FR2720742A1 - Poly:glycerol amido:amine(s) - Google Patents

Abstract

Polyglycerolated amidoamines of formula (I) in which R<1> is an alkylaryl, cycloalkyl, straight or branched alkenyl or alkyl C2-C22 hydrocarbonated group, R<2> and R<3> are a hydrogen atom, a C1-C4 alkyl group, a 2-hydroxy ethyl, 2-hydroxy propyl or polyhydroxyoxaalkyl group with 1-10 hydroxyoxaalkyl units; <u>n</u> is an integer from 2-6; <u>m</u> is an integer from 1-5; <u>p</u> is greater than 1, preferably in the order of 1.1 to 50. The amidoamines of the invention are obtained by polycondensing an activated glycerol derivative on an amindoamine of formula R<1>-CO-NR<2>-[(CH2)n-NR<3>]-OH. Said amidoamines can be used as surface-active agents in detergents, cosmetics and the like.

Description

The present invention relates to novel amidoamines

polyglycerolates and their use as surfactants; these surfactants are of particular interest in detergency, in cosmetics, as an agent for dispersing agrochemical active materials, as a surface agent for textiles (lubrication, fireproofing, softening, etc.), as a surface agent for metals (anti -corrosion, lubrication ...) and as an antistatic agent for fibers and films of mineral polymers

or organic.

It is known to use salts of hydroxyalkylated amino acids as cationic agents in cosmetic preparations, in particular for washing the hair (FR 1,134,848 and 1,134,849). These salts are prepared from aminoamides

hydroxyalkylated of the type hydroxyethylamino-ethyl-lauroylamide, hydroxyethylamino-ethyl -

stearoylamide. These two hydroxyalkylated aminoamides can be represented by the formula R-CO-NH-CH2-CH2-NH-CH2-CH2-OH The present invention relates to polyglycerolated amidoamines of formula (I) OH R1-CO-NR2 [(CH2) n-NR3] m- (CH2- CH-CH2-O) pH (I) formula in which - R1 represents a hydrocarbon group, C2-C22, preferably C8-C22, linear or branched alkyl or alkenyl, cycloalkyl or alkylaryl - R2 and R3 are the same or different and represent a hydrogen atom, a C! -C4 alkyl group, a 2-hydroxyethyl, 2-hydroxypropyl or polyhydroxyoxaalkyl group with a number of hydroxyoxaalkyl units from 1 to 10, from preferably from 2 to 5 - n is an integer which may range from 2 to 6, preferably equal to 2 or 3 - m is an integer which may range from 1 to 5, preferably equal to 1 or 2 - is an integer or decimal greater than 1, preferably of the order of 1.1 to 50

and most particularly of the order of 2 to 5.

These polyglycerolated amidoamines of formula (I) can be prepared by polycondensation of an activated derivative of glycerol, such as an epoxidized derivative of glycerol (epichlorohydrin or preferably glycidol), on an amidoamine of formula (II) R1-CO-NR2 - [(CH2) n-NR3] m-OH (II)

formula in which R1, R2, n and m have the definition given above.

This operation can be carried out at a temperature of the order of 70 to 180 ° C., preferably of the order of 110 to 150 ° C., by continuously adding the activated derivative of glycerol in a proportion of the order of 1.1 to 50 molar equivalents, preferably of the order of 2 to 5 molar equivalents, of activated derivative of glycerol relative to

amidoamine of formula (II).

If desired, this operation can be carried out in the presence of a third solvent inert to

screw of the activated derivative of glycerol; by way of example of a solvent, mention may be made of saturated aliphatic hydrocarbons (heptane, octane, etc.), aromatic hydrocarbons (toluene, cumene, etc.), ketones (2-octanone, etc.), secondary alcohols or tertiary

(isopropanol, tertiobutanol ...).

This reaction can be carried out in the absence of a catalyst, or if necessary in the presence of an acid catalyst (preferably a Lewis acid such as boron trifluoride, tin tetrachloride, antimony pentachloride, etc.) or of a basic catalyst (alkali metal hydroxide such as NaOH, KOH, alkali metal alcoholate such as sodium methoxide, potassium tert-butoxide, etc.), and this in an amount corresponding to approximately 0.05 to 10%, preferably about 0.1 to 1% by weight based on the reaction mass. When the activated derivative of glycerol used is epichlohydrin, it is necessary to neutralize the halogen formed continuously using a base such as alkali metal or alkaline earth hydroxides, tertiary amines such as triethylamine . If desired, the halides formed can be separated from the medium by any known method, such as for example by precipitation with a third solvent of the alcohol type such as isopropyl alcohol, by electrodialysis or by any other known process for the desalification of the salts.

surfactants such as reverse osmosis.

Another method of preparing said polyglycerolated amidoamines of formula (I) consists in reacting a monohalohydrin of glycerol, such as 1,2-monochlorohydrins or 1,2-monobromhydrins of polyglycerol having an average degree of polycondensation of 1.1 to 50 , preferably from 2 to 5, on the amidoamine of

formula (II) above.

Polyglycerol 1,2-monochlorohydrins are the preferred raw materials.

This operation can be carried out at a temperature of the order of 70 to 180 C, preferably of the order of 110 to 150 C, by continuous addition of the monohalohydrin of the glycerol in a proportion of the order of 1.1 to 50 molar equivalents, preferably of the order of 2 to 5 molar equivalents, of activated derivative of glycerol relative to

amidoamine of formula (II).

If desired, this operation can be carried out in the presence of a third solvent inert to

screw of the activated derivative of glycerol; by way of example of a solvent, mention may be made of saturated aliphatic hydrocarbons (heptane, octane, etc.), aromatic hydrocarbons (toluene, cumene, etc.), ketones (2-octanone, etc.), secondary alcohols or tertiary

(isopropanol, tertiobutanol ...).

This reaction can be carried out in the absence of a catalyst, or if necessary in the presence of an acid catalyst (preferably a Lewis acid such as boron trifluoride, tin tetrachloride, antimony pentachloride, etc.) or of a basic catalyst (alkali metal hydroxide such as NaOH, KOH, alkali metal alcoholate such as sodium methoxide, potassium tert-butoxide, etc.), and this in an amount corresponding to approximately 0.05 to 10%, preferably about 0.1 to 1% by weight based on the reaction mass. It is necessary to neutralize the halogen formed continuously using a base such as alkali metal or alkaline earth hydroxides, tertiary amines such as triethylamine. If desired, the halides formed can be separated from the medium by any known method, such as for example by precipitation with a third solvent of the

alcohol type such as isopropyl alcohol, or by electrodialysis.

A more particular subject of the present invention is the polyglycerolated amidoamines of formula (111)

CH2-CH2-OH

R1-CO-NH-CH2-CH2- N OH (III) (CH2- CH-CH2-O) pH formula in which R1 represents a linear or branched alkyl or alkenyl group in C2-C22, preferably in C8-C22 and 2 is an integer or decimal greater than 1,

preferably of the order of 1.1 to 50 and very particularly of the order of 2 to 5.

These polyglycerolated amidoamines of formula (111) can be obtained according to one of the processes described above from the amidoamine of formula

R1-CO-NH-CH2-CH2-NH-CH2-CH2-OH

amidoamine which can be prepared by amidification of aminoethylethanolamine with a C2-C22 fatty acid, preferably C8-C22 or one of its derivatives such as ester,

triglyceride or acid chloride.

The polyglycerolated amidoamines forming the subject of the invention are surfactants very well tolerated by biological systems, generally exhibiting in particular good foaming, dispersing and detergent power, which makes their field

very varied application.

Thus, N-laurylamidoethyl N- (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamrnine, prepared from laurylimidazoline or cocoylimidazoline, can be used in detergents, in cosmetics, as a surface agent for textiles (lubrication). , fireproofing, softening ...) and as an antistatic agent for fibers and films of mineral polymers

or organic.

N-palmitylamidoethyl N- (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamine, prepared from palmitylimidazoline, can be used more particularly in detergents, in cosmetics and as an antistatic agent for fibers and films of mineral polymers or organic. N-stearylamidoethyl N- (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamine, prepared from stearyllimidazoline, can preferably be used in detergents, in cosmetics, as a surface agent for textiles (lubrication, fireproofing, softening ...) and

as a metal surfactant (anti-corrosion, lubrication, etc.).

N-oleylamidoethyl N- (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamine, prepared from oleylmidazoline, can be used more particularly in cosmetics, as an antistatic agent for fibers and films of inorganic or organic polymers and as

metal surfactant (anti-corrosion, lubrication, etc.).

N-behenylamidoethyl N- (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamine, prepared from behenylimidazoline, can be used in particular in cosmetics, as a surface agent for textiles (lubrication, fireproofing, softening, etc. ) and like

metal surfactant (anti-corrosion, lubrication, etc.).

A subject of the present invention is also cosmetic compositions with

base of the polyglycerolated amidoamines forming the subject of the invention.

The term cosmetic composition or formulation is understood to mean all cosmetic products or preparations such as those described in Annex I ('Illustrative list by category of cosmetic products') of European Directive 76/768 / EEC of July 27.

1976 known as the 'cosmetic directive'.

The polyglycerolated amidoamines, which are the subject of this invention, can be used more particularly in formulations of lotions, toilet milks, make-up removing compositions, care creams or creams or lotions for protection against the sun and ultraviolet radiation, foams, styling gels or any formulation used for styling or to facilitate combing the hair, hair or body shampoos, facial or body cleansing gels, liquid soaps, bath foaming compositions, formulations used for cleansing

teeth or oral cavity such as mouthwashes or toothpaste.

Said polyglycerolated amidoamines can also be used alone or in combination in the formulation of soaps or toilet bars. Due to their cationic activity at acidic pH, they can also be used for the preparation of

rinse formulations or conditioner balms for hair or skin.

Cosmetic compositions generally contain surfactants which serve to disperse, emulsify, solubilize and stabilize various compounds used for their emollient or humectant properties. The surfactants are used in these compositions at concentrations varying from 0.05 to 10% by weight of the preparation. Among the humectants, mention may be made of glycerol, sorbitol, urea, collagen,

gelatin, aloe vera, hyaluronic acid, ...

The emollients are generally chosen from alkylmonoglycerides, alkyldiglycerides, triglycerides such as oils extracted from plants and vegetables (palm, copra, cottonseed, soybean, sunflower, olive and grape seed oils , sesame, peanut, castor, etc.) or oils of animal origin (tallow, fish oils, etc.), derivatives of these oils such as hydrogenated oils, lanolin derivatives, mineral oils or paraffinic oils, perhydrosqualane, squalene, diols such as 1-2-propanediol, 1-3-butanediol, cetyl alcohol, stearyl alcohol, oleic alcohol, polyethylene glycols or

polypropylene glycols, fatty esters such as isopropyl palmitate, ethyl cocoate

2-hexyl, myristyl myristate, lactic acid esters, stearic acid, behenic acid, isostearic acid, silicone oils including cyclic polydimethylsiloxanes, as hydroxylated polydimethylsiloxanes, a- "ô polydimethylsiloxanes trimethylsilylls, polyorganosiloxanes such as polyalkylmethylsiloxanes, polymethylphenylsiloxanes, polydiphenylsiloxanes, amino derivatives of silicones, silicone waxes, silicone copolyethers (such as SILBIONE 70646 oil sold by the company RHONEN-POULENC marketed by the company RHONEN-POULENC or DOWENC marketed by the company RHONEN-POULENC or DOWENC) mixed silicones such as

mixed polyalkylmethylsiloxane-silicone copolyethers copolymers.

To these compounds, one can add powders or mineral particles such as calcium carbonate, mineral oxides in powder form or in colloidal form (particles smaller in 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, GERMABEN 'or any chemical agent preventing bacterial proliferation or mold and traditionally used in cosmetic compositions are generally introduced into these compositions with

height of 0.01 to 3% by weight.

As an alternative to these chemical agents, it is sometimes possible to use agents which modify the activity of water and greatly increase the osmotic pressure, such as

carbohydrates or salts.

To protect the skin or the hair from the aggressions of the sun and UV rays, we can add to these formulations sun filters which are either chemical compounds which strongly absorb UV radiation such as the compounds authorized in European Directive N 76/768 / EEC, its annexes and subsequent amendments to this directive, either titanium dioxide or cerium oxides under

powder or colloidal particle form.

Perfumes, dyes or pigments can also be added.

Viscosity or gelling polymers may also be present (such as the crosslinked polyacrylates CARBOPOL 'marketed by GOODRICH-, cellulose derivatives such as hydroxypropylcellulose, carboxymethylcellulose, guars and their derivatives, carob, tara or cassia gum , xanthan gum, alginates,

carrageenans, chitin derivatives such as chitosan ...

A toothpaste may contain, in addition to abrasive agents such as silica or calcium carbonate (used at 5 to 25% by weight of the total composition), from 0.1 to% by weight of said surfactants of the invention, taken alone or in admixture with the usual surfactants such as anionic, nonionic or zwitterionic surfactants such as alkyl betaines or alkylamidopropyl betaines or amphoterics or combinations of these compounds. These surfactants which are used as foaming agents when using the composition, as well as for their cleaning and disinfecting power. Sometimes they are used specifically for a therapeutic action like the alkyl sarcosinates which protect the teeth by inhibiting the enzymatic activity.

bacteria responsible for infections of the teeth or gums.

The toothpaste compositions also contain from 5 to 85% of so-called humectants

such as glycerol, sorbitol, polyethylene glycols, lactilol, xylitol.

The rheological behavior of the dental paste, that is to say its viscosity, its hold on the brush, the ease of its extrusion at the exit of the tube or the dispenser, the non-stringing character of the paste is controlled by thickening agents such as certain silica used for this purpose (TIXOSIL 438 marketed by RHONE-POULENC) and / or polymers used alone or in combination such as xanthan gum, guar gum, cellulose derivatives (Carboxymethylcellulose for example), crosslinked polyacrylates such as CARBOPOL distributed by GOODRICH, alginates or carrageenans, VISCARIN. The total of thickening agents represents 0.1

to 15% by weight of the composition of a toothpaste.

Therapeutic agents such as certain fluorine or potassium salts, flavors, agents and agents are also generally found associated with these various constituents.

sweeteners and water.

The polyglycerolated amidoamines of this invention can also be used in toilet bar formulations called bar soaps or soaps. Conventional toilet bar compositions generally comprise fatty acid salts used in combination with surfactants of the invention and optionally surfactants other than the salts of fatty acids or the fatty acids themselves. These compositions may even contain no fatty acid or fatty acid salt and their formulations are then based on other surfactants such as for example sodium C8-C22 alkyl isethionates or sodium alkyl sulphates in

C8-C22.

To these compositions one can also add various constituents useful for reducing irritation or aggression of the skin such as alkali metal salts or isethionates or for promoting hydration of the skin such as certain carbohydrates (glycerol, sorbitol for example) , polyethylenes glycol or polypropylene glycol, alkoxylated derivatives of sugars or their derivatives (methyl glucose for example), water-soluble or water-dispersible polymers such as collagen or certain non-allergenic derivatives of animal or plant proteins (hydrolisates of wheat proteins for example ), natural hydrocolloids (guar, locust bean, tara gum, etc.) or resulting from fermentation processes such as xanthan gum and derivatives of these polycarbohydrates such as modified celluloses (for example hydroxyethylcellulose, carboxymethylcellulose, cationic celluloses such as POLYMER JR 'marketed by the company UNION CARBIDE), guar or carob derivatives such as their cationic derivatives (JAGUAR C13S, JAGUAR C162 marketed by RHONE-POULENC) or nonionic derivatives (for example hydroxypropylguar),

anionic derivatives (carboxymethylguar) or mixed non-

ionic / anionic such as carboxy-hydroxypropyl-guars or not

ionic / cationic. It is also possible to add, alternately or in combination, synthetic polymers such as polyacrylates or synthetic cationic polymers, known under the generic CTFA name of "Polyquatemrnium ', for example.

the polymers MIRAPOL A15 or MIRAPOL 550 from the company RHONE-POULENC.

It is also advantageously possible to add to these compositions these metal sequestering agents, more particularly those sequestering calcium such as citrate ions or emollient agents such as silicones or oils or fatty substances used for this purpose in the cosmetics industry (mineral oils, esters of fatty acids, triglycerides, silicones, etc.). To these ingredients are generally added one or more perfumes, dyes and / or opacifying agents such as pigments (titanium oxide particles). Bactericidal or fungicidal agents can also be incorporated into the composition in order to improve the

skin disinfection.

In a toilet bar whose formulation consists mainly of soaps

monocarboxylic fatty acids (sodium, potassium, mono-, di- or tri-

ethanolammonium); the fatty acid soap contents are generally more than

% by weight of the formulation, generally 30 to 95% by weight.

In a toilet bar whose formulation is based on other main constituents than fatty acid soaps, there is in the formulation from 0 to 50% by weight,

preferably from 1 to 40% by weight of these fatty acid soaps.

These toilet bar compositions can also contain from 0 to 95%,

preferably from 0 to 60% of surfactants other than soaps, in particular C8-

C22 aikyl or alkenyl isethionates, as well as alkylethersulphates, alkylbétaines,

alkylamidopropylbétaines, alkylampho-acetates, -diacetates, propionates or -

dipropionates used to decrease irritation that may be caused by other

surfactants, mainly anionic surfactants.

From 1 to 15% of free fatty acids C8-C22 can also be introduced into the soap compositions as superfatting agents or to modify the appearance and the

creaminess of the foam when washing.

Waxes such as paraffin waxes, natural waxes such as beeswax or ozokerite or silicone waxes can also be found in these compositions. These waxes are advantageously used to improve the appearance, hold,

processability and conservation in storage of toilet bars.

Shampoos, and more generally detergent compositions for personal use may contain, in addition to the amidoamines of the invention,

usual additives present in these types of formulations.

Mention may be made in particular of: - aronic surfactants, such as water-soluble salts of alkylsulphates, of alkylethersulphates, alkylisethionates and alkyltaurates or their salts, alkylcarboxylates, alkylsulfosuccinates or alkylsuccinamates, alkylsarcosinates, alkylated derivatives of protein hydrolysates, acylaspartates - zwitterionic or amphoteric surfactants, such as alkylbetaines, alkylamidopropylbetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates, alkylamphopropionates, alkylamphodipropidopropylaines or alkylhydroxy-hydroxypropionates, nonionic surfactants, such as polyoxyethylenated derivatives of C8-C22 aliphatic or arylaliphatic alcohols, alkylpolysaccharides having a C6-C30 hydrophobic group, preferably C10-C16 and a polysaccharide group, for example polyglycoside, as hydrophilic group as well as from 1 to 3 u sugar nities, alkylated derivatives of aminosugars, such as alkylglucamides produced by the amidification reaction of a fatty acid with N-methylglucarnine - amides derived from fatty acids generally used for their ability to improve the foaming of compositions or increasing the viscosity of said compositions; these amides are generally chosen - cationic conditioning agents (improving combability, styling, feel and volume of the hair) such as synthetic cationic polymers of the MIRAPOL AD1 or MIRAPOL A550 type marketed by RHONE-POULENC, natural cationic polymers such as cationic guar derivatives (JAGUAR C135, JAGUAR C162e sold by RHONE-POULENC) or derivatives

cationic cellulose (POLYMER JR4008 sold by UNION CARBIDE).

- organopolysiloxanes used as such or in solution in one of their usual solvents (silicone oils of low masses, highly branched paraffinic oils, fatty esters for example of the isopropyl palmitate type, etc.), as conditioning agents or

shine.

- anti-dandruff agents, such as pyridinesthiones, more especially zinc pyridinethione, selenium-based compounds such as selenium sulphide or r'OCTOPYROX, marketed by HOECHST - anti-parasitic agents (anti-lice), such as LINDANE or different pyrethrins

used in this connection.

These compositions can also contain agents modifying the appearance or the viscosity of the formulations such as pearlscent compounds based on polyethylene glycol stearate or polymers improving viscosity or stability such as the CARBOPOL marketed by GOODRICH, hydrocolloids and their derivatives such as guar or modified guars, carob, xanthan gum, cellulose derivatives

(hydroxyethylcellulose, marboxymethylcellulose).

The conventional shampoo compositions containing the glycerolated amidoamines of the invention can consist of (weight percentages) glycerolated amidoamine of the invention 1-15% anionic surfactant 0-15% amphoteric surfactant 0-10 % fatty acid alkanolamide 0-5% 35. thickening agent 0-5% conditioning agent 0-3% perfume 0-2% preservative 0-2% anti-dandruff agent 0-2% water supplement to 100% The polyglycerolated arnidoamines of l The invention can also be used in formulations where it is necessary to maintain finely divided solids in suspension in water, such as formulations of agrochemical active materials (herbicides, insecticides, fungicides, etc.) known under the generic name of suspensions. concentrated '. In addition to a dispersing surfactant, additives such as those described in the commercial brochure "Auxiliaries for agrochemical formulations" published by RHÈNE-POULENC are found as additives in a concentrated suspension formulation.

GERONAZZO SpA.

Mention may be made, for example, of a wetting surfactant, taken from alkoxylated derivatives of arylaliphatic alcohols, aryl sulfone derivatives such as isopropylnaphthalene

sodium sulfonate, marketed under the name SUPRAGIL WP by RHONE-

POULENC GERONAZZO, dialkyl sulfosuccinates such as sodium di-ethyl-2-hexyl sulfosuccinate, dispersing polymers, such as polyacrylic acids and their salts, maleic anhydride (or acid) - diisobutylene copolymers and their salts such as GEROPON T36 (RHONE) -POULENC GERONAZZO), condensed sodium methylnaphthalenesulphonate such as SUPRAGIL MNS90 (RHONE-POULENC GERONAZZO), dispersing polymers derived from lignin such as sodium or calcium lignosulphonates or other dispersing surfactants such as alkoxylated derivatives, optionally sulphated or phosphated with tristyrylphenols. One can also find in these formulations, antifreeze additives such as propylene glycol and thickening additives, modifying 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

the bentones.

Among the active materials which can be formulated in this way, there are generally found those whose melting point is greater than 45 C, preferably greater than 60 C and

whose solubility in water is less than 10 g / l, preferably less than 1 g / l.

The phytosanitary active ingredients concerned are herbicides, fungicides and

insecticides, such as those described in THE PESTICIDE MANUAL (9th edition, C.R.

WORKLING and R.J. HANCE, editors, published by The British Crop Protection Council) and

meeting the above criteria.

A subject of the present invention is also detergent compositions based on

polyglycerolated amidoamines forming the subject of the invention.

By detergent composition is meant any detergent formulation, powder or liquid, intended for use both in washing machine, dishwasher and for

general household cleaning.

Besides said polyglycerolated amidoamines of the invention, other additives of the type described below may be present in the detergent compositions. - Other surfactants, in amounts corresponding to approximately 3-40% by weight relative to the detergent composition, surfactants such as anionic surfactants, alkyl esters sulfonates of formula R-CH (SO3M) -COOR ' , o R represents an alkyl radical in C8-20, preferably in C10-C16, R 'an alkyl radical in C1-C6, preferably in C1-C3 and M an alkali cation (sodium, potassium, lithium), substituted ammonium or unsubstituted (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative of an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...). Mention may very particularly be made of methyl ester sulfonates in which the R radical is C14-C16; alkylsulphates of formula ROSO3M, o R represents an alkyl radical or

C10-C24 hydroxyalkyl, preferably C12-C20 and very particularly C12-

C18, M representing a hydrogen atom or a cation of the same definition as above

above, as well as their ethoxylenated (EO) and / or propoxylenated (OP) derivatives, exhibiting on average from 0.5 to 6 units, preferably from 0.5 to 3 EO and / or OP units; alkyl amide sulfates of formula RCONHR'OSO3M o R represents a C2-C22, preferably C6-C20, alkyl radical, R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (OP) derivatives, exhibiting on average from 0.5 to 60 EO and / or OP units; salts of saturated or unsaturated C8-C24 fatty acids, preferably C14-C20,

C9-C20 alkylbenzenesulfonates, primary or secondary C8- alkylsulfonates

C22, alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates, N-acyl Nalkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulffosuccinates, monoesters or diesters of sulfosuccinates, sulfosuccinates or monoesters N-acyl sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ... ) or derivative of an alkanolamine (monoethanolamine, diethanolamine, triethanolamine, etc.); nonionic surfactants polyoxyalkylenated alkylphenols (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) in which the alkyl substituent is C6-C12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the TRITON X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy .; 5. glucosamide, glucamide, glycerolamide; polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene); by way of example, mention may be made of the TERGITOL 15-S-9, TERGITOL 24-L-6 NMW sold by Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by

Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy.

the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with propylene glycol, such as the PLURONICs sold by BASF; the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with ethylenediamine, such as TETRONIC sold by BASF; amine oxides such as oxides of C1 0-C18 alkyl dimethylamines, oxides of C8-C22 alkoxy ethyl dihydroxy ethylamines; the alkylpolyglycosides described in US-A-4,565,647; 20. amides of C8-C20 fatty acids ethoxylated fatty acids ethoxylated fatty amides ethoxylated amines cationic surfactants 25. alkyldimethylammonium halides amphoteric and zwitterionic surfactants alkyldimethylbetaines, alkylamidopropyldimethyltretainsobetaines , the condensation products of fatty acids and hydrolysates

protein.

- BUILDERS AGENTS, in amounts corresponding to approximately 5-50%, preferably approximately 5-30% by weight for liquid detergent formulas, or approximately 10-80%, preferably 15-50% by weight for detergent formulas in powders, builders agents - as inorganic builders polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines tetraborates or borate precursors silicates, in particular those with a SiO2 ratio / Na20 of the order of 1.6 / 1 to 3.2 / 1 and the lamellar silicates described in US-A-4,664,839 the carbonates (bicarbonates, sesquicarbonates) alicalins or alkaline earth metals cogranules of hydrated metal silicates alkali metals and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868, crystalline or amorphous aminosilicates of alkali metals (sodium, potassium) or ammonium, such as s zeolites A, P, X ...; zeolite A with a particle size of the order of 0.1-10 micrometers is preferred. builders organioues water-soluble polyphosphonates (ethane 1-hydroxy-1, 1-diphosphonates, salts of methylene diphosphonates ...) water-soluble salts of polymers or of carboxylic copolymers or their water-soluble salts such as 15. polycarboxylate ethers (oxidisuccinic 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 esters carboxylic acid polyaspartic acid, polyglutamic acid and their salts 25. polyimides derived from the polycondensation of aspartic acid and / or glutamic acid the s polycarboxymethylated derivatives of glutamic acid or other amino acids - BLEACHING AGENTS, in amounts of about 0.1-20%, preferably about 1-10% by weight, optionally combined with BLEACH ACTIVATORS, in amounts of about 0.1-60%, preferably about 0.5-40% by weight, agents and activators such as bleaches perborates such as sodium perborate monohydrate or tetrahydrate peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate preferably combined with a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid; among these activators, there may be mentioned tetraacetylethylene diamine, tetraacetyl methylenediamine, tetraacetyl glycoluryl,

sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, octaacetyl lactose ...

percarboxylic acids and their salts (called percarbonates') such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, acid nonylamide

peroxysuccinic, I decyldiperoxysuccinic acid.

These agents can be combined with at least one of the anti-fouling or anti-

redeposition mentioned below.

Mention may also be made of non-oxygenated bleaching agents, acting by photoactivation in the presence of oxygen, agents such as sulfonated aluminum and / or zinc phthalocyanines ANTI-SOILING AGENTS, in amounts of the order of 0.01- 10%, preferably approximately 0.1-5%, and very particularly of the order of 0.2-3% by weight, agents such as cellulose derivatives such as cellulose hydroxyethers, methylcellulose, 1 ' ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose polyvinyl esters grafted on polyalkylene backbones such as polyvinylacetates grafted on polyoxyethylene backbones (EP-A-219 048) polyvinyl alcohols 20. polyester copolymers based on terephate and ethylene units / or propylene terephthalate and polyoxyethylene terephthalate, with a molar ratio (number of units) ethylene terephthalate and / or propylene terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 to 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 ( US-A-3

959,230, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US-A-4,770,666);

sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1,2 propylene diol, having 1 to 4 sulfonated groups (US Pat. No. 4,968,451) 30. copolymers polyesters based on propylene terephthalate and polyoxyethylene terephthalate units and terminated by ethyl units. methyl (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or anionic sulfopolyethoxy (US-A-4,721,580), sulfoaroyl groups

(US-A-4 877 896)

35. polyesters-polyurethanes obtained by reaction of a polyesters of molecular mass in number of 300-4000 obtained from adipic acid and / or tereptalic acid and / or sulfoisophthalic acid and a diol of mass less than 300, on a prepolymer containing terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular mass of 6004000 and a diisocyanate ((FR-A-2

334,698)

- ANTI-REDEPOSITION AGENTS, in amounts of approximately 0.01-10% by weight for a powder detergent composition, of approximately 0.01-5% by weight for a liquid detergent composition, agents such as monoamines or polyamines ethoxylated, polymers of ethoxylated amines

(US-A-4,597,898, EP-A-11,984)

carboxymethylcellulose polyestersulfonated oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol (FR-A-2 236 926) polyvinylpyrollidones - CHELATING AGENTS of iron and magnesium, in quantities of the order of 0.1-10%, preferably of the order of 0.1-3% by weight, agents such as aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethyl ethylenediaminetriacetates, nitrilotriacetates aminophosphonates such as nitrilotris (methylene phosphonates) aromatic compounds polyfunctionals such as dihydroxydisulfobenzenes - POLYMERIC DISPERSANTS, in an amount of the order of 0.1-7% by weight, to control calcium and magnesium hardness, agents such as 20. water-soluble salts of polycarboxylic acids of molecular mass of the order of 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, ac ide or maleic anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and most particularly polyacrylates with a molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067) , copolymers of arylic acid and maleic anhydride with a molecular mass of the order of 5,000 to 75,000

(EP-A-66 915)

polyethylene glycols with a molecular mass of the order of 1,000 to 50,000 AGENTS OF FLUORESCENCE (BRIGHTENERS), in an amount of approximately 0.05-1.2% by weight, agents such as derivatives of stilbene, pyrazoline, coumarin, acid fumaric acid, cinnamic acid, azoles, methinecyanines, thiophenes ... ('The production and application of fluorescent brightening agents' - M. Zahradnik, published by John Wiley & Sons, New York-1982-) - FOAM SUPPRESSORS, in quantities up to 5% by weight, agents such as C1 0-C24 monocarboxylic fatty acids or their alkali, ammonium or alkanolamine salts, fatty acid triglycerides, saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic, such as paraffins, waxes N-alkylaminotriazines monostearylphosphates, monostearyl alcohol phosphates polyorganosiloxane oils or resins optionally combined with silica particles - SOFTENING AGENTS, in quanti teas of approximately 0.5-10% by weight, agents such as ENZYMES clays in an amount which may range up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of composition detergent, enzymes such as proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139,

US-A-4,101,457, US-A-4,507,219, US-A-4,261,868

- OTHER ADDITIVES such as alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin) buffering agents for perfumes pigments The polyglycerolated amidoamines of the invention can also be used as a surface agent for textiles (lubrication). , fireproofing, softening, etc.), as a metal surfactant (anti-corrosion, lubrication, etc.) and as an agent

antistatic for fibers and films of mineral or organic polymers.

The following examples are given as an indication.

The methods for measuring the dispersing power, the detergency and the emulsifying power of the polyglycerolated amidoamines of the invention were carried out as follows

DISPERSING POWER

PRINCIPLE

The dispersing power is quantified by noting the stability over time of a powder dispersed in an aqueous medium (here hard water at 30 HT [120 mg of Ca ++ per liter D]) in

using a suspensivity test.

Suspensivity is defined as the quantity of particles suspended after a given time in a column of liquid of given height, expressed as a percentage relative to the quantity present at the start. This test, derived from the CIPAC (Collaborative International Pesticides Analytical Council Ltd) MT 15-1970- method, has been adapted for a draft standard by the Commission for Test Methods (ASPA)

Method for evaluating the dispersing power of surfactants ".

This test makes it possible to classify the surfactants as dispersing agents or not.

PROCEDURE

- Solid extra

The powder selected is rutile titanium oxide RL 68 8 sold by RHONE-

POULENC. It is a surface treated white pigment. It is coated with silica (SiO2: 0.79%) and alumina (Al2O3: 2.82%) and has been surface treated with an organic treatment which makes this pigment compatible with lipophilic media. This product is not

dispersible in water.

The main properties of RL 688 are defined as follows: Average particle size: 0.35 pm% <0.17 Pm% <1.02 pm - Total TiO2: 93.8% -pH: 7.2 - Specific surface area: 15, 5 m2 / g - Density 3.9 to 4.1 g / cm3 - Preparation of a concentrated pre-dispersion 2.5 g of TiO2 are weighed out in a 50 ml beaker. 0.50 or 0.75 or 1.25 grams of hard water containing 10% by mass of the product to be tested is added, so as to obtain a mixture containing 2, 3 or 5% of this product relative to the oxide titanium. Thus: For 2% of product, it is necessary. .................

...: 0.50 g of 10% solution For 3% of product, it is necessary. ............ DTD: ..........: 0.75 g of 10% solution .. DTD: For 5% of product, it is necessary. .................: ...... 1.25 g of 10% solution.

The whole is dispersed manually using a glass stirrer, adding, if necessary, a little water at 30 HT until a very smooth and homogeneous flowable paste is obtained. - Dilute dispersion The concentrated dispersion is poured into a 250 ml graduated cylinder with ground-glass stopper, rinsing the beaker with water at 30 HT. The level of the test piece

is made up to 250 ml with the same hard water at 30 HT.

The concentration of titanium oxide dispersed in water is then 1% by weight.

The test tube, held by the neck and its stopper, is inverted 30 times in a row, in approximately 5 seconds for each phase. It is left to stand for 1 hour at the

laboratory temperature.

After this time has elapsed, the upper 225 ml are withdrawn, taking care not to stir the suspension. The aspiration is carried out with a sufficiently long glass tube, connected to a water pump via a vacuum flask with a capacity of 3 liters. The lower 25 ml are then poured into an aluminum capsule (70 × mm), the empty weight of which has previously been measured with a balance accurate to within 1/10 mg. The test tube is rinsed with distilled water, and the rinsing water is collected in the capsule.

The capsule is placed for drying in an oven at 105 ° C. for 3 hours.

- Calculation of the suspensivity M0 is the mass initially introduced in grams of the TiO2 powder and of the product to be tested, M1 is the mass of the dry extract found in the lower 25 ml of the test tube,

weighed on a precision scale at 1/10 rmg.

The suspensivity is given by the following calculation formula: suspensivity = (M0-M1) / 225 x 250 / M0 x 100 We consider that: 15. a suspensivity greater than 90%, with 3% of product to be tested corresponds to a good dispersant with a suspensivity greater than 90%, with 5% of product to be tested corresponds to an average dispersant a suspensivity of less than 90% with 5% of product to be tested corresponds to a poor dispersant

DETERGENT POWER

PRINCIPLE

The test simulates a simplified machine wash, using a tergotometer. It consists of washing test pieces of soiled tissue at 40 ° C. in a standard and uniform manner, with only the product to be tested and sodium bicarbonate to stabilize the pH. The washing lasts thirty minutes and the detergency is evaluated by measuring the whiteness of the

pieces of fabric, before and after washing, using a colorimeter.

EQUIPMENT AND MATERIAL

Equipment:

- Tergotometer: U.S. TESTING Co Inc 'HOBOKEN N.J. Model 7243.

- Ice machine for ironing fabric samples after washing.

- "Dr Lange LUCI 100" color measuring device.

Fabrics Standard fabrics are manufactured by the CFT (Center For Test materials) or by the

company 'Test Fabric' They have the following characteristics.

Standard soiled fabrics (soiling) number of pieces per test - soiled cotton CS-3 CFT (wine) 2 - soiled cotton K 1 OD CFT (mineral oil and carbon black) 2 - soiled cotton AS-2 CFT (mineral oil and black carbon) 2 EMPA 104 CFT cotton polyester (mineral oil and carbon black) 2 Dacron type 54 Polyester Test Fabric (mineral oil and carbon black) 2 Standard white fabrics - Cotton CN 1 white, unstained, CFT 5 - Polyester cotton PCN 1, white, unsullied, CFT 5

that is, for each test, a total of 20 pieces of tissue.

Products - 'LABS', Technical Sodium Dodecylbenzenesulfonate (ALDRICH) is the product

witness taken for reference.

- PROLABO Rectapur 99% NaHCO3 sodium bicarbonate. Used to stabilize the

pH of the cleaning baths at a constant value of 8.6.

PROCEDURE

Detergency test The tergotometer is a device made up of 4 stainless steel 2-liter pots on which are fitted stirrers that are set at 50 cycles per minute (100 back and forth). The

pots are placed in a tank of water regulated at 40 C.

In each pot we put 1 liter of permuted water containing: - 1 gram of surfactant

- 1 gram of baking soda.

When the water is at temperature, the pots are introduced into the thermostatically controlled bath.

simultaneously triggering agitation and a stopwatch.

At the end of washing (30 minutes) the baths are recovered (250 cc) for pH control.

The fabrics are rinsed three times in tap water, then hand-wrung and dried flat

individually between two sheets of absorbent white paper.

The tissues are again put between two sheets of clean absorbent paper, and

ironed in the icebox at a temperature of around 110 C.

Color measurement The measurements are carried out with the "LUCI 100 'colorimeter before and after washing according to the' L ',' a ', b' system (Scale from black to white, from green to red, and from blue to yellow) for measure the detergent power of the surfactants tested (increase in the

whiteness of soiled pieces of fabric).

Calculation of the detergency The DE (detergency) value is calculated for each type of fabric by making the geometric sum of the color differences DL, Da and Db before and after washing on soiled fabrics: Either DE detergency = (DL2 + Da2 + Qb2) 1/2

EMULSIFYING POWER

The test described below makes it possible to determine whether or not a product has good emulsifying properties with respect to a given lipophilic phase.

PROCEDURE

The emulsifying power is determined using a 100 ml graduated cylinder with ground-glass stopper. The test tube is filled with 90 ml of distilled water. 10 ml of the oil + surfactant mixture are added with a pipette. 20 successive turns are carried out while holding the test piece by its stoppered end. The behavior of

mixing is observed after 1 minute, 5 minutes, 15 minutes and 1 hour.

The amount of emulsifier product to be tested used is approximately 1% relative to the

total mixture.

Under these severe test conditions (no optimization of the concentration of the product to be tested, little energy supplied to the system), a good emulsifier gives a milky dispersion that is stable for at least 5 minutes. The creaming phenomenon is slow and no significant coalescence or lightening is observed over the entire height of the specimen.

for at least 24 hours.

Example 1

148 g of glycidol are introduced into a solution of 286 g of N-lauroyl N '- (2-hydroxyethyl) ethylene diamine in g of toluene, heated to 110 ° C., in the space of 2 hours.

* The solution obtained is heated at 110 C for 4 hours.

After evaporation of the solvent under reduced pressure (2700Pa), a viscous liquid is obtained consisting of N-laurylamidoethyl N- (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamine containing - <0.1% by weight of polyglycerols - < 0.05% by weight of laurylamidoamine (measurements by high performance liquid chromatography, using an evaporative light scattering detector) and having a cloud point> 90 C (measurement at

1% in distilled water).

Its ohysiaues properties are the following critical micellar concentration: 0.1g / I 35. surface tension: 31 mN / m wetting power: 2, 9g / l (Standard NFT 73-406) foaming power at 1 g / I and at pH 7 = 300ml (Standard NFT 73-404, in accordance with Standard ISO 696) dispersing power measured according to the procedure described above (dispersion of TiO2) without addition of polyglycerolated amidoamine (water at 30 HT), the suspensivity is 2.3% with 3% polyglycerolated amidoamine (example 1) 90.5% 5.with 5% polyglycerolated amidoamine (example 1) 94.7% (the product of example 1 is therefore a good dispersant) detergency power measured according to the detergency test described above (simulated washing using a tergotometer): the cumulative detergency, measured on the different types of fabrics, leads to the following results, taking the LABS for reference with a detergency "DE 'equal to 100" DE'

LABS 100

NaHCO3 39.9 glycerolated amidoamine (example 1) 106 15. glycerolated amidoamine + 30% free polyglycerol 101 (the detergent power of the product of example 1 is therefore at least equal to that of LABS, the presence of polyglycerol does not affect little detergent power of this product)

Example 2

At 286g of N-lauroyl N '- (2-hydroxyethyl) ethylene diamine, heated to 110 C, we

introduced 89g of glycidol, over 2 hours.

The mixture obtained is heated at 110 ° C. for 3 hours.

A viscous liquid is obtained consisting of N-laurylamidoethyl N (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamine containing - <1% by weight of polyglycerols - <0.5% by weight of laurylamidoamine

and exhibiting a cloud point> 90 ° C. (measured at 1% in distilled water).

Its emulsifying power measured according to the procedure described above, using xylene; the results are as follows: xylene time 1 minute stable minutes stable minutes stable 1 hour 2ml creaming By way of comparison, by replacing, in xylene (HLB required of 14), the product of example 2 by the same quantity of nonylphenol with 10 ethylene oxides of HLB similar to that of the product of Example 2 (HLB of the order of 14), it is observed that under the same operating conditions, a stable, milky emulsion is obtained.

minutes; after 1 hour, 4ml of creaming is observed.

Example 3

To 286g of N-lauroyl N '- (2-hydroxyethyl) ethylene diamine, heated to 130 ° C., one adds simultaneously in the space of 2 hours, 185 g of epichlorohydrin on the one hand and 160

g of a 50% by weight aqueous solution of NaOH on the other hand, while removing the water.

The mixture obtained is taken up in 500 g of isopropanol.

After filtration and evaporation of the solvent, a viscous liquid is obtained consisting of N-

laurylamidoethