WO2008135646A1

WO2008135646A1 - Novel alkyl glycoside-based compositions, preparation method thereof and use of same as surfactants

Info

Publication number: WO2008135646A1
Application number: PCT/FR2008/000315
Authority: WO
Inventors: Sinisa Marinkovic; Boris Estrine
Original assignee: Agro Industrie Recherches Et Developpements; Ernenwein, Cédric
Priority date: 2007-03-20
Filing date: 2008-03-11
Publication date: 2008-11-13
Also published as: EP2139594A1; FR2913896A1; FR2913896B1

Abstract

The invention relates to a composition containing at least one alkyl glycoside and at least one alcohol ester of amino acid, peptide or protein.

Description

NEW COMPOSITIONS BASED ON ALKYL GLYCOSIDES, PROCESS FOR THEIR PREPARATION AND USE AS AGENTS

SURFACE

The present invention relates to a novel family of compositions based on alkyl glycosides and alcoholic esters of amino acids, peptides or proteins.

Another aspect of the invention relates to an advantageous mode of preparation of these compositions.

Finally, the invention also relates to the use of the compositions as surface-active agents, in particular in the fields of detergency, agrochemistry and cosmetics.

Alkyl glycosides or polyglycosides are well known nonionic surfactant compounds (J.A.C.S. 60, 2076, 1938; US 6156543; US 5688930). They can be used alone or in combination with other surfactants in a wide range of industrial applications. The properties sought by users depend essentially on the application sectors.

For example, alkyl glycosides are used as surfactants in the formulation of detergents, cosmetics or agrochemical formulations.

Detergent is an important sector of use of alkyl glycosides. This use is motivated inter alia by the search for a high surfactant power, by the generation of large foam volumes, by the search for solubilization properties of non-water-soluble compounds and by a favorable ecotoxicity and biodegradability.

Alkyl glycosides are especially used as an emulsifier in the manufacture of emulsions, mini-emulsions or microemulsions with an aqueous or oily continuous phase (US 6087403, US 6596779, WO 2005110588, WO 2005121294). Emulsions are known and widely used in industry either as materials to be consumed or to be applied to surfaces as non-water soluble agents. We find emulsions in cosmetics (milks, creams, ointments), in cooking (sauces, creams), in galenics (ointments, creams), in paint (paint without odor), in the road industry (bitumen in emulsion), in agrochemicals (phytosanitary products), detergents, rolling mills, steelmaking and the manufacture of various deposits (printing, adhesives, etc.). In cosmetics and pharmacy, for the design of hygiene or care products, emulsions are an effective way to obtain the harmonious combination of ingredients of different nature and properties in a homogeneous and easy-to-use presentation. Many phytosanitary compounds are insoluble in water and, being previously solubilized in an organic solvent, they can be emulsified in water at the time of application or formulation by a suitable choice of glycoside-type emulsifiers. alkyl.

However, among these areas of application, there are many cases for which the alkyl glycosides have technical deficiencies.

For example, the good foaming power of alkyl glycosides is a tare in the cleaning of surfaces by auto-washer, high-pressure lance or in the "washing in place" operations of the food industry, washing bottles or automatic washing of dishes. For these applications, foam volumes interfere with washing and rinsing and decrease the efficiency of operations. Thus, the formulator will have to add to the detergent based on alkyl polyglycosides a compound with non-foaming properties or "anti-foams" to reduce the phenomenon. The anti-foam agents generally used are of petrochemical origin and expensive. They also have an unacceptable environmental profile. There is therefore a need for new compositions based on alkyl glycosides whose foaming capacity can be controlled.

In this same type of application, the alkyl glycosides sometimes exhibit instability at dilution which results in a loss of the effectiveness of the detergents, in particular with regard to the surfactant activity. There is therefore still a need for new compositions based on stable alkyl glycosides whose efficiency makes it possible to lower the surface tension at low concentrations.

In other sectors, alkyl glycosides do not always make it possible to formulate emulsions that are sufficiently stable over time (WO 92/06778, WO 95/13863, WO / 9822207). These emulsions are also known to not tolerate the presence of electrolytes. The formulator, to overcome this defect, will combine its emulsifying system with additives such as polymers or complexing agents that are expensive and difficult to implement. There is therefore also a need for compositions based on alkyl glycosides whose emulsifying power is improved, especially in the presence of electrolyte.

In its research to prepare surfactants with improved performance over alkyl glycosides of the state of the art, the Applicant has found that the properties of alkyl glycosides can be improved by association with alcoholic esters of amino acids, peptides or proteins.

The present invention also relates to an advantageous mode of obtaining these compositions.

Finally, the invention relates to the uses of these compositions as surfactants for the preparation of detergents, cosmetics or agrochemical formulations.

A first aspect of the invention relates to new compositions based on alkyl glycosides whose physicochemical properties and biodegradability are improved by the presence of at least one compound chosen from alcoholic acid amino acid, peptide or protein.

The compositions according to the invention are characterized in that they comprise: i) from 70 to 99% by weight of the composition of at least one compound of formula (1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

R1 is a linear or branched, saturated or unsaturated hydrocarbon-based radical having from 1 to 4 ethylenic unsaturations, having from 1 to 36 carbon atoms, preferably having from 4 to 22 carbon atoms;

• Gl, G2, G3, G4, G5 are independently of each other, the remains of an ose selected from hexoses, parabinose and xylose

Where a, b, c, d and e are equal to 0 or 1, the sum of a, b, c, d and e being at least equal to 1 ii) from 1 to 30% by weight of the composition of at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) n-O-R3 (2) in which:

When X = NH, then R2 is a radical chosen from: -CH3, - (CH2) 3-NH- C (NH) -NH2, -CH2-CO-NH2, -CH2-CO-OR3, -CH2-SH - (CH 2) 2 -CO-NH 2, - (CH 2) 2 -CO-OR 3, H, -CH 2 - (C 3 H 3 N 2), -CH (CH 3) -CH 2 -CH 3, -CH 2 -CH (CH 3) -CH 3, - (CH2) 4-NH2, - (CH2) 2-S-CH3, -CH2-C6H5, -CH2-OH, -CH (OH) -CH3, -CH2- (C8H6N), -CH2- (C6H4) - OH, -CH (CH3) -CH3 And when X = N, then R2 is the following cyclic radical: - (CH2) 2 -Y-, Y represents a methylene group -CH2- linked to X

R3, being optionally identical to R1, is a linear or branched, saturated or unsaturated hydrocarbon-based radical having from 1 to 4 ethylenic unsaturations, having from 1 to 36 carbon atoms, preferably having from 4 to 22 carbon atoms;

Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other.

For the compounds of formula (1):

Particularly preferred for R 1 are alkyl radicals and particularly those derived from alcohols or primary or secondary acids having from 1 to 36 carbon atoms, preferably having from 4 to 22 carbon atoms. Typical examples of alkyl radicals are the methyl, ethyl, butyl, octyl and decyl radicals, as well as the radicals derived from alcohols or capric, lauric, myristic, palmitic, stearic, oleic and erucic acids and more generally the radicals derived from carboxylic acids. vegetable origin or alcohols synthesized by hydrogenation of fatty acids or esters of fatty acids of vegetable origin or radicals from alcohols of terpene origin such as citronellol, geraniol or tetrahydrogeraniol. It is also possible to choose alkyl radicals from technical alcohols such as Guerbet alcohols, or those derived from the hydrogenation of aldehydes of petrochemical origin.

For Gl, G2, G3, G4 and G5, the remnants of reducing sugars, in particular hexoses and or pentoses, such as glucose, galactose, mannose, sorbose, arabinose or xylose, are preferred. The reducing sugars may in particular be derived from the hydrolysis of oligosaccharides or polysaccharides.

The alkyl glycosides or polyglycosides used in the present invention may be synthesized by the many methods of organic chemistry known to date. For example, a route conventionally used for the preparation of alkyl glycosides is an acetalization reaction. This method consists in bringing into contact one or more reducing sugars and one or more excess alcohols (molar ratio of sugars / alcohols between 1 / 1.5 and 1/10) in the presence of a catalytic amount of acid (from 0 , 1 to 5% by weight relative to the weight of the sugars engaged), at a temperature of between 50 and 140 ⁰ C for a period of 15 minutes to 6 hours and to remove water from the reaction medium to obtain a solution of alkyl glycosides and optionally to separate the alkyl glycosides from this solution.

We prefer to use as the acid catalyst, sulfuric acid, sulfonic acid such as methanesulfonic acid, hydrochloric ^acid, hypophosphorous acid or any other acid catalyst for effecting the reaction.

It is preferable to carry out the reaction in the total absence of solvents, but it is possible, if appropriate, to use a solvent such as an ether-oxide such as tetrahydrofuran, diethyl ether, 1,4-dioxane, isopropyl ether, methyl- tert-butyl ether, ethyl tert-butyl ether or diglyme, a halogenated hydrocarbon or a solvent of the amide family such as N, N-dimethylformamide, an alkane such as hexane or an aromatic solvent such as toluene.

To recover the mixture of alkyl glycosides the reaction solvent can be removed, if it is present. The acid catalyst can then be neutralized and the solution filtered. The neutralization will be carried out, for example, with an alkali metal or alkaline earth metal hydrogencarbonate or carbonate, especially sodium hydrogen carbonate, with an alkali or alkaline earth metal hydroxide, in particular sodium hydroxide, or with an organic base such as than triethanolamine.

It may then be purified glycosides ^alkyl or by evaporation of excess alcohol under vacuum of between 0.1 and 100 mbar to a temperature of between 60 and 200 ° C, preferably using a thin film evaporator or by column chromatography on silica gel, alumina, activated charcoal or ion exchange resin, or by crystallization in a solvent.

If necessary, the alkyl glycosides can be decolorized by adding, at a temperature of between 15 and 100 ^° C., 0.05 to 10% by weight and preferably from 0.5 to 8% by weight of hydrogen peroxide, alkali or alkaline earth metal peroxodisulphates, perborates, persulfates, perphosphates, percarbonates, ozone or even periodates. Hydrogen peroxide will be preferred at 30 or 50%.

The alkyl glycosides can be prepared from sources of pure or mixed sugars. Accordingly, compositions based on alkyl glucosides, alkyl xylosides, alkyl arabinosides or mixtures of these three types of alkyl glycosides can be prepared. Thus, the alkyl glycosides used for the preparation of the compositions may in particular correspond to the surfactants or compositions described in US 6156543, US 5688930, US 6596779, US 6087403, WO 2005110588 and WO 2005121294 in the name of the applicant. We therefore prefer to use glycosides alkyls obtained from reducing sugar syrups derived from vegetable raw materials rich in starch and hemicellulose, or products or co-products of agricultural origin such as bagasse, co-products of corn (bran, fibers and corn stover), sorghum co-products, co-products of barley (bran), co-products of rice or co-products of wheat, oats (bran and straw) containing hexose polymers and pentoses. Mixtures of alkyl glycosides derived from wheat bran and wheat straw or corn bran, fibers and fibers and comprising from 1 to 99% by weight of alkyl hexosides in respect of all glycosides and from 1 to 99% by weight of alkyl pentosides.

The average degree of polymerization (DP _m ) of the alkyl glycosides used in the invention is preferably between 1 and 5 and more particularly between 1 and 3.

The alkyl glycosides used will be in the form of aqueous solutions preferably having a solids content of 30 to 90% by weight. Depending on the nature of the alcohol or mixture of alcohols used for the synthesis, they may also be in the form of a solid, pasty or liquid wax, optionally mixed with the alcohol or the starting fatty alcohols. .

By compound of formula (2) or a salt thereof is meant that any compound of formula (2) may be in a salt form of its amine function. It may in particular be an ammonium salt whose counterion is a halide such as, for example, the chloride ion, a bromide, an iodide, a sulphate, an alkylsulphate such as, for example, CH ₃ OSO ₃ -, an alkyl sulphonate, for example Example CH ₃ SO ₃ -, CH ₃ C ₆ H ₄ SO ₃ -, a phosphate, an alkylphosphate, a nitrate, a hydroxide, an alkoxide or a carboxylate.

The compound of formula (2) may be in its "free amine" form or in a partially or totally salified form.

The compounds of formula (2) are known from the state of the art, they can in particular be obtained by esterification of compounds of formula (3) according to the procedures of the state of the art or of their salts, in the presence an alcohol of formula R 3 OH with R 3 as defined above.

H- (X-CHR2-CO) n-OH (3)

Compounds of formula (3) such as:

When X = NH, then R2 is a radical chosen from: -CH3, - (CH2) 3-NH- C (NH) -NH2, -CH2-CO-NH2, -CH2-CO-OR3, -CH2-SH - (CH2) 2-CO-NH2, - (CH2) 2-CO-OR3, H, -CH2- (C3H3N2), -CH (CH3) -CH2-CH3, -CH2- CH (CH3) -CH3, - (CH2) 4-NH2, - (CH2) 2-S-CH3, -CH2-C6H5, -CH2-OH, -CH (OH) -CH3, -CH2- (C8H6N), -CH2- (C6H4) -OH, -CH (CH3) -CH3

And when X = N, then R2 is the following cyclic radical: - (CH2) 2 -Y-, Y represents a methylene group -CH2- linked to X

When n is 1, the compound of formula (3) represents an amino acid selected from glycine, alanine, serine, aspartic acid, glutamic acid, glutamine, valine, threonine, arginine, lysine, proline, leucine, phenylalanine, isoleucine, histidine, tyrosine, tryptophan, asparagine, cysteine, cystine, methionine, hydroxyproline, hydroxylysine, ornithine.

When n is greater than 1, the compound of formula (3) represents a peptide or a protein.

These amino acids, peptides or proteins may be of animal origin, such as, for example, collagen, elastin, fish flesh protein, fish gelatin, keratin or casein.

However, amino acids, peptides and proteins of vegetable origin, such as, for example, those derived from soybean, rapeseed, sunflower, oats, wheat, maize, barley, potato, alfalfa, lupine, faba bean, sweet almond, silk, and more generally, those derived from all lignocellulosic plant material constituting the bulk of annual and perennial plants.

Annual plant means any plant with a vegetative life of the order of a year (such as cereals and various grasses, hemp, flax, sugar cane ...) and perennial plant, plants whose development extends over a longer period (such as bamboo, hardwoods, softwoods ...).

Ligno-cellulosic material refers to whole plants or parts of the said plants (stems, bark, ...) or by-products of the industrial sector of production for food purposes (wheat straw, barley rice, bagasse of sugar cane bagasse sorghum sugar ...).

The amino acids or peptides may themselves be obtained by total or partial hydrolysis of a protein of any origin. This hydrolysis can be carried out for example by heating at temperatures between 60 and 130 ° C. of a protein placed in an acidic or alkaline medium. It can also be carried out enzymatically using a protease.

The esterification reaction of the amino acids, peptides or proteins will be carried out by the methods known to those skilled in the art. For example, among the known methods of the state of the art, the enzymatic methods described in the patents WO 9318180 and WO 9517518, or the chemical methods described in "Interfacial phenomena in biological systems, edition M. Bender, the method described in J. Biol. Chem. 161, 259-269, 1945 or in US Patent 5780658.

It will be preferred, however, to synthesize the compounds of formula (2) by the following method which consists in bringing into contact one or more compounds of formula (3) and one or more alcohols of formula R 3 OH in excess (molar ratio (3) / R 3 OH between 1 and 1/10) in the presence of a quantity of acid (acid / (3) molar ratio between 1.1 and 2), at a temperature of between 50 and 200 ° C. for a period of 15 minutes at 12. hours and remove the water from the reaction medium until a solution of esters of formula (2) and optionally to separate the esters of this solution.

It is preferred to use as the acid catalyst, sulfuric acid, a sulfonic acid such as methanesulfonic acid, hydrochloric acid, hypophosphorous acid or any other acid catalyst for carrying out the reaction.

It is preferable to carry out the reaction in the total absence of a solvent, but it is possible, if appropriate, to use a solvent such as an ether ether such as tetrahydrofuran, diethyl ether, 1,4-dioxane, isopropyl ether, methyl- tert-butyl ether, ethyl tert-butyl ether or diglyme, a halogenated hydrocarbon or a solvent of the amide family such as N, N-dimethylformamide, an alkane such as hexane or an aromatic solvent such as toluene.

In order to recover the ester or the mixture of esters of formula (2), the reaction solvent may be removed, if it is present. The acid catalyst can then be neutralized and the solution filtered. The neutralization, for example, with an alkali metal or alkaline earth metal hydrogencarbonate or carbonate, especially sodium hydrogen carbonate, with an alkali metal or alkaline earth metal hydroxide, especially sodium hydroxide, or with an organic base such as than triethanolamine.

The ester or mixture of esters of formula (2) can then be purified either by evaporation of the excess alcohols in a vacuum of between 0.1 and 100 mbar at a temperature of between 60 and 200 ^° C., preferably by means of a layer evaporator thin, either by column chromatography on silica gel, alumina, activated charcoal or ion exchange resin, or by crystallization in a solvent.

The compounds of formula (2) can be characterized by the establishment of molecular masses by mass spectrometry. Their concentration can also be determined by nitrogen determination according to the known Kjeldahl method, for example.

The second aspect of the invention is a process for the advantageous preparation of the compositions according to the invention.

As a reminder, there are already in the state of the art processes for preparing surfactant compositions from plant materials. These compositions are predominantly composed of alkyl pentosides but comprise only a very small amount of compounds of amino acid esters, peptides or proteins type. Patents EP 0699472 (which we will call Dl document), and Patent WO 9729115 (which we will call D2 document) in the name of the applicant, describe processes for the preparation of glycoside surfactants which consist in bringing wheat bran into contact with a wheat. acidic aqueous solution and / or an enzymatic complex. Thus, a pentose juice is obtained which must be removed from the marc (lignocellulosic residue). The juice freed from its marc must then be concentrated (distillation of water) before being used in glycosylation of an alcohol having from 6 to 22 carbon atoms, which makes it possible to obtain a mixture of pentosides. The pentosides are obtained from the pentoses by a first glycosylation reaction with butanol and then by transglycosylation with a fatty alcohol. The compositions obtained as in Examples 1 of D1 and D2 do not contain more than 0.5% of amino acid esters, peptides or proteins, since their nitrogen levels, measured using the method Kjeldhal nitrogen is not greater than 0.01% by weight with respect to the surfactant composition.

The series of unit operations detailed by example 1 of the document D1 is recalled below:

1: Wheat bran: dilution in water and acid catalyst => hydrolysis reaction of pentosanes in pentoses

2: Obtaining a diluted pentose juice containing a marc => removal of the marc by filtration

3: The juice freed from its marc is optionally purified by chromatography, then it is concentrated by distillation of the water (from 13.8% to 72% of dry matter is thus obtained as in Example 1 of Dl)

4: Reaction of glycosylation firstly with butanol, then with fatty alcohols. The mechanism of this conversion reaction of Pentosanes into Pentosides according to the Dl and D2 patents is shown schematically below:

Pentosanes of Wheat Bran

pentosides

Mechanism of the D1 process

The surfactant yield obtained by these methods is not sufficient. As in Example 1 of the Dl document, only 21 grams of pentosides are obtained from 326 grams of Son. Similarly, in Example 1 of D2, 147 grams of pentosides are obtained from 231 grams of barley bran.

The process according to the present invention makes it possible to obtain better yields of surfactants and furthermore has a reduced number of unit operations compared to the state of the art, and therefore a significant economic advantage.

This method consists in putting the plant material in direct contact with an alcohol in the presence of a catalyst to obtain the pentoside solution. Here, the material is not brought into contact with water, as is the case in D1 and D2. The mechanism is very different from D1 and D2 because it is a direct transglycosylation of pentosans in pentosides in fatty alcohol. The process does not pass through "Pentoses juice". It then becomes unnecessary to purify and concentrate the pentoses since they are directly converted into glycoside surfactants. In addition, the reaction is carried out without butanol solvent as is the case in Dl and D2. The method according to the present invention is therefore easier to implement since it comprises a single unit operation and moreover, makes it possible to obtain better yields. The mechanism concerned by the process according to the present invention is schematized below, and accounts for the advantage thereof in comparison with the method described in D1 and D2:

Pentosanes of Wheat Bran

HO ^' H ^ O0-X ^ * "" ^ "- \ ^ 0R

pentosides

Mechanism of the process according to the present invention

More specifically, the present process is characterized in that it consists in putting one or more lignocellulosic plant materials constituting most of the annual and perennial plants and comprising at least starch and / or hemicelluloses and at least one protein or a peptide, in contact with an excess of at least one alcohol having from 1 to 36 carbon atoms (mass ratio of vegetable materials / alcohol of between 1/100 and 1) in the presence of an amount of acid (ratio mass of plant / acid materials between 1 and 100) between 20 and 200 ° C, preferably between 70 and 150 ° C, for at least 5 seconds to obtain a composition according to the invention, if necessary, to neutralize the acid, to rid the composition of a solid marc and / or unreacted alcohol. Annual plant means any plant with a vegetative life of the order of one year (such as cereals and various grasses such as maize, sorghum, barley and wheat, hemp, hn, cane sugar ...) and perennial plant, plants whose development extends over a longer period (such as bamboo, hardwoods, softwoods ...).

Ligno-cellulosic plant materials are whole plants or parts of the said plants (stems, bark, ...) or co-products of industrial production chain for food purpose (wheat straw, rice, barley, bagasse cane sugar, bagasse sorghum sugar ...).

The process according to the invention has the advantage of obtaining in a single unit operation effective surfactant compositions unlike the processes described in the Dl and D2 patents on behalf of the applicant, which require the execution of several operations of hydrolysis and consumption concentration of water and complex glycosylation, especially in the case of the use of higher fatty alcohols.

One or more alcohols having alkyl radicals of 1 to 36 carbon atoms, preferably having 1 to 22 carbon atoms, will be used. Typical examples of alkyl radicals are the methyl, ethyl, butyl and octyl radicals, as well as the radicals derived from alcohols or capric, lauric, myristic, palmitic, stearic, oleic and erucic acids and more generally the radicals derived from the original acids. vegetable or alcohols synthesized by hydrogenation of fatty acids or esters of fatty acids of vegetable origin. It is also possible to choose alkyl radicals originating from alcohols of terpene origin or technical alcohols resulting from the hydrogenation of aldehydes of petrochemical origin.

At least one acid selected from hydrogen chloride, hydrobromic acid, sulfuric acid, phosphoric acid, sulphonic acids such as benzenesulphonic acid, para-toluenesulphonic acid, camphorsulphonic acid, alkylbenzene sulphonic acid, sulphosuccinic acid or an alkyl sulphosuccinate such as decyl or lauryl sulfosuccinate, perhalohydric acids, such as perchloric acid. It is also possible to use the acid form of anionic surfactants such as alkyl ether sulfates, such as lauryl ether sulfate also known under the acronym LES, sodium dodecyl sulphate, also known under the acronym SDS, or the sulfuric or phosphoric esters of alcohols.

The contacting is carried out for at least 5 seconds and preferably for 5 to 240 minutes in a mixer. We can operate at atmospheric pressure, under partial vacuum or in a reactor under pressure of 2 to 100 bar. Is preferred to conduct the reaction in the total absence of solvents, but it may optionally use a solvent such as an ether oxide such as tetrahydrofuran, diethyl ether, 1,4-dioxane, 1 ^"isopropyl ether, methyl- tert-butyl ether, ethyl-tertiarybutyl ether or diglyme, a halogenated hydrocarbon or a solvent of the amide family such as N ₅ N- dimethylformamide, an alkane such as hexane or an aromatic solvent such as toluene.

To collect the composition thus obtained it will be possible to eliminate the reaction solvent, if it is present. The acid catalyst can then be neutralized and the solution filtered. The filtration residue may also be treated so as to recover the solvents, alcohols or compounds of the compositions. The composition will be neutralized before or after possible filtration, for example by an alkali metal or alkaline earth metal hydrogencarbonate or carbonate, especially sodium hydrogencarbonate, with an alkali metal or alkaline earth metal hydroxide. especially soda, or with an organic base such as triethanolamine.

Then, if necessary, the excess alcohols can be evaporated under vacuum between 0.1 and 100 mbar at a temperature of between 60 and 200 ° C., preferably by means of a thin-film evaporator. The composition may also be purified either by column chromatography on silica gel, alumina, activated charcoal or ion exchange resin, or by crystallization in a solvent.

If necessary, the compositions according to the invention can be bleached by adding, at a temperature of between 15 and 100 ° C., 0.05 to 20% by weight and preferably from 0.5 to 10% by weight of hydrogen peroxide. , peroxodisulfates of alkali or alkaline earth metals, perborates, persulfates, perphosphates, percarbonates, ozone or even periodates. Hydrogen peroxide will be preferred at 30 or 50% solids.

The compositions according to the invention may be used in the form of an aqueous solution comprising, for example, from 30 to 80% of dry matter.

Similarly, the compositions according to the invention may be used in a form of non-aqueous solution, that is to say solubilized in a solvent.

The invention therefore relates to a composition characterized in that it comprises: i) from 30 to 95% by weight of the solvent composition ii) from 4 to 69.3% by weight of the composition of at least one compound of formula

(1) R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) in which :

• G1, G2, G3, G4, G5 are independently of each other, the remains of an ose chosen from hexoses, arabinose and xylose

A, b, c, d and e being equal to 0 or 1, the sum of a, b, c, d and e being at least equal to 1 iii) of 0.05 to 14% by weight of the composition at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) n-O-R3 (2) in which:

When X = NH, then R2 is a radical chosen from: -CH3, - (CH2) 3-NH- C (NH) -NH2, -CH2-CO-NH2, -CH2-CO-OR3, -CH2-SH - (CH 2) 2 -CO-NH 2, - (CH 2) 2 -CO-OR 3, H, -CH 2 - (C 3 H 3 N 2), -CH (CH 3) -CH 2 -CH 3, -CH 2 -CH (CH 3) -CH 3, - (CH2) 4-NH2, - (CH2) 2-S-CH3, -CH2-C6H5, -CH2-OH, -CH (OH) -CH3, -CH2- (C8H6N), -CH2- (C6H4) - OH, -CH (CH3) -CH3

It is particularly preferred as a solvent:

-Oils of vegetable origin, such as coconut oil, castor oil, rapeseed oil, sunflower oil, soybean oil,

-Essential oils of lavender, thyme, savory, sage, mint, caraway, caraway, green anise, fennel, dill, eucalyptus, cajeput, niaouli, clove, pine, cedar, cypress, juniper, lemon, orange, bergamot, cinnamon, laurel, chamomile. Mineral oils, such as liquid paraffin, liquid petroleum jelly and mineral oils, especially from petroleum cuts,

Synthetic oils, such as poly-α-olefins,

Alkanediols having 2 to 10 carbon atoms, such as 1,2-propanediol or 1,3-butanediol,

Alcohols of formulas R 4 OH where R 4 is a saturated or unsaturated aliphatic radical having 1 to 4 ethylenic unsaturations, linear or branched, having 1 to 36 carbon atoms, such as myristic alcohol, cetyl alcohol, alcohol stearic, oleic alcohol,

Polyethylene glycols or polypropylene glycols,

Fatty esters of formula R 5 -O-CO-R 6 where R 5 and R 6 are, independently of one another, saturated or unsaturated aliphatic radicals having 1 to 4 linear or branched ethylenic initiations having from 1 to 22 atoms of carbon, such as alkyl myristates including butyl myristate, propyl myristate, alkyl palmitates such as isopropyl palmitate, alkyl stearates including hexadecyl stearate, alkyl oleates , especially dodecyl oleate, alkyl laurates, in particular hexyl laurate, propylene glycol dicaprylate, 2-ethylhexyl cocoate, esters of lactic acid, succinic acid , behenic acid, isostearic acid such as isostearyl isostearate, fatty acid esters of rapeseed, sunflower fatty acids, linseed fatty acids, cotton fatty acids , of soya fatty acids,

And silicone oils comprising cyclic polydimethylsiloxanes, hydroxylated polydimethylsiloxanes, trimethylsilylated polydimethylsiloxanes, polyorganosiloxanes such as polyalkylmethylsiloxanes, polymethylphenylsiloxanes, polydiohénilsiloxanes, amino derivatives of silicones, silicone copolyethers or mixed silicone derivatives such as mixed copolymers polyalkylmethylsiloxane silicones copolyethers.

The compositions of the present invention have properties or surfactant performance enhanced and variable depending on the nature of the constituents. The term "enhanced surfactant properties or performance" means properties or surfactant performance superior to the surfactant properties or performance of compositions similar in all respects to the compositions of the present invention but not comprising any compound of formula (2). These enhanced properties are obtained through the combination of alkyl glycosides of formula (1) and surfactants of formula (2). The compositions of the present invention possess critical micellar concentrations (CMCs) below the CMCs of APGs known in the art. By critical micellar concentration is meant the minimum concentration of surfactants required to obtain micellar aggregates and from which a more or less abrupt variation of the physicochemical properties of the surfactant solution, for example surface tension, is observed. .

In detergency, the soil solubilization mechanism intervenes only when the concentration of the surfactants is higher than the critical micelle concentration. The lower the critical micellar concentration of a detergent composition will be, the lower the composition will be effective at low concentration. The first advantage of the compositions of the invention is that products such as detergents with reduced surfactant doses can be prepared.

At concentrations below the CMC, the lowering of the surface tension is observed. At these concentrations, the surfactants are not organized in the form of micelles and are responsible for this phenomenon by their absorption at the interfaces. At these low concentrations, it is not uncommon to observe the precipitation of surfactants, which renders them inactive. The compositions according to the invention have improved stability at low concentrations, and therefore, increased performance. C20 is a criterion for evaluating the surfactant performance of a composition at low concentrations. It corresponds to the concentration of composition required to lower the surface tension of water by 20 mN / m. The compositions according to the invention have improved C20s with respect to the alkyl glycosides of the state of the art.

The surface tension is measured using a platinum blade called Wilhelmy's blade and a tensiometer such as the KlOO tensiometer marketed by the company KRUSS. Critical Micellar Concentration (CMC) can be determined by measuring the surface tension at 25 ° C for a series of different concentrations of surfactant compositions. The surfactants of the composition present in solution give rise to a specific curve of the surface tension as a function of the concentration. Initially, for low concentrations, the surfactant molecules preferentially enrich the surface of the water. During this phase a linear decrease of the surface tension is observed as a function of the logarithm of the concentration of surfactants. When a surface tension of 53 mN / m is attained, C20, the concentration of surfactant composition necessary to lower the surface tension by 20 mN / m, is then detected. Once the value of the CMC is reached, the surface is saturated with surfactants and any increase in the concentration then has only a very small effect on the surface tension. It is specified here that a surfactant is all the more efficient when its CMC and / or C20 are low.

The compositions according to the invention, characterized in that they comprise: i) from 80 to 99% by weight of the composition of a mixture of compounds of formula

(1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

R 1 is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 5 to 22 carbon atoms,

A, b, c, d and e being equal to 0 or 1, the sum of a, b, c, d and e being at least equal to 1 arabinosides and alkyl xylosides representing at least 30% by weight of all the compounds of formula (1). ii) from 1 to 20% by weight of the composition of at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) n-O-R3 (2) in which:

R3, being optionally identical to R1, is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 5 to 22 carbon atoms, Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other. and characterized by CMC lower than 800 mg / l and C20 lower than 100 mg / l.

The compositions described above are also characterized by a wetting power superior to APG of the state of the art. The wetting power is measured according to the ISO 8022 or NFT 73420 standard describing the measurement of wetting power on cotton support. The wetting power corresponds to the wetting time of an unbleached cotton disc placed in a solution of surfactants at a defined concentration. In general, 700 ml of a 1 g / l test solution of surfactant composition in distilled water are placed in a beaker thermostated at the desired temperature (20 ° C). The experimental measurement can be carried out at the neutral pH of the distilled water or in basic medium (NaOH).

An unbleached cotton disc meeting the standard NFT 73-406 (30 mm in diameter) and supplied by the company MORTELECQUE, is placed on the surface of the previously prepared solution using a specific immersion tong for this purpose. test. The wetting time is experimentally determined by means of a stopwatch, t 0 corresponds to the moment when the lower part of the disc touches the solution and t is final when the disc sinks by itself into the solution, t final is also called wetting time. Ten consecutive measurements are made with the same solution while taking care however to discard the used cotton discs after each measurement. It is specified here that a surfactant is all the more wetting that the measured wetting time is short. The compositions according to the invention have wetting times according to the NFT 73-406 standard of less than 100 seconds and more particularly less than 80 seconds.

Another particularity of the compositions of the invention relates to their foaming property. By foaming property is meant the property of a composition to form foam under the effect of a mechanical action (stirring, falling of liquid, dispersion of gas). Foam can be an advantage when it represents, for example, an indication of the effectiveness of a product (dishwashing liquid, laundry for washing by hand ...) or when it brings a feeling of comfort to the user (soap, shampoo). On the other hand, it is a disadvantage when it provokes for example the overflow of a washing machine or the stopping of an industrial machine for washing the floors. The compositions of the present invention will be custom-made for the application. We will therefore choose to prepare compositions according to the invention having the property of forming either low quantities, ie large amounts of foam. The foam formed will either be stable or unstable over time and may be more or less resistant to the hardness of the water.

The foaming properties of the compositions are evaluated by the test of foaming power called the Ross Miles test, according to the French standard NF-T-73-404 of November 1966. This test can for example consist of measuring over time and at a temperature of 50 ^° C., the volume of foam obtained after the fall, from a height of 450 mm, of 500 ml of a surfactant solution at 0.1% by weight of surfactant composition in demineralized water, on a liquid surface of the same solution (50ml) contained in a thermostated test tube. The volume measured just after the liquid drop represents the foaming capacity expressed in foam volume and foaming stability is the foam volume ratio at 20 minutes on foaming capacity expressed as a percentage.

(1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

• G1, G2, G3, G4, G5 are independently of each other, the remains of an ose selected from hexoses, arabinose and xylose

A, b, c, d and e being equal to 0 or 1, the sum of a, b, c, d and e being at least equal to 1, the alkyl hexosides then representing less than 90% by weight of all of the compounds of formula (1). ii) from 1 to 20% by weight of the composition of at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) n-O-R3 (2) in which:

R3, being optionally identical to R1, is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 5 to 22 carbon atoms,

Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other. and in that they have a foam volume greater than 200 ml and a stability of the foam at 20 minutes of at least 70% according to the Ross Miles test of the NF-T-73-404 standard carried out at 50 ^° C. with a demineralised water solution comprising 0.1% by weight of composition described above.

Likewise, the compositions according to the invention, characterized in that they comprise: i) from 80 to 99% by weight of the composition of a mixture of compounds of formula, will therefore be preferred for their weakly and non-foaming properties;

(1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

R1 is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 2 to 10 carbon atoms,

In particular, R1 corresponding to the radical ethyl, propyl, butyl, 2 or 3 methyl-butyl, 2 ethyl-hexyl, is preferred.

A, b, c, d and e being equal to 0 or 1, the sum of a, b, c, d and e being at least equal to 1 arabinosides and alkyl xylosides then representing at least 65% by weight of all the compounds of formula (1). ii) from 1 to 20% by weight of the composition of at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) nO-R3 (2) in which :

R3, being optionally identical to R1, is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 2 to 10 carbon atoms,

In particular, R3 corresponding to ethyl, propyl, butyl, 2 or 3 methyl-butyl, 2-ethylhexyl is preferred.

Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other. and in that they have a foam volume of less than 50 ml and a stability of the foam at 20 minutes of less than 10% according to the Ross Miles test of standard NF-T-73-404 carried out at 50.degree. demineralised water solution comprising 0.1% by weight of composition as described above.

The compositions of the invention also have remarkable emulsifying properties, especially in the presence of electrolytes. An emulsion is a dispersion of a liquid in another immiscible liquid. The compositions of the invention make it possible to obtain stable emulsions (that is to say having no phase shift after three months of aging at 45 ° C.) even using less than 5% by weight of emulsifying composition with respect to total weight of the emulsion and even when the emulsion contains more than 0.3% by weight of salts relative to the total weight of emulsion. The stable emulsions thus obtained will not contain any polymer or chelating agent.

The emulsifying power of the compositions according to the invention will be evaluated by the method described in standard NF T 73409. This method consists in preparing emulsions, which may comprise increasing salt levels (NaCl), by mixing at 70 ^° C. at 4% by weight of emulsifying composition relative to the total weight of the emulsion, 15 to 18% by weight of oil relative to the total weight of the emulsion and 81% by weight of water demineralized with respect to the total weight of the emulsion. The emulsions are made by vigorous stirring (8000 rpm) using a mechanical stirrer for one minute. They are then put to rest for 15 hours at 20 ° C. The emulsions are considered stable if a phase separation of less than 5% relative to the total volume of the emulsion is observed after 30 minutes of centrifugation at 4,000 G, ie a residual emulsion volume of 95%.

(1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

R 1 is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 8 to 36 carbon atoms,

In particular, R 1 corresponding to the dodecyl, tetradecyl, hexadecyl and octadecyl radical is preferred.

A, b, c, d and e being equal to 0 or 1, the sum of a, b, c, d and e being at least equal to 1 arabinosides and alkyl xylosides then representing at least 25% by weight of all the compounds of formula (1). ii) from 1 to 20% by weight of the composition of at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) n-O-R3 (2) in which:

And when X = N, then R2 is the following cyclic radical: - (CH2) 2 -Y-, Y represents a methylene group -CH2- linked to X R3, being optionally identical to R1, is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 8 to 36 carbon atoms,

In particular, R3 corresponding to the dodecyl, tetradecyl and hexadecyl radical, of octadecyl, is preferred.

According to one particular aspect of the invention, the compositions having emulsifying properties improved with respect to the APGs of the state of the art, in the form of self-emulsifiable base, will be used. The term "self-emulsifiable" is intended to mean a composition which makes it possible to obtain a water-in-oil or oil-in-water emulsion by simple mixing with moderate stirring at hot (between 40 and 80 ° C.) or at cold temperature (at a temperature below 40 ^° C.), with an aqueous phase.

Selfemulsifiable compositions will be obtained by solubilization of a composition of the invention in an appropriate polar phase (mass ratio compositions / polar phase of between 1/100 and 1) such as a polar organic solvent such as formamide, dimethylformamide or a branched fatty alcohol such as Guerbet alcohols of the Isofol type marketed by Sasol, or in an oil by agitation, in particular mechanical or by sonication.

The self-emulsifiable compositions according to the invention are preferably characterized in that they comprise: i) from 4 to 58% by weight of the composition of a mixture of compounds of formula (1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

Where a, b, c, d and e are equal to 0 or 1, the sum of a, b, c, d and e being at least 1 the arabinosides and alkyl xylosides then representing at least 25% by weight of all the compounds of formula (1). ii) from 0.1 to 12% by weight of the composition of at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) n-O-R3 (2) in which:

R3, being optionally identical to R1, is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 8 to 36 carbon atoms,

In particular, R3 corresponding to the dodecyl, tetradecyl, hexadecyl or octadecyl radical is preferred.

Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other. iii) from 30 to 95.9% by weight of the composition of at least one compound of formula

(4)

R4-OH (4) wherein,

R 4 is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 1 to 36 carbon atoms and more particularly having from 8 to 20 carbon atoms. R4 may be different or identical to R1 and R3.

Particularly preferred for R4 are alkyl radicals and particularly those derived from primary or secondary alcohols having from 1 to 36 carbon atoms. Typical examples of alkyl radicals are methyl, ethyl, butyl and octyl radicals as well as radicals derived from capric, lauric, myristic, palmitic and stearic alcohols. oleic and erucic and more generally radicals derived from acids of vegetable origin or radicals from alcohols of terpene origin such as citronellol, geraniol or tetrahydrogeraniol. It is also possible to choose alkyl radicals originating from alcohols synthesized by hydrogenation of fatty acids or esters of fatty acids of vegetable origin. Alkyl radicals derived from Guerbet alcohols or technical alcohols derived from the hydrogenation of aldehydes of petrochemical origin can also be selected.

Finally, the compositions according to the invention exhibit improved biodegradability compared to the alkyl glycosides of the state of the art. For example, the ultimate biodegradability test results can be taken from OECD 301 tests (A, B, C, D, E and F).

The determination of the biodegradability of surfactants according to the above standards consists in reconstituting, in the laboratory, the degradation processes that can occur in the treatment plants. This type of study can predict the behavior of products in these centers, their persistence in the environment and therefore assess their impact on ecosystems.

The study of the biodegradability of the compositions according to the invention was carried out by evaluating the ultimate aerobic biodegradability according to the OECD directive 301F on chemicals. This is equivalent to the European directive n ° 92/69 part C4-D and the standard AFNOR NF EN ISO 9408.

To calculate this biodegradability, the following data must be available:

The Biological Oxygen Demand (BOD) that is determined using a closed respirometer. A measured volume of mineral medium, containing both bacteria from sludge from a domestic wastewater treatment plant and a known concentration of test substance as the sole nominal source of organic carbon, is agitated in a closed bottle at 20 ^° C. for 28 days. If the biodegradation takes place, the microorganisms consume oxygen and produce carbon dioxide absorbed by natron (Na ₂ CO ₃ ), which causes a drop in the pressure in the container. This decrease in pressure is detected by a manometer that triggers the production of oxygen by electrolysis. When the initial pressure is restored, the electrolysis is interrupted and the amount of electricity used measured by the monitor. This quantity of electricity is proportional to the quantity of oxygen consumed (mg / mg of product). This is recorded over time by a computer.

Theoretical Oxygen Demand (DthO) calculated from the raw formula of the product. This is the total amount of oxygen needed to achieve oxidation complete with a chemical and is expressed in mg of oxygen required per mg of test substance. It is calculated from the molecular formula by applying Equation (A) where H, C, Cl, N, S, P, Na and O represent the number of each of these atoms in one mole of product.

_{DthO = 16 χ} (2xC + 0.5x (H-Cl-3xN) + 3xS + 2.5xP + 0.5xNa-θ)

PM (A)

Biodegradability is expressed by Equation (B).

A respirometer makes it possible to follow the biodegradability of the products as well as that of the chosen control, sodium acetate.

The interpretation of the results is only possible if the criteria of validity of the technique stated in the standard are checked, that is to say if: The degradation of the control (sodium acetate) reaches 60% in less than 14 days . The consumption of inoculum alone (white) is less than 60 mg / L at 28 days and is between 20 and 30 mg / L.

The pH in the reactors at the end of the handling is between 6 and 8.5; Product degradation is greater than 60% within 10 days as soon as 10% of biodegradability is reached and maximum within 28 days according to the standard.

By their improved properties, the compositions of the present invention allow the formulation of surfactants and detergent, agrochemical or cosmetic products. That is to say, it is advantageous to formulate any product allowing the cleaning or wetting of the surface of a solid object or a part of the body following a process involving a physicochemical action other than the simple dissolution of soiling with the compositions of the invention.

A final aspect of the invention therefore relates to detergent, cosmetic or agrochemical products, characterized in that they contain from 0.1% to 50% by weight of specific base of formulation (detergent base, cosmetic or agrochemical) and 1 99% by weight of surfactant composition according to the invention.

The specific bases of formulation are chosen according to the envisaged application (cosmetic, textile, industrial cleaning, household products). For example, one or more formulation adjuvants such as those described in "Detergents and Body Care Products" by L. Ho Tan Taï, Paris 1999, will be chosen as detergent base or cosmetic base. Among these adjuvants there may be mentioned, for example: thickeners , ionic gelling agents, or nonionic, such as cellulose derivatives (carboxymethylcellulose, hydroxyethylcellulose), guar (hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar ...), carob, tree exudates (gum arabic, karaya ... ), marine algae extracts (alginates, carrageenates ...), exosudates of microorganisms (xanthan gum), hydrotropic agents, such as short C2-C8 alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol, skin moisturizers or humectants such as glycerol, sorbitol, collagen, gelatin, aloe vera, hyaluronic acid, urea or skin-protecting agents, such as proteins or protein hydrolysates, cationic polymers, such as cationic guar derivatives (Jaguar C13S®, Jaguar C 162®, Hicare 1000® sold by Rhodia), glycolipids such as sophoroses lipids, fillers such as powders or mineral particles such as calcium carbonate, mineral oxides in the form of powder or in colloidal form (particles of smaller size or of the order of a micrometer, sometimes of a few tens of nanometers) such as titanium dioxide, silica, aluminum salts generally used as antiperspirants, kaolin, talc, clays and their derivatives, preservatives such as methyl, ethyl, propyl and butyl esters of p-acid. -hydroxybenzoic acid, sodium benzoate or any chemical agent avoiding bacterial growth or mold and traditionally used in cosmetic compositions from 0.01 to 3% by weight, photoprotective mineral monopigers, such as titanium dioxide or cerium oxides in the form of powder or colloidal particles, softeners, antioxidants, self-tanning agents such as dihydroxyacetone, repellents against insects, vitamins, perfumes, fillers, sequestering agents, dyes, buffering agents, abrasives such as ground apricot kernels, microbeads, polyphosphates (tripolyphosphates, pyrophosphates) orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines, tetraborates or borate precursors, silicates, in particular those having a SiO ₂ / Na ₂ O ratio of the order of 1.6 / 1 to 3.2 / 1 and the lamellar silicates described in US-A -4 664 839, the alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates), the cogranules of alkali metal hydrated silicates and of alkali metal carbonates (sodium or potassium) rich in silicon atoms in the Q2 or Q3 form, as described in EP-A-488 868, crystalline or amorphous aminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X, etc .; particle size zeolite A of the order of 0.1-10 micrometers is preferred, the water-soluble polyphosphonates (emanates 1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts, etc.), the water-soluble polymer salts, or of carboxylic copolymers or their water-soluble salts such as: polycarboxylate ethers (oxydisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts), hydroxypolycarboxylate ethers, citric acid and its salts, mellitic acid, succinic acid and their salts, salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2-hydroxyethyl) -nitrilodiacetates), C5-C20 alkyl succinic acids and their salts (2-dodecenylsuccinates, lauryl succinates, ), polyacetal carboxylic esters, polyaspartic acid, polyglutamic acid and their salts, polyimides derived from the polycondensation of aspartic acid and / or glutic acid polycarboxymethyl derivatives of glutamic acid or other amino acids, optical brighteners conventionally in the field, especially stilbene disulfonic acid or derivatives of bis (styryl) biphenyl, bleaching agents optionally associated with bleaching activators such as: perborates such as sodium perborate monohydrate or tetrahydrate, peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, preferably sodium persulfate a bleach activator generating in situ in the washing medium, a carboxylic peroxyacid; among these activators, mention may be made of tetraacetylethylene diamine, tetraacetylmethylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, octaacetyl lactose, percarboxylic acids and their salts (called "percarbonates") such as that magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamine-4-oxoperoxybutyric acid, 6-nonylamine-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide of peroxysuccinic acid, decyldiperoxysuccinic acid, antifouling agents such as: derivatives cellulosics such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose, polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048), polyvinyl alcohols, polyester copolymers based on ethylene terephthalate and / or propylene terephthalate units and polyoxyethylene terephthalate units ... anti-redeposition agents such as: ethoxylated monoamines or polyamines, ethoxylated amine polymers (US-A-4) 597,898, EP-A-1 984), carboxymethylcellulose, sulfonated polyester oligomers obtained by condensation of isophthalic acid e, dimethyl sulphosuccinate and diethylene glycol (FR-A-2,236,926), polyvinylpyrrolidones, chelating agents of iron and magnesium, such as: nitrilotriacetates, ethylenediaminetetraacetates, hydroxyethylethylenediaminetriacetates, nitrilotris- (methylenephosphonates) polyfunctional aromatic compounds such as dihydroxydisulfobenzenes, fluorescent agents such as stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanines, thiophenes, foam suppressants such as: fatty acids C10-C24 monocarboxylic or their alkali metal, ammonium or alkanolamine salts, triglycerides of fatty acids, saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic hydrocarbons, such as paraffins, waxes, N-alkylaminotriazines, monostearylphosphates, monostearyl alcohol phosphates, polyol oils or resins organosiloxanes optionally combined with silica particles, softening agents such as clays, enzymes such as: proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139, US-A-4,101,457, US Pat. -A-4,507,219, US-A-4,261,868),

Among the specific adjuvants for the formulation of phytosanitary or agrochemical products constituting the agrochemical base of the final products, mention will be made of phytosanitary active ingredients such as herbicides, fungicides and insecticides as well as other formulation adjuvants described in THE PESTICIDE MANUAL (9th edition, CR.WORKING and RJ HANCE, eds., published by The British Crop Protection Council). The invention finally relates to emulsions which comprise by weight: a. from 0.1 to 20% relative to the total weight of the emulsion, of the composition according to the invention, and preferably from 1 to 10% b. from 0 to 95% relative to the total weight of the emulsion, of oil, and preferably between 0 and 50% c. from 0 to 50% relative to the total weight of the emulsion, active substance, and preferably between 0 and 20% d. water in addition to 100%.

The emulsions prepared from the compositions of the invention can be used in various cosmetic or dermatological or industrial applications, for example in the form of creams for the face, for the body, for the scalp or for the hair or in the form of milk. for the body or for removing make-up or in the form of ointments for example for pharmaceutical use or finally in the road industry for the preparation of road surfaces. These emulsions can also be used for makeup, especially in the form of foundation, after addition of pigments. They can also be used as sunscreens after addition of UVA and / or UVB and / or DHA filters, or as creams or milks after sun after addition of soothing compounds such as panthenol or shea butter.

The emulsions may also contain surfactants, foaming or ionic or nonionic detergents such as sodium lauryl ether sulphate, alkyl betaines to make washing emulsions such as moisturizing washing creams, or emulsions for shaving.

The emulsions may further contain, in order to increase their cosmetic qualities, a cosmetic wax such as, for example, rice wax, candelilla wax, Japanese wax or wheat straw wax.

The compositions of the invention can also be used in formulations where it is necessary to maintain in suspension in water finely divided solids, such as agrochemical active ingredient formulations (herbicides, insecticides, fungicides, etc.) or bitumen, known under the generic name of "concentrated suspensions". In addition to a dispersing surfactant, additives such as, for example, a wetting surfactant, taken from the alkylated derivatives of aliphatic alcohols, the aryl sulphonated derivatives, are found as additives in a concentrated suspension formulation. such as sodium isopropylnaphthalene sulfonate, dialkyl sulfosuccinates such as sodium di-ethyl-2-hexyl sulfosuccinate, dispersing polymers, such as polyacrylic acids and their salts, anhydride (or acid) maleic-diisobutylene copolymers and their salts, condensed sodium methylnaphthalenesulfonates, lignin-derived dispersing polymers such as sodium or calcium lignosulfonates or other dispersing surfactants such as alkoxylated derivatives, optionally sulphated or phosphated with tristyrylphenols. In addition, these formulations may contain antifreeze additives such as propylene glycol and thickening additives which modify the rheological behavior of the suspension, such as xanthan gum, cellulose derivatives (carboxymethylcellulose), guar gum or its derivatives, clays or modified clays such as bentonite and bentones.

The oily phase of the emulsions according to the invention may consist of the linear or branched fatty alcohol or alcohols which may be present in the emulsifying composition of the invention without it being necessary to use another oil. But more generally we will use an oil or a mixture of oils, chosen without the intention to be limited to, among the following oils:

Vegetable oils, such as sweet almond oil, coconut oil, castor oil, jojoba oil, olive oil, rapeseed oil, hazelnut oil, palm oil, shea butter, apricot kernel oil, calophylum oil, safflower oil, avocado oil, walnut oil, lemon oil grape seed oil, wheat germ oil, sunflower oil, corn germ oil, soybean oil, cottonseed oil, alfalfa oil, oil of barley, poppy oil, pumpkin oil, sezame oil, rye oil, evening primrose oil, passionflower oil, derivatives of these oils such as hydrogenated oils ,

Oils of animal origin, such as tallow oil, fish oil,

Mineral oils, such as liquid paraffin, liquid petroleum jelly and mineral oils especially from petroleum cuts,

Synthetic oils, such as poly-α-olefins,

The derivatives of lanolin,

Alkanediols having from 2 to 10 carbon atoms such as 1,2 propanediol, 1,3-butanediol,

Alcohols having a saturated or unsaturated aliphatic radical having 1 to 4 ethylenic unsaturations, linear or branched, having 12 to 22 carbon atoms, such as myristic alcohol, cetyl alcohol, stearyl alcohol, oleic alcohol , Polyethylene glycols or polypropylene glycols,

Fatty esters such as alkyl myristates, especially butyl myristate, propyl myristate, alkyl palmitates such as isopropyl palmitate, alkyl stearates, in particular hexadecyl stearates, alkyl oleates , especially dodecyl oleate, alkyl laurates, especially hexyl laurate, propylene glycol dicaprylate, 2-ethylhexyl cocoate, esters of lactic acid, behenic acid , isostearic acid such as isostearyl isostearate, fatty acid esters of rapeseed, sunflower fatty acids, linseed fatty acids, cotton fatty acids, soy,

Silicone oils comprising cyclic polydimethylsiloxanes, α-ω hydroxylated polydimethylsiloxanes, α-ω trimethylsilylated polydimethylsiloxanes, polyorganosiloxanes such as polyalkylmethylsolixanes, polymethylphenylsiloxanes, polydiohénilsiloxanes, amino derivatives of silicones, silicone copolyethers or mixed derivatives of silicones such as mixed polyalkylmethylsiloxane-silicone copolyether copolymers.

Essential oils of lavender, thyme, savory, sage, mint, caraway, caraway, green anise, fennel, dill, eucalyptus, cajeput, niaouli, clove, pine, cedar, cypress, juniper, lemon, orange, bergamot, cinnamon, laurel , chamomile, cedar.

Bitumen

The emulsions will comprise, as active substance, specific agents according to the application envisaged (cosmetics, textiles, industrial cleaning, household products, road industry) such as anti-scale, alkaline, bleaching agents, enzymes, polymers (or thickening agent). ), anti-foam agents or foam promoters, optical brighteners, opacifiers, dyes, various fillers for adjusting the pH, flavors, preservatives or therapeutic or touching agents, and especially the formulation adjuvants mentioned previously.

The emulsions may be manufactured either by directly mixing the solid or liquid ingredients at a temperature of between room temperature and 200 ^° C. and by homogenizing the preparation by vigorous stirring or by means of a high-pressure homogenizer, or by preparing independently the lipophilic and hydrophilic phases at a temperature between room temperature and 90 ° C and homogenizing the preparation by adding one of the phases on the other with stirring. The following examples illustrate the invention, without limiting it: EXAMPLE 1 Surfactant composition according to the invention comprising decyl glycosides derived from desamylated wheat bran and a decyl ester of L-Proline

A surfactant composition No. 1 is prepared by dissolving L-Proline decyl ester (PRO ClO) and decyl glycosides derived from the desamylated wheat bran (APP ClO).

PRO ClO is obtained by esterification of decanol with proline in the presence of a catalytic amount of methanesulfonic acid according to a protocol adapted from J. Biol. Chem. 161, 259-269, 1945.

APP ClO is a mixture of alkyl glycosides obtained by grafting decanol onto a syrup of pentoses obtained according to the method described in Example 1 of application FR 2723858. The main components are described below. Their proportion is determined by gas chromatography.

Components / dry matter% by weight

Decyl glucosides 7

Decyl Xylosides 54

Decylating Arabinosides 31

Other glycosides and impurities 8

Description of APP ClO

Decyl glucosides correspond to the compounds of formula (1) in which R 1 is a decyl radical, Gl is the rest of glucose, a is equal to 1 and b, c, d and e are equal to 0.

Decyl xylosides correspond to the compounds of formula (1) in which R 1 is a decyl radical, Gl is the residue of xylose, a is equal to 1 and b, c, d and e are equal to 0.

Decyl arabinosides correspond to the compounds of formula (1) in which R 1 is a decyl radical, Gl is the rest of arabinose, a is equal to 1 and b, c, d and e are equal to 0.

The other glycosides correspond to the polyglycosides of formula (1) where R 1 is the decyl radical and the sum a, b, c, d, e is greater than or equal to 2.

In 100 g of water were dissolved 80 g ^"ClO APP and 20g Proclo by mechanical stirring at 60 ⁰ C for 5 minutes then obtained composition No. liters by weight relative to the dry matter the following proportions.: Components / dry matter% by weight

PRO ClO 20 APP ClO 80

Description of Composition No. 1

EXAMPLE 2 Surfactant composition according to the invention comprising dodecyl and tetradecyl glycosides derived from desamylated wheat bran and alcoholic esters of amino acids.

Compositions according to the invention comprising dodecyl and tetradecyl glycosides (APP C12 / C14), dodecyl and tetradecyl amino acid esters (C12 / C14 AAE) are prepared.

APP C 12 / Cl 4 is a mixture of alkyl glycosides obtained by grafting a mixture of dodecyl alcohol and tetradecyl alcohol (LOROL 1214S from the company COGNIS) on a syrup of pentoses obtained according to the method described in Example 1 of the application FR 2723858. The proportion of each main constituent is determined by gas chromatography.

AAE C 12 / Cl 4 is obtained by esterification of a mixture of dodecyl alcohol and tetradecyl alcohol (LOROL 1214S from the company COGNIS) with a mixture of amino acids derived from the hydrolysis of wheat gluten in the presence of a catalytic amount of sulfuric acid according to the protocol of J. Biol. Chem. 161, 259-269, 1945 applied to a mixture of amino acids.

Components / dry matter% by weight

Dodecyl glucosides 5.6

Tetradecyl glucosides 2,8

Dodecyl xylosides 43.9

Tetradecyl Xylosides 12.1

Arabinosides of dodecyl 27.1

Tetradecyl arabinosides 8.5

Description of APP C12 / C14

The dodecyl glucosides correspond to the compounds of formula (1) in which R 1 is a dodecyl radical, Gl is the rest of the glucose, a is equal to 1 and b, c, d and e are equal to O. Tetradecyl glucosides correspond to the compounds of formula (1) in which R 1 is a tetradecyl radical, Gl is the rest of glucose, a is equal to 1 and b, c, d, and e are equal to O.

The dodecyl xylosides correspond to the compounds of formula (1) in which R1 is a dodecyl radical, Gl is the residue of xylose, a is equal to 1 and b, c, d and e are equal to O.

Tetradecyl xylosides correspond to the compounds of formula (1) in which R 1 is a tetradecyl radical, G 1 is the residue of xylose, a is 1 and b, c, d and e are equal to 0.

The dodecyl arabinosides correspond to the compounds of formula (1) in which R 1 is a dodecyl radical, Gl is the rest of arabinose, a is equal to 1 and b, c, d and e are equal to 0.

Tetradecyl arabinosides correspond to the compounds of formula (1) in which R 1 is a tetradecyl radical, Gl is the rest of arabinose, a is equal to 1 and b, c, d and e are equal to 0.

Components / dry matter% by weight

L-Proline 10.1

L-GIutamine 30.3

L-Leucine 6.3

L-Asparagine 4.7

L-Phenylalanine 4,6

L-Serine 4,2

Other <to 4% 39.8

Description of the main constituents of the amino acid mixture of wheat gluten.

94.5 g of APP C12 / C14 and 5.5 g of C12 / C14 AAE are solubilized in 100 g of water by mechanical stirring at 60 ^° C. for 5 minutes. Composition No. 2 is then obtained having, by weight relative to the dry matter, the following proportions:

Components / dry matter% by weight

APP C12 / C14 94.5 AAE C12 / C14 5.5

Description of Composition No. 2 EXAMPLE 3 Process for preparing a surfactant composition according to the invention

350 g of its désamylacé containing 1% of starch, 16% of proteins, 47% of hemicelluloses in the form of pentosanes, 3040 g of a mixture of octanol and decanol at 45/55 are suspended (LOROL C8 / C10 from the company COGNIS) and 33 g of 96% sulfuric acid at a temperature of 109 ° C for 1 hour in a stirred reactor. After neutralization of the excess acid with aqueous sodium hydroxide (30.5%) at pH 8 and filtration of the lignocellulosic residue, the excess fatty alcohols are separated from the filtrate by distillation on a thin-film evaporator.

325 g of composition no. 3 according to the invention are obtained, which is dissolved in demineralized water until a solution of 30% by weight of dry matter is obtained. After bleaching with hydrogen peroxide, a composition having the following characteristics is obtained:

Appearance: clear yellow liquid

Stability greater than 3 months (4 ° C / 20 ° C / 45 ° C)

Nitrogen content in the composition (Kjeldhal nitrogen) = 0.8% by weight relative to the dry matter, which corresponds to a concentration of 13.3% of amino acids esterified by octanol and decanol (AAE C8 / C10). The proportion of each alkyl glycoside is determined by gas chromatography.

Components% by weight

Octyl glucosides 2.9

Decyl glucosides 2,7

Xylosides of octyl 19,9

Decyl Xylosides 25.3

Octyl arabinosides 16.5

Decino Arabinosides 13.3

AAE C8 / C10 13.3

Impurities (ash, alcohols, other glycosides and residual sugars) Qs 100%

Description of the composition n ° 3

The octyl glucosides correspond to the compounds of formula (1) in which R1 is an octyl radical, Gl is the rest of the glucose, a is equal to 1 and b, c, d and e are equal to 0.

Decyl glucosides correspond to the compounds of formula (1) in which R 1 is a decyl radical, Gl is the rest of glucose, a is equal to 1 and b, c, d and e are equal to 0. Octyl xylosides correspond to the compounds of formula (1) in which R1 is an octyl radical, Gl is the residue of xylose, a is equal to 1 and b, c, d and e are equal to 0.

Octyl arabinosides correspond to the compounds of formula (1) in which R1 is an octyl radical, G1 is the rest of arabinose, a is equal to 1 and b, c, d and e are equal to 0.

EXAMPLE 4 Process for preparing a surfactant composition according to the invention

269 g of its deaamylamide containing, by weight relative to the dry matter, 1% of starch, 16% of proteins, 47% of hemicelluloses in the form of pentosanes and 2377 g of an octanol mixture are suspended. of 45/55 decanol (LOROL C8 / C10 from the company COGNIS) and 26 g of 96% sulfuric acid at a temperature of 109 ° C. for 3 hours. After neutralization of the excess acid with aqueous sodium hydroxide (30.5%) at pH 8 and filtration of the lignocellulosic residue, the excess fatty alcohols are separated from the filtrate by distillation on a thin-film evaporator.

310 g of surfactant composition No. 4 are obtained which are dissolved in demineralized water until a solution of 30% by weight of dry matter is obtained. After bleaching with hydrogen peroxide, a composition having the following characteristics is obtained:

Appearance: clear yellow liquid

Stability greater than 3 months (4 ° C / 20 ° C / 45 ° C)

Nitrogen content in the composition (Kjeldhal nitrogen) = 0.91% by weight relative to the dry matter, which corresponds to a concentration of 15.1% of amino acids esterified by the octanol and decanol mixture (C8 / C10). The proportion of each alkyl glycoside is determined by gas chromatography. Components% by weight

Octyl Glucosides 4

Decyl glucosides 4,6

Xylosides of octyl 22,6

Decyl Xylosides 23.2

Octyl arabinosides 10.6

Decino Arabinosides 13.3

AAE C8 / C10 15.1

Impurities (ash, alcohols, other glycosides and residual sugars) Qs 100%

Description of Composition No. 4

Octyl xylosides correspond to the compounds of formula (1) in which R1 is an octyl radical, Gl is the residue of xylose, a is equal to 1 and b, c, d and e are equal to 0.

EXAMPLE 5 Process for preparing a surfactant composition according to the invention

269 g of crude containing, by weight relative to the dry matter, 26% of starch, 14% of proteins, 23% of hemicelluloses in the form of pentosanes and 2401 g of an octanol mixture are suspended. 45/55 decanol (LOROL C8 / C10 from COGNIS) and 52 g of 96% sulfuric acid at a temperature of 109 ° C. for 3 hours. After neutralization of the excess acid with aqueous sodium hydroxide (30.5%) at pH 8 and filtration of the lignocellulosic residue, the excess fatty alcohols are separated from the filtrate by distillation on a thin-film evaporator. 325 g of surfactant composition No. 5 are obtained, which is dissolved in demineralized water until a solution containing 70% by weight of dry matter is obtained. After bleaching with hydrogen peroxide, a composition having the following characteristics is obtained:

Appearance: clear yellow liquid

Stability greater than 3 months (4 ° C / 20 ° C / 45 ° C)

Nitrogen content in the composition (Kjeldhal nitrogen) = 1.3% by weight relative to the dry matter, which corresponds to a concentration of 22% of amino acids esterified by octanol and decanol (C8 / AAE) C10). The proportion of each alkyl glycoside is determined by gas chromatography.

Components% by weight

Octyl glucosides 11

Decyl glucosides 10.25

Xylosides of octyl 11

Decyl Xylosides 11.1

Octylether arabinosides 8.8

Decino arabinosides 8.3

AAE C8 / C10 22

Impurities (ash, alcohols, other glycosides and residual sugars) Qs 100%

Description of Composition No. 5

Octyl arabinosides correspond to the compounds of formula (1) in which R1 is an octyl radical, G1 is the rest of arabinose, a is equal to 1 and b, c, d and e are equal to 0. Decyl arabinosides correspond to the compounds of formula (1) in which R 1 is a decyl radical, Gl is the rest of arabinose, a is equal to 1 and b, c, d and e are equal to 0. EXAMPLE 6 : Process for preparing a surfactant composition according to the invention.

53.8 g of its deamidate containing, by weight relative to the dry matter, 1% of starch, 16% of proteins, 47% of hemicelluloses in the form of pentosanes and 473.6 g of a mixture are suspended. of hexadecanol and octadecanol at 30/70 (HYDRENOL D from the company COGNIS) and 5.2 g of 96% sulfuric acid at a temperature of 109 ^° C. for 3 hours.

After neutralization of the excess acid with aqueous sodium hydroxide (30.5%) at pH 8, the solid lignocellulosic residue is removed by filtration.

500 g of self-emulsifying surfactant composition No. 6 having the following characteristics are obtained:

Appearance: light beige solid

Stability greater than 3 months (4 ° C / 20 ° C / 45 ° C)

Nitrogen content in the composition (Kjeldhal nitrogen) = 0.049% by weight relative to the dry matter, which corresponds to a concentration of 1.21% of amino acids esterified by the mixture of hexadecanol and octadecanol ( AAE C 16 / Cl 8). The proportion of each alkyl glycoside is determined by gas chromatography.

Components% by weight

Hexadecyl glucosides 0.2

0.4 octadecyl glucosides

Hexadecyl xylosides 1,8

Octadecyl xylosides 3,5

Hexadecyl arabinosides 1

Octadecyl arabinosides 1,5

AAE C16 / C18 1.21 hexadecanol 24.7 octadecanol 63.2

Impurities and other glycosides Qs 100

Description of Composition No. 6 • Hexadecyl glucosides correspond to the compounds of formula (1) where R1 is hexadecyl, Gl is the rest of glucose, a is 1 and b, c, d, and e are 0.

Octadecyl glucosides correspond to the compounds of formula (1) in which R 1 is an octadecyl radical, Gl is the rest of glucose, a is equal to 1 and b, c, d, and e are equal to 0.

The hexadecyl xylosides correspond to the compounds of formula (1) in which R 1 is a hexadecyl radical, Gl is the residue of xylose, a is 1 and b, c, d and e are 0.

Octadecyl xylosides correspond to the compounds of formula (1) in which R 1 is an octadecyl radical, G 1 is the residue of xylose, a is equal to 1 and b, c, d and e are equal to 0.

• Hexadecyl arabinosides correspond to the compounds of formula (1) where R1 is a hexadecyl radical, G1 is the rest of arabinose, a is 1 and b, c, d, and e are 0.

Octadecyl arabinosides correspond to the compounds of formula (1) in which R1 is an octadecyl radical, G1 is the rest of arabinose, a is equal to 1 and b, c, d, and e are equal to 0.

EXAMPLE 7 Process for preparing a surfactant composition according to the invention

53.8 g of its disaminated material are suspended, having by weight, relative to the dry matter, 1% of starch, 16% of proteins, 47% of hemicelluloses in the form of pentosanes and 470 g of natural isoamyl alcohol. (mixture of 2 and 3 methyl-butanol 70/30) and 5.2 g of 96% sulfuric acid at a temperature of 109 ° C for 3 hours. After neutralization of the excess acid with aqueous sodium hydroxide (30.5%) at pH 8, the solid lignocellulosic residue is removed by filtration.

35 g of surfactant composition No. 7 are obtained, which is dissolved in demineralised water until a solution of 64.5% by weight of dry matter is obtained. After bleaching with hydrogen peroxide, a composition having the following characteristics is obtained:

Appearance: clear yellow liquid

Stability greater than 3 months (4 ° C / 20 ° C / 45 ° C) Nitrogen content in the composition (Kjeldhal nitrogen) = 0.25% by weight relative to the dry matter, which corresponds to a concentration of 3.2% amino acids esterified with amyl alcohol (AAE C5) .

The proportion of each alkyl glycoside is determined by gas chromatography.

Components% by weight

Amyl glucosides 3.1

Amyl Xylosides 14.1

Amyl arabinosides 24.4

AAE C5 3.2

Impurities and other glycosides Qs 100

Description of Composition No. 7

• Amyl glucosides correspond to the compounds of formula (1) where R1 is a 2 or 3 methylbutyl radical, Gl is the rest of glucose, a is equal to 1 and b, c, d, and e are equal to 0.

• Amyl xylosides correspond to the compounds of formula (1) where R1 is a 2 or 3 methylbutyl radical, Gl is the residue of xylose, a is equal to 1 and b, c, d, and e are equal to 0.

Amyl arabinosides correspond to the compounds of formula (1) in which R1 is a 2 or 3 methyl-butyl radical, G1 is the rest of arabinose, a is equal to 1 and b, c, d and e are equal to 0.

EXAMPLE 8 Efficiency and stability of composition No. 1 in weakly concentrated solution

C20 (expressed in mg / l) is measured for Composition No. 1 and APG ClO by the Wilhelmy blade technique at 25 ° C. using a K100 tensiometer marketed by KRUSS.

The surfactant solutions were made with ultra-permuted water.

Solutions at 20% by weight of dry matter are also placed at 25 ° C for 12 hours and their stability evaluated visually. C20 (mg / 1) Appearance (25 ° C, 20% dry matter)

COMPOSITION No. l 14 Homogeneous solution

APP ClO 20 Precipitation

The composition No. 1 according to the invention has an efficiency and stability greater than APP ClO at low concentrations. EXAMPLE 9 Foaming Power of Composition No. 2

The foaming properties are determined using a foaming power test according to the French standard NF-T-73-404 of November 1966.

The foam volumes are measured at 50 ^° C. of the solutions to be studied and the foaming stability is also determined at 20 minutes. The foaming stability at 20 minutes corresponds to the ratio of the foam volume to 20 minutes by the volume of foam obtained immediately after the flow (t = 0 min) multiplied by 100.

A solution comprising, by weight, 99.9% of demineralised water and 0.1% of composition No. 2 is prepared. A solution comprising, by weight, 99% of demineralized water and 0.1% of APP C12 / C14 glycosides described in Example No. 2 is also prepared.

The table below gives the results for the solutions described above and for the composition 7.

Duration (min) 0 1 2 3 5 10 15 20

Volumes Composition n ° 2 (ml) 210 200 200 200 190 180 180 170 Volume APP C12 / C14 (ml) 70 60 50 50 40 40 40 40

Foaming stability at 20 min.

Composition No. 2 81% APP C12 / C14 57%

It is noted that the surfactant compositions according to the invention have superior foaming properties and foaming stability to dodecyl and tetradecyl glycoside surfactants not containing amino acid derivatives (APP C 12 / Cl 4). EXAMPLE 10 Emulsifying Properties of Composition No. 2

An emulsion is prepared by mixing, at 70 ° C., 1.5 g of emulsifying composition of Example No. 2, 3.75 g of oil (Miglyol 812N fatty acid triglycerides marketed by Hiils), and 19.75 g of osmosis water. The emulsion is made by vigorous stirring (8000 rpm) using a mechanical stirrer for one minute. It is then rested for 15 hours at 20 ^° C. The stability of the emulsion is evaluated by determining the residual emulsion volume relative to the total volume after 30 minutes of centrifugation at 4000G.

The emulsion produced from composition No. 2 is 100% stable after centrifugation. EXAMPLE 11 Surfactant Properties of the Compositions Nos. 3, 4 and 5

The critical micellar concentration and the C20 (expressed in mg / l) are measured for each composition by the Wilhelmy blade technique at 25 ° C. The critical micellar concentrations (CMC) and C20 as well as the surface tensions were determined at 25 ° C. using a K100 tensiometer marketed by KRUSS. The surfactant solutions were made with ultra-permuted water. The CMC, C20 and surface tension of a solution of alkyl glycosides obtained according to Example 1 of the application FR 2723858 will also be measured by way of comparison.

The wetting power is appreciated by measuring the wetting time of a cotton disc placed within a solution of surfactants at a defined concentration. 700 ml of a test solution containing 1 g / l of surfactant material in distilled water are placed in a beaker at a temperature of 25 ^° C. The wetting time is determined experimentally with the aid of a stopwatch. Ten consecutive measurements were made with the same solution while taking care however to discard the used cotton discs after each measurement.

The comparative examples are carried out with glycosides having the same fatty chain from octanol and decanol (APP C8 / C10) and having not more than 0.5% of nitrogen according to the Kjeldhal method, and obtained according to US Pat. example No. 1 of the patent FR 2723858 (or Dl) Components / dry matter% by weight

Octyl glucosides 23.7

Decyl glucosides 29,3

Octyl Xylosides 10.1

Decyl Xylosides 12.1

Arabinosides octyl 6,7

Decinos Arabinosides 8.1

Other glycosides and impurities Qs 100

Description of APP C8 / C10

The overall results are reported in the following table:

CMC C20 γ CMC Power

(mg / 1) (mg / 1) (mN / m) Wetting (dry)

Composition No. 3,365 19 27,7 43

Composition No. 4,595 17 27,4 51

Composition No. 5 780 28 28 72

APP C8 / C10 950 75 28 145 It is noted that the surfactant compositions according to the invention are more effective (C20, CMC and wetting power) than octyl and decyl glycosides having no amino acid derivatives (Example 1 of application FR 2723858). EXAMPLE 12 Emulsifying Properties of Composition No. 6

Emulsions containing possibly increasing levels of salt (NaCl) are prepared by mixing at 70 ^° C., 0.75 g of emulsifying composition (I g in the case of sunflower oil), 3.75 g of oil ( Miglyol 812N fatty acid triglycerides marketed by Hϋls / sunflower oil / Dimethicone), and 20.375 g (20.125 g for sunflower oil) of osmosis water with varying amounts of salt. The emulsions are made by vigorous stirring (8000 rpm) using a mechanical stirrer for one minute. They are then put to rest for 15 hours at 20 ° C. The stability of the emulsions is evaluated by determining the residual emulsion volume relative to the total volume after 30 minutes of centrifugation at 4000G.

A comparative example is carried out with a self-emulsifying composition equivalent to composition No. 6 but not containing amino acid derivatives, as APP C 16 / Cl 8. This composition is obtained by glycosylation of a mixture of hexadecanol and octadecanol with D-xylose according to the protocol of example 4 of patent EP 1027921. this protocol was applied at a xylose / fatty alcohol molar ratio to obtain a composition as described below.

Components% by weight

Hexadecyl xylosides 2.9

Octadecyl xylosides 6.7 hexadecanol 24.7 octadecanol 63.2 impurities Qs 100

Description of APP C16 / C18

The hexadecyl xylosides correspond to the compounds of formula (1) in which R 1 is a hexadecyl radical, Gl is the residue of xylose, a is 1 and b, c, d and e are 0. Octadecyl xylosides correspond to the compounds of formula (1) in which R 1 is an octadecyl radical, G 1 is the residue of xylose, a is equal to 1 and b, c, d and e are equal to 0.

In summary, the emulsions are produced with proportions relative to the total weight of the emulsion of 3 to 4% of self-emulsifying base, ie 0.29 to 0.38% of surfactants (pentosides for APP C 16 / Cl 8 and pentosides and amino acid esters for composition No. 6).

The following table gives the stability of the emulsions expressed in% by volume of residual emulsion:

NaCl

Oil Composition No. 6 APP C16 / C18

(%)

Mygliol 0 93 75

Myglyol 0.3 65 0

Dimethicone 0 98 55

Sunflower 0 97 80

Residual emulsion (% by volume)

It is noted that despite a very small amount of surfactants in the self-emulsifying compositions studied, the emulsions produced from the composition according to the invention exhibit good stability even in the presence of electrolytes. EXAMPLE 13 Non-Foaming Power of Composition No. 7

A solution comprising, by weight, 99.9% of deionized water and 0.1% of composition No. 7 is prepared.

Duration (min) 0 1 2 3 5 10 15 20

Volumes Composition No. 7 (ml) 0 0 0 0 0 0 0 0 It is noted that the surfactant composition according to the invention is completely non-foaming. EXAMPLE 14 Biodegradability

The following table shows the ultimate biodegradability results conducted according to OECD 301F guidelines for the compositions of Examples 3, 4 and 5 in comparison with a mixture of octyl and decyl pentosides not containing amino acid derivatives.

Composition% to 28 days Biodegradability according to OECD 301 F

Composition No. 3 76.6 Readily biodegradable

Composition No. 4 66 Readily biodegradable

Composition No. 5 66 Readily biodegradable

APP C8 / C10 58 Not readily biodegradable

EXAMPLE 15 Preparation of a cosmetic cream from a composition according to the invention

3 g of the composition No. 6 of Example 6 are suspended in 47 g of osmosis water. The mixture is brought to 50 ° C and is then stirred (500 rpm) for 2 minutes. The emulsion thus formed is then cooled to room temperature. This emulsion remains stable for 3 months in an oven at 45 ° C.

EXAMPLE 16 Preparation of a Cosmetic Emulsion from a Composition According to the Invention

The lipophilic phase (10 g of isostearyl isostearate from Gattefossé) which contains 4 g of composition No. 2 of Example 2 and the hydrophilic phase (86 g of osmosis water) are separately heated to a temperature of 7O ⁰ C. the lipophilic phase is stirred vigorously using a mechanical stirrer (800 rpm) and thereto was added in 2 minutes the hydrophilic phase until the phase inversion characterized by an abrupt change viscosity. The addition can then be faster (1 minute). Finally, the emulsion is allowed to cool with slow stirring (300 rpm) to a temperature of the order of 25 ° C.

This emulsion remains stable for 3 months in an oven at 45 ° C. EXAMPLE 17 Preparation of a Concentrated Phytosanitary Emulsion from Composition According to the Invention

3 g of composition No. 6 of Example 6, 70 g of rapeseed oil of the company OLEON and 27 g of water osmosed at the same time at a temperature of 75 ^° C. are heated and then allowed to homogenize (10,000 rpm) at the same temperature for 2 minutes and finally allowed to cool with slow stirring (300 rpm) to a temperature of about 25 ⁰ C. This emulsion remains stable for 2 months in a drying oven. 45 ° C. EXAMPLE 18 Preparation of a Concentrated Phytosanitary Emulsion from Composition According to the Invention

4 g of composition No. 6 of Example 6, 70 g of rapeseed methyl ester (from the company OLEON) and 26 g of water osmosed at the same time at a temperature of 75 ^° C. are heated and then homogenized. using a mechanical stirrer (10000 rpm) at the same temperature for 2 minutes and finally allowed to cool with slow stirring (300 rpm) to a temperature of about 25 ° C. This emulsion remains stable for 2 months in an oven at 45 ^° C.

EXAMPLE 19 Preparation of a self-tanning and moisturizing cream from the composition of the invention

A - Composition No. 2 of Example 2 4.0%

Aloe vera 1, 0%

Shea butter 0.2%

Dimethicone (Brentag) 2.0% 2-octyldodecyl myristate (MOD) 3.0%

Propylglycol stearate (Stepan PGMS) 1, 0%

Stearic acid 1, 0%

0.1% Vitamin E

Hyaluronic acid (VITALHYAL) 1, 0%

B - Glycerol 10%

Water qs 100%

C - Dihydroxyacetone 5.0%

Water 10.0%

D - Fragrance QS Process for making the cream:

Weigh all the ingredients of A. Weigh all B ingredients and homogenize. Heat to

75 ° C separately. Stir at 800 rpm with the mechanical stirrer.

Add B in mesh in A. Mix at 1300 rpm a few minutes at 75 ⁰ C.

Cool to 40 ° C with stirring at 300 rpm. Prepare solution C at room temperature. Add C and D to the emulsion. Correct the pH if necessary.

EXAMPLE 20 Preparation of a preservative-free hydrating milk from a composition according to the invention

Composition No. 2 of Example 2 2.0%

Miglyol 812 N (HuIs) 3.0%

Isostearyl isostearate 3.0%

Dimethicone (Brentag) 2.0%

Stearic acid 1.0%

Hyaluronic acid (VITALHYAL) 1, 0%

Water QSP 100%

Milk production process:

Weigh all the ingredients. Heat to 75 ° C. Mix at 3000 rpm with a mechanical stirrer for a few minutes at 75 ° C. Cool to 30 ° C with stirring at 500 rpm. Correct the pH if necessary.

EXAMPLE 21 Preparation of a nutritive hair balm without preservative from the composition according to the invention

Composition No. 6 of Example 6 3.0%

Dimethicone (Brentag) 1, 0%

Wheat oil 0.5%

Wheat peptides 0.5%

ParfumQS

Water QSP 100%

Manufacturing process :

Weigh everything but the perfume. Heat 75 ^° C. Agitate at 1300 rpm with mechanical stirrer for 1 minute. Cool at 300 rpm until 25 ⁰ C.

Add the fragrance. EXAMPLE 22 Composition of a shower gel from a composition according to the invention

Composition No. 5 of Example 5 8%

Composition 2 of Example 2 2%

- Soybean fatty acid diethanolamide 7%

- Dyes, perfumes qs - Water qs 100%

EXAMPLE 23: Liquid detergent composition from a composition according to the invention

Soaps 15%

Ether sulphate of fatty alcohols 5%

Composition No. 3 of Example 3 7%

Composition No. 7 of Example 7 3%

Sodium citrate 5%

Ethanol - qs

Polycarboxylates 5%

Optical brighteners qs

Stabilizers (mono ethanolamide) 3%

Perfumes qs dyes qs

Water qs 100%

EXAMPLE 24 Dishwashing Composition From a Composition According to the Invention

Composition No. 2 of Example 2 5%

Polyoxyethylene 10% sodium lauryl sulphate

Sodium chloride 3%

0.2% sodium acrylate

Ethanol 3%

Perfumes qs

Dyes qs

Water qs 100% EXAMPLE 25: Composition of liquid soap from a composition according to the invention

Composition No. 5 of Example 5 10%

Composition No. 7 of Example 7 5%

Sodium cocoyl isothionate 5%

Sodium chloride 3%

E.D.T.A 0.3%

Cocoamidodiethanolamide 5%

Perfumes qs

Water qs 100%

EXAMPLE 26 Composition of a Foaming Bath from a Composition According to the Invention

Composition No. 2 of Example 2 15%

Cocoyl monoethanolamide 5%

Triethylene glycol • 2%

Sweet almond oil 6%

2% ethoxylated sorbitan laurate

Ethoxylated propylene glycol dioleate 2%

Lauryl myristyl at 30 E 2%

E.D.T.A 0.3%

Sodium chloride 2%

Oleyl acrylate 1%

Hexadecanol 1%

Perfumes qs

Water qs 100%

Claims

A surfactant composition comprising: i) from 70 to 99% by weight of the composition of at least one alkyl glycoside of formula (1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

H- (X-CHR2-CO) n-O-R3 (2) in which:

2. Composition according to claim 1, characterized in that the alkyl glycoside of formula (1) is an alkyl pentoside.

3. Composition according to any one of claims 1 and 2, characterized in that the alkyl glycoside of formula (1) is an alkyl xyloside, a arabinoside ^alkyl or a mixture thereof.

4. Composition according to any one of claims 1 to 3, characterized in that it comprises an alkyl glycoside of formula (1) in the form of mixture ^of alkyl and alkyl hexosides pentosides.

5. Composition according to any one of claims 1 to 4, characterized in that the alkyl glycosides of formula (1), are derived from agricultural products or co-products or are derived from sugar syrups obtained by hydrolysis of co -products of plant origin rich in starch and or hemicellulose.

6. Process for the preparation of surfactant compositions according to any one of claims 1 to 5 characterized in that it consists in putting one or more lignocellulosic plant materials constituting most of the annual or perennial plants and comprising at least 1 starch and / or hemicelluloses and at least one protein or peptide, in contact with at least one alcohol having 1 to 36 carbon atoms in the presence of an acid catalyst between 20 and 200 ⁰ C, preferably between 70 and 150 ° C, for at least 5 seconds to obtain a composition according to the invention.

7. Process according to claim 6, characterized in that the unreacted alcohol is neutralized and removed from the surfactant composition.

8. Method according to any one of claims 6 and 7, characterized in that the composition is freed from a solid marc.

9. Process according to any one of Claims 6 to 8, characterized in that the lignocellulosic plant material or materials are chosen from annual or perennial plants such as maize, sorghum, barley, wheat and hemp. , flax, sugarcane, bamboos, hardwoods, softwoods and may designate parts of annual or perennial plants, such as stems or bark, or they refer to co-products of food production industries such as wheat, rice or barley straw, sugar cane bagasse or sugar sorghum, or

10. Process according to any one of claims 6 to 9 characterized in that the alcohol or alcohols used are chosen from alcohols having, as alkyl radicals, methyl, ethyl, butyl and octyl radicals, as well as radicals originating from alcohols or capric acids. , lauric, myristic, palmitic, stearic, oleic and erucic and more generally the radicals derived from acids of plant origin or alcohols synthesized by hydrogenation of fatty acids or esters of fatty acids of plant origin, the alkyl radicals originating from of alcohols of terpene origin or technical alcohols derived from the hydrogenation of aldehydes of petrochemical origin.

11. Process according to any one of Claims 6 to 10, characterized in that the acidic catalyst is composed of at least one acid chosen from hydrochloric, hydrobromic, sulfuric and phosphoric acids, and sulphonic acids such as benzenesulphonic and para-toluenesulphonic acids. , camphorsulfonic acid, alkylbenzene sulphonic acid, sulphosuccinic acid or an alkyl sulphosuccinate such as decyl or lauryl sulphosuccinate, perhalohydric acids, such as perchloric acid, the acid form of anionic surfactants such as alkyl ether sulphates, such as lauryl ether sulphate known as LES, sodium dodecyl sulfate also known as SDS or sulfuric or phosphoric esters of alcohols.

12. Method according to any one of claims 6 to 11 characterized in that the contacting is carried out for 5 to 240 minutes in a mixer.

13. Method according to any one of claims 6 to 12 characterized in that one operates at atmospheric pressure, under partial vacuum or in a reactor pressure of 2 to 100 bar.

14. Process according to any one of Claims 6 to 13, characterized in that the reaction is carried out in the total absence of a solvent.

15. Process according to any one of Claims 6 to 14, characterized in that the neutralization is carried out using at least one base chosen from an alkali metal or alkaline earth metal hydrogencarbonate or carbonate, in particular sodium hydrogencarbonate, an alkali or alkaline earth metal hydroxide, especially sodium hydroxide, or an organic base such as triethanolamine.

16. A solution characterized in that it comprises: i) from 30 to 95% by weight of the solvent composition, ii) from 4 to 69.3% by weight of the composition of at least one alkyl glycoside of Formula 1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

H- (X-CHR2-CO) n-O-R3 (2) in which:

R3, being optionally identical to R1, is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 unsaturations ethylenic, having from 1 to 36 carbon atoms, preferably having from 4 to 22 carbon atoms

17. Composition according to any one of claims 1 to 5 characterized in that it comprises: i) from 80 to 99% by weight of the composition of a mixture of compounds of formula

(1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

H- (X-CHR2-CO) n-O-R3 (2) in which:

And when X = N, then R2 is the following cyclic radical: - (CH2) 2 -Y-, Y represents a methylene group -CH2- linked to X R3, being optionally identical to R1, is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 5 to 22 carbon atoms,

Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other. and in that it has a CMC of less than 800 mg / l, a C20 of less than 100 mg / l and a wetting power according to the NF T 73406 standard of less than 100 seconds.

18. Composition according to any one of claims 1 to 5, characterized in that it comprises: i) from 80 to 99% by weight of the composition of a mixture of compounds of formula

(1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

• Gl, G2, G3, G4, G5 are independently of each other, the remains of an ose chosen from hexoses arabinose and xylose

H- (X-CHR2-CO) n-O-R3 (2) in which:

Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other. and in that it has a foam volume greater than 200 ml and a stability of the foam at 20 minutes of at least 70% according to the Ross Miles test of the standard NF-T-73-404 carried out at 50 ° C. with a demineralized water solution comprising 0.1% by weight of composition.

19. Composition according to any one of claims 1 to 5, characterized in that it comprises: i) from 80 to 99% by weight of the composition of a mixture of compounds of formula

(1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

In particular, it is preferred that Rl be preferably ethyl, propyl, butyl, 2 or 3 methyl-butyl, 2-ethylhexyl

H- (X-CHR2-CO) nO-R3 (2) in which: When X = NH, then R2 is a radical chosen from: -CH3, - (CH2) 3-NH- C (NH) -NH2, -CH2-CO-NH2, -CH2-CO-OR3, -CH2-SH - (CH 2) 2 -CO-NH 2, - (CH 2) 2 -CO-OR 3, H, -CH 2 - (C 3 H 3 N 2), -CH (CH 3) -CH 2 -CH 3, -CH 2 -CH (CH 3) -CH 3, - (CH2) 4-NH2, - (CH2) 2-S-CH3, -CH2-C6H5, -CH2-OH, -CH (OH) -CH3, -CH2- (C8H6N), -CH2- (C6H4) - OH, -CH (CH3) -CH3

In particular, R3 corresponding to the alkyl residue of ethanol, propanol, butanol, 2 or 3 methyl butanol, 2-ethylhexanol, is preferred.

Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other. and in that it has a foam volume of less than 50 ml and a stability of the foam at 20 minutes of less than 10% according to the Ross Miles test of standard NF-T-73-404 carried out at 50.degree. demineralized water solution comprising 0.1% by weight of composition.

20. Composition according to any one of claims 1 to 5, characterized in that it comprises: i) from 80 to 99% by weight of the composition of a mixture of compounds of formula

(1)

R10 (Gl) a (G2) b (G3) c (G4) d (G5) e (1) wherein:

• G1, G2, G3, G4, G5 are independently of each other, the remains of an ose selected from hexoses, arabinose and xylose A, b, c, d and e being equal to 0 or 1, the sum of a, b, c, d and e being at least equal to 1 arabinosides and alkyl xylosides then representing at least 25% by weight of all the compounds of formula (1). ii) from 1 to 20% by weight of the composition of at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) n-O-R3 (2) in which:

R3 being preferably the dodecyl, tetradecyl, hexadecyl, octadecyl radical

Where n is an integer greater than or equal to 1; and when n is greater than 1, then R2 represents several radicals as defined above identical or different from each other. and allowing the production of stable emulsions as described in standard NF T 73409.

21. Self-emulsifiable composition characterized in that it comprises:

i) from 4 to 58% by weight of the composition of a mixture of compounds of formula (1) R10 (G1a) (G2) b (G3) c (G4) d (G5) e (1) in which:

R 1 is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 8 to 36 carbon atoms, In particular, R 1 corresponding to the dodecyl, tetradecyl, hexadecyl and octadecyl radical is preferred.

A, b, c, d and e being equal to 0 or 1, the sum of a, b, c, d and e being at least equal to 1 arabinosides and alkyl xylosides then representing at least 25% by weight of all the compounds of formula (1). ii) from 0.1 to 12% by weight of the composition of at least one compound of formula (2) or a salt thereof,

H- (X-CHR2-CO) n-O-R3 (2) in which:

When X = NH, then R2 is a radical chosen from: -CH3, - (CH2) 3-NH- C (NH) -NH2, -CH2-CO-NH2, -CH2-CO-OR3, -CH2-SH - (CH 2) 2 -CO-NH 2, - (CH 2) 2 -CO-OR 3, H, -CH 2 - (C 3 H 3 N 2), -CH (CH 3) -CH 2 -CH 3, -CH 2 -CH (CH 3) -CH 3, - (CH2) 4-NH2, - (CH2) 2-S-CH3, -CH2-C6H5, -CH2-OH, -CH (OH) -CIB, -CH2- (C8H6N), -CH2- (C6H4) - OH, -CH (CH3) -CH3

In particular, R3 corresponding to the dodecyl, tetradecyl, hexadecayl, octadecyl radical is preferred.

(4)

R4-OH (4) wherein,

R4 is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 4 ethylenic unsaturations, having from 1 to 36 carbon atoms and more particularly having from 8 to 20 carbon atoms. R4 may be different or identical to R1 and R3.

22. Detergent product characterized in that it contains from 0.1 to 50% by weight of a detergent base, and from 1 to 99.9% by weight of surfactant composition according to any one of claims I to 5 and 17 to 21.

23. Cosmetic product characterized in that it contains from 0.1 to 95% by weight of a cosmetic base, and from 1 to 99.9% by weight of surfactant composition according to any one of claims I to 5 and 17 to 21.

24. agrochemical product characterized in that it contains from 0.1% to 95% by weight of an agrochemical base, and from 1 to 99.9% by weight of surfactant composition according to any one of claims I to 5; and 17 to 21.

25. Emulsion which comprises by weight: a. from 0.1 to 20% by weight relative to total weight of ^"emulsion composition according to any one of claims 1 to 5 and 17 to 21, and preferably between 1 and 10% b. from 0 to 95% by weight relative to the total weight of emulsion, of oil, and preferably between 0 and 50% of 0 to 50% by weight relative to the total weight of emulsion, of active substance, and preferably between 0 and 50% by weight. and 20% d and water in addition to 100%.