent for fabric. The softening agent can be applied as 10 such, using conventional techniques. It can furthermore be applied also without subsequent cleaning with a conventional washing agent or the washing agent according to this invention, although this manner of operating is not preferred. 15 The present invention also relates to the application of the softening agent according to this invention to the softening and/or detaching of hydrocarbon patches or concentrates on the plumage or coat of animals. Thus, the present invention provides a method for 20 softening or detaching concentrated sludge of chemical compounds, for example hydrocarbons, on the plumage or coats of animals, comprising the steps of: a) applying to said animal a softening and detaching agent according to this invention; 25 b) allowing said softening and detaching agent to act for at least 5 minutes; c) rinsing said animal; d) optionally, repeating steps a) and b); e) optionally drying said animal. 30 In one embodiment, during step a) of the method, the softening agent is applied to the animal by spraying. Unlike the washing agent which is applied diluted in an aqueous composition, the softening agent is applied in the pure state although dissolving it in a suitable 35 solvent can nevertheless be envisaged. It is possible to repeat the application of the softening agent when there are numerous areas of high hydrocarbon concentration on 12 the animal or when the hydrocarbons are particularly difficult to eliminate. Preferably, in this method, the agent is allowed to act for 5 to 30 minutes during step b). This applies 5 particularly to the case where pre-washing is followed immediately by washing, using, for example, a washing agent according to this invention. In an alternative embodiment, step b) requires from 1 to 5 hours. This applies when the washing phase does not 10 immediately follow the pre-washing operation, or where the animal is covered with chemical compounds that are particularly difficult to remove. Thus, after the creatures have been caught, they can be kept in a waiting area prior to being cleaned. The flexibility of use of 15 the pre-washing agent according to this invention can thus be seen. It is possible to dry the animal if subsequent cleaning is not envisaged. Where the animal is to be cleaned, it is not necessary to dry it. 20 The application of the softening or pre-washing agent is not limited to hydrocarbons or fats, but applies to any chemical compound for which a softening and detaching action is useful. The operating conditions are then adapted to the chemical compound to be eliminated. 25 The present invention also provides a method comprising a preliminary pre-washing step and a second washing step. Thus, in the present invention, a method for cleaning soiled animals is provided comprising the steps of: 30 a) applying to said animal a softening and detaching agent according to the invention; b) allowing said softening and detaching agent to act for at least 5 minutes; c) applying to said animal a washing agent according 35 to this invention; d) allowing said washing agent to act for 1 to 60 minutes; e) optionally repeating steps a) to d); 13 f) rinsing and, optionally, drying said animal. The expression "optionally repeating steps a) to d)" should be taken to mean that it is in fact possible to repeat steps a) and b) only, or c) and d) only, or a), 5 b), c) and d), or any combination thereof. The manner in which this method is applied can be readily determined from the manners of operation employed in the methods described above. This is a routine matter for those skilled in the art. 10 Although the applicant does not in any way wish to apply limitations, the present method is particularly preferably applied to hydrocarbons. The invention also relates to the use of a washing agent according to this invention for cleaning soiled 15 animals, preferably birds that have been soiled by hydrocarbons. The invention also concerns the use of a softening and detaching agent according to the invention for detaching concentrated chemical compound sludge on 20 animals, particularly hydrocarbon sludge on birds. This invention also makes it possible to save species such as: the seal, sea-calf, penguin, albatross, seagull, gull, gannet, guillemot, petrel, puffin, duck, diving duck or pochard, garrot or goldeneye, long-tailed duck 25 and others. The following examples are provided simply by way of illustration of the present invention and should in no manner be considered as limiting the scope thereof. In these examples, the international CTFA nomenclature is 30 employed. EXAMPLE 1 - Preparation of washing agent. The washing agent prepared had the following composition, for 100 parts by weight: 35 Shampoo base anionic surfactant g ammonium lauryl sulfate (70%) ........ 2.5 magnesium lauryl ether sulfate (70%). 1.5 14 . disodium ricinoleamido MEA sulfo succinate (40%) ...... ...................... 0.5 . amphoteric surfactant . cocoamidopropylhydroxy sultaine (50%) ... 0.75 5 . disodium cocoamphodiacetate (50%) ..... 1.0 Wetting agent . dioctylsodium sulfosuccinate (70%) .... 25 Conditioner . cyclic silicone and dimethyl gum ...... 0.5 10 . hydroxypropyl guar hydroxypropyltri monium chloride .... ....................... 0.2 Solvent . ethanol (95%) ...... ....................... 7 Others 15 . Na 4 EDTA .... .............................. 0.05 . citric acid... .. ........................ 0.05 . Steareth 100 .... .......................... 0.25 . PEG 200 tallow glycerides ................. 0.25 . perfuming agent............................ 1.5 20 . imidazolidinyl urea ....................... 0.1 . Kathon CG .................................. 0.06 Water.......................................... qsp 100 g The procedure was as follows. The shampoo base, citric acid (pH regulator) and the water were introduced 25 into a recipient and were heated to 750C and left to cool after homogenization. The Steareth 100 (thickener) was melted in a first melting pot at around 70 0 C and the cyclic silicone and dimethyl gum (conditioner) were added. The PEG 200 tallow glycerides (thickener) and the 30 perfuming agent were mixed at around 500C in a second melting pot after which the hydroxypropyl guar hydroxypropyltrimonium chloride (conditioner) was added. After homogenization, the content of the second melting pot was introduced into the first. Following this, the 35 content of the first melting pot was added to the recipient at around 50-55 0 C. The dioctylsodium sulfosuccinate and the ethanol were mixed and the resulting mixture was added to the recipient, at around 15 30 0 C. Finally, the imidazolidinylurea and the Kathon CG (both preservatives) were added. EXAMPLE 2 - Preparation of the softening and detaching agent 5 . ethylhexyl cocoate.. .................... 50 dioctylsodium sulfosuccinate (70%) .... 50 The softening and detaching agent was obtained by simply mixing the constituents. EXAMPLE 3 - Toxicity of washing agent 10 Acute toxicity (single-dose administration) tests were carried out on rats by oral route. The ingested product was pure. Eye tolerance tests were carried out using the primary eye irritation method in the rabbit and using the 15 EYTEX method (in vitro test). The results were as follows: acute toxicity ... 5 ml/kg is a non-lethal and non-toxic dose; the lethal dose is not 20 defined but is distinctly higher than 5 ml/kg eye tolerance: primary irritation in the rabbit ...... product very slightly irritating 25 . Eytex .............. slightly irritating EXAMPLE 4 - Toxicity of softening and detaching agent The same tests were carried out as above. The results were as follows: acute toxicity . 2 ml/kg is a non-lethal and 30 non-toxic dose; 5 mg/kg is a dose producing 20% mortality rate and digestive problems the lethal dose is over 5 ml/kg 35 . eye tolerance: primary irritation in the rabbit.. product very slightly irritating Eytex ........ slightly irritating 16 EXAMPLE 5 Effectiveness of washing and pre-washing agents The tests were carried out with feathers in order to test the various products in a process for cleaning birds. 5 Duck feathers were used. In order to come close to real conditions, a packet of 5 feathers was employed. Furthermore, the crude oil was allowed to dry for 11 days. Mechanical agitation (Heydolph agitator) was employed. 10 The test procedure was as follows. After weighing the feathers they were immerse in crude consisting of BAL 150 Arabian Light, for several seconds. They were then allowed to drain and weighed again. The oil was allowed to dry for 10 days. The feathers, which were fixed to 15 the agitator, were agitated for a period of time expressed in minutes in the aqueous composition containing a cleaning product, at a concentration C expressed in weight %, at a temperature T expressed in 0 C. A similar procedure was employed for rinsing with 20 pure water. The residual amount of crude was estimated using chloroform extraction of the BAL 150 and colorimetric hydrocarbon assay (X = 580 nm). The operating conditions were as follows, for a 25 packet of 5 feathers on which the crude had dried for 10 days: duration of washing ............ 10 min washing temperature .............. 40 0 C duration of rinsing ............ 10 min 30 . rinsing temperature ............ .. 20 0 C speed of agitation ............. 50 rpm Various compositions were tested. The DOSS is available in an ethyl alcohol composition at a concentration of 70%; it was diluted to provide an 35 aqueous composition with 1% active compound. The foaming and detergent agent, in other words the shampoo, corresponded to the composition given in example 1, in 17 which the DOSS was absent. The products were employed at a 1% active compound concentration. Influence of wetting agent on effectiveness of cleaning Products Hydrocarbon elimination % 5 DOSS ...... ........................... 39.3 DOSS for pre-washing + shampoo ... 61.5 DOSS + shampoo... ................... 72.5 Shampoo ...... ........................ 26.4 It can be seen that two formulations give good 10 results. The first involves applying the wetting agent followed by the shampoo; the second consists in mixing the wetting agent and the shampoo, in other words the washing agent according to this invention. The solvent is provided by the DOSS in solution in alcohol. 15 Manner of using softening and detaching agent In order to soften the hydrocarbons which had been allowed to dry for an excessive period on the bird feathers, the pre-washing agent according to the present invention, which should facilitate washing of the bird 20 with shampoo, was tested. The use of the pre-washing agent or pre-shampoo made it possible to eliminate 68% of crude that had dried on a packet of feathers. The results are given in the table below. The softening agent was applied by spraying and 25 allowed to act for 10 min. The washing conditions were the same as those given above for the test of the influence of the wetting agent on effectiveness of shampooing. Products hydrocarbon elimination % 30 softening and detaching agent..... 50.0 Shampoo/DOSS ..................... .59.5 softening agent for pre-wash + shampoo/DOSS ...................... 67.8 softening agent + shampoo/DOSS 35 mixed ...... .......................... 34.0 It will be noted that the mixture of all the components is inactive. It will also be seen that the softening agent alone already has a high degree of 18 effectiveness, and that the action of the softening agent prior to washing increases the effectiveness of the washing agent. Tests carried out in situ on living birds showed that 5 the use of the products according to this invention makes it possible to obtain birds that were almost dry after washing.

Claims (25)

1.- A washing agent comprising, by weight based on the total weight of said washing agent: (a) 1 to 10% of a foaming and detergent agent; 5 (b) 5 to 50% of a wetting agent; (c) 0 to 25% of a water-miscible solvent; (d) the balance consisting of water and optionally additives. 10 2.- A washing agent comprising, by weight based on the total weight of said washing agent: (a) 2 to 5% of a foaming and detergent agent; (b) 15 to 20% of a wetting agent; (c) 10 to 20% of a water-miscible solvent; 15 (d) the balance consisting of water and optionally additives.
3.- A washing agent according to claim 1 or 2, in which the foaming and detergent agent comprises, by 20 weight: (a) 60 to 95% of an anionic surfactant; (b) 40 to 5% of an amphoteric surfactant.
4.- A washing agent according to claim 3, in which in 25 said foaming and detergent agent, said anionic surfactant is ammonium lauryl sulfate and/or magnesium lauryl ether sulfate and said amphoteric surfactant is a sulfobetaine and/or cocoamphodiacetate. 30 5.- A washing agent according to any one of claims 1 to 4, in which said wetting agent is dioctylsodium sulfosuccinate.
6.- A washing agent according to any one of claims 1 35 to 5, in which said solvent is a water-miscible solvent for fats. 20
7.- A washing agent according to claim 6, in which said solvent for fats is an alcohol.
8.- A washing agent according to any one of claims 1 5 to 7, further comprising a conditioner in an amount of from 0.1 to 5% by weight, based on the weight of said washing agent.
9.- A washing agent according to claim 8, in which 10 said conditioner comprises, by weight: (a) 20 to 50% of a cationic polymer; and (b) 80 to 50% of a silicone.
10.- A washing agent according to claim 9, in which, 15 in said conditioner, said cationic polymer is a quaternized guar gum and said silicone is a silicone gum in solution in a cyclic silicone oil.
11.- An aqueous composition comprising, by weight, 20 based on the total weight of aqueous composition, 0.1 to 20% of a washing agent according to any one of claims 1 to 10.
12.- A method for cleaning soiled animals, said 25 method comprising the steps of: a) applying a washing agent according to any one of claims 1 to 10 to said animal; b) leaving said Washing agent to act for 1 to 60 minutes; 30 c) optionally repeating steps a) and b); d) rinsing and optionally drying said animal.
13.- A method for cleaning animals according to claim 12, in which, during said step a), said washing agent is 35 in an aqueous composition and makes up from 0.1 to 20% by weight of said composition. 21
14.- A method for cleaning animals according to claim 12 or 13, in which, during said step a) , the composition is applied to the animal by immersing said animal in the composition. 5
15.- A method for cleaning according to any one of claims 12 to 14, in which said agent is left to act for 5 to 20 minutes during said step b). 10 16.- A method for cleaning according to any one of claims 12 to 15 in which, during said step b), the animal is subjected to mechanical action.
17.- A method according to any one of claims 12 to 16 15 in which, during said step c), said steps a) and b) are repeated twice.
18.- A method for cleaning soiled animals, said method comprising the steps of: 20 a) applying a wetting agent to said animal; b) allowing said wetting agent to act for 1 to 60 minutes; c) applying a foaming and detergent agent to said animal; 25 d) leaving said foaming and detergent agent to act for 1 to 60 minutes; e) optionally repeating steps a) to d); f) rinsing and, optionally, drying said animal. 30 19.- The method according to any one of claims 12 to 18, carried out at a temperature of from 20 to 450C.
20.- The method according to any one of claims 12 to 19, carried out on animals that have been soiled by 35 hydrocarbons.
21.- A softening and detaching agent comprised, by weight, based on the total weight of said agent: 22 (a) 10 to 90% of a fatty acid ester; (b) 90 to 10% of a wetting agent.
22.- The softening and detaching agent according to 5 claim 21, comprising, by weight, based on the total weight of said agent: (a) 30 to 70% of a fatty acid ester; (b) 70 to 30% of a wetting agent. 10 23.- The softening and detaching agent according to claim 21 or 22, in which said fatty acid ester is ethylhexyl cocoate.
24.- The softening and detaching agent according to 15 any one of claims 21 to 23, in which said wetting agent is dioctyl sodium sulfosuccinate.
25.- A method for softening or detaching concentrated sludge of chemical compounds on the coat or plumage of 20 animals, comprising the steps of: a) applying to said animal a softening and detaching agent according to any one of claims 21 to 24; b) allowing said softening and detaching agent to act for at least 5 minutes; 25 c) rinsing said animal; d) optionally, repeating steps a) and b); e) optionally drying said animal.
26.- The method according to claim 25, in which, 30 during said step a), said softening agent is applied to said animal by spraying.
27.- The method according to claim 25 or 26, in which said softening agent is allowed to act during step b) for 35 5 to 30 minutes. 23
28.- The method according to claim 25 or 26, in which said softening agent is allowed to act, during step b), for 1 to 5 hours. 5 29.- A method for cleaning soiled animals, said method comprising the steps of: a) applying to said animal a softening and detaching agent according to any one of claims 21 to 24; b) allowing said softening and detaching agent to act 10 for at least 5 minutes; c) applying to said animal a washing agent according to any one of claims 1 to 10; d) allowing said washing agent to act for 1 to 60 minutes; 15 e) optionally repeating steps a) to d); f) rinsing and, optionally, drying said animal.
30.- The method according to claim 29, carried out on animals soiled by hydrocarbons. 20
31.- The use of a washing agent according to any one of claims 1 to 10 for cleaning soiled animals, preferably birds soiled with hydrocarbons. 25 32.- The use of a softening and detaching agent according to any one of claims 21 to 24 for detaching concentrated sludge of chemical compounds on animals, preferably hydrocarbon sludge on birds. 30 Translation of claims modified after chapter II 1 CLAIMS 1.- A method for cleaning animals soiled by hydrocarbons comprising the steps of: a) applying to said animal a washing agent 5 comprising, by weight based on the total weight of said washing agent: (a) 1 to 10% of a foaming and detergent agent; (b) 5 to 50% of a wetting agent; (c) 0 to 25% of a water-miscible solvent; 10 (d) the balance consisting of water and optionally additives. b) leaving said washing agent to act for 1 to 60 minutes; c) optionally repeating steps a) and b); 15 d) rinsing and, optionally, drying said animal. 2.- The method according to claim 1, in which said washing agent comprises, by weight based on the total weight of said washing agent: 20 (a) 2 to 5% of a foaming and detergent agent; (b) 15 to 20% of a wetting agent; (c) 10 to 20% of a water-miscible solvent; (d) the balance consisting of water and optionally additives. 25 3.- The method according to claim 1 or 2, in which the foaming and detergent agent comprises, by weight: (a) 60 to 95% of an anionic surfactant; (b) 40 to 5% of an amphoteric surfactant. 30 4.- The method according to claim 3, in which in said foaming and detergent agent, said anionic surfactant is ammonium lauryl sulfate and/or magnesium lauryl ether sulfate and said amphoteric surfactant is a sulfobetaine 35 and/or cocoamphodiacetate. 2 5.- The method according to any one of claims 1 to 4, in which the wetting agent in said washing agent is dioctylsodium sulfosuccinate. 5 6.- The method according to any one of claims 1 to 5, in which the solvent in said washing agent is a water miscible solvent for fats. 7.- The method according to any one of claims 1 to 6, 10 in which said washing agent further comprises a conditioner in an amount of from 0.1 to 5% by weight, based on the weight of said washing agent. 8.- The method for cleaning animals according to any 15 one of claims 1 to 7, in which, during said step a), said washing agent is in an aqueous composition and makes up from 0.1 to 20% by weight of said composition. 9.- The method for cleaning animals according to any 20 one of claims 1 to 8, in which, during said step a), the composition is applied to the animal by immersing said animal in the composition. 10.- The method for cleaning according to any one of 25 claims 1 to 9, in which said agent is left to act for 5 to 20 minutes during said step b). 11.- The method for cleaning according to any one of claims 1 to 10 in which, during said step b), the animal 30 is subjected to mechanical action. 12.- The method according to any one of claims 1 to 11 in which, during said step c), said steps a) and b) are repeated twice. 35 13.- A method for cleaning animals soiled by hydrocarbons, comprising the steps of: a) applying a wetting agent to said animal; 3 b) allowing said wetting agent to act for 1 to 60 minutes; c) applying a foaming and detergent agent to said animal; 5 d) leaving said foaming and detergent agent to act for 1 to 60 minutes; e) optionally repeating steps a) to d); f) rinsing and, optionally, drying said animal. 10 14.- The method according to any one of claims 1 to 13, carried out at a temperature of from 20 to 45*C. 15.- A method for softening and detaching concentrated hydrocarbon sludge on animals comprising the 15 steps of: a) applying to said animal a softening and detaching agent comprising, by weight based on the total weight of said agent: (a) 10 to 90% of a fatty acid ester; 20 (b) 90 to 10% of a wetting agent. b) leaving said agent to act for at least 5 minutes; c) rinsing said animal; d) optionally repeating steps a) and b); e) optionally, drying said animal. 25 16.- The method according to claim 15, wherein said softening and detaching agent comprises, by weight, based on the total weight of said agent: (a) 30 to 70% of a fatty acid ester; 30 (b) 70 to 30% of a wetting agent. 17.- The method according to claim 15 or 16, in which said fatty acid ester in said softening and detaching agent is ethylhexyl cocoate. 35 18.- The method according to any one of claims 15 to 17, wherein the wetting agent in said softening and detaching agent is dioctylsodium sulfosuccinate. 4 19- The method according to any one of claims 15 to 18, in which, during said step a), said softening agent is applied to said animal by spraying. 5 20.- The method according to any one of claims 15 to 19, in which said softening agent is allowed to act during step b) for 5 to 30 minutes. 10 21.- The method according to any one of claims 15 to 19, in which said softening agent is allowed to act, during step b), for 1 to 5 hours. 22.- A method for cleaning animals soiled by 15 hydrocarbons comprising the steps of: a) applying to said animal a softening and detaching agent as used in the method of any one of claims 15 to 21; b) allowing said softening and detaching agent to act 20 for at least 5 minutes; c) applying to said animal a washing agent as used in the method of any one of claims 1 to 14; d) allowing said washing agent to act for 1 to 60 minutes; 25 e) optionally repeating steps a) to d); f) rinsing and, optionally, trying said animal.
AU58359/94A 1993-01-11 1994-01-10 Compositions for cleaning soiled animals and method therefor Abandoned AU5835994A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR9300168 1993-01-11
FR9300168A FR2700342B1 (en) 1993-01-11 1993-01-11 Compositions for cleaning soiled animals and process for their use.
FR9305275 1993-05-04
FR9305275A FR2700341B1 (en) 1993-01-11 1993-05-04 Compositions for cleaning soiled animals and process for their use.
PCT/FR1994/000024 WO1994016043A1 (en) 1993-01-11 1994-01-10 Compositions for cleaning soiled animals and method therefor

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AT (1) ATE158811T1 (en)
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CA (1) CA2153665A1 (en)
DE (1) DE69405980D1 (en)
FR (1) FR2700341B1 (en)
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FR2749508B1 (en) 1996-06-07 2001-09-07 Oreal DETERGENT COSMETIC COMPOSITIONS FOR HAIR USE AND USE

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US2969332A (en) * 1957-02-05 1961-01-24 American Cyanamid Co Dioctyl sulfosuccinate compositions containing antifoaming agents
DE2525996C2 (en) * 1975-06-11 1983-11-24 Henkel KGaA, 4000 Düsseldorf Cold cleaner
US4246131A (en) * 1978-11-20 1981-01-20 Inolex Corporation Low-irritant surfactant composition
GB2121779B (en) * 1982-06-12 1985-06-19 British Petroleum Co Plc Dispersant composition
GB2172298B (en) * 1985-03-01 1988-11-23 Procter & Gamble Mild detergent mousse
FR2601885B1 (en) * 1986-07-24 1988-11-04 Labofina Sa DISPERSANT COMPOSITIONS FOR THE TREATMENT OF OIL SHEETS ON THE SURFACE OF WATER
US4992213A (en) * 1989-06-23 1991-02-12 Mallett G Troy Cleaning composition, oil dispersant and use thereof
JP2761799B2 (en) * 1990-08-13 1998-06-04 株式会社ヤクルト本社 Washing soap
GB9024162D0 (en) * 1990-11-07 1990-12-19 Unilever Plc Detergent composition
AU650564B2 (en) * 1991-06-07 1994-06-23 Minnesota Mining And Manufacturing Company Disinfecting shampoo composition for animals
CA2131174C (en) * 1992-03-25 1999-01-12 Michel Joseph Giret Cleansing compositions

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ATE158811T1 (en) 1997-10-15
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FR2700341B1 (en) 1995-05-12
CA2153665A1 (en) 1994-07-21
FR2700341A1 (en) 1994-07-13
EP0690908A1 (en) 1996-01-10
NO952737L (en) 1995-09-04
EP0690908B1 (en) 1997-10-01
WO1994016043A1 (en) 1994-07-21
NZ259534A (en) 1997-05-26

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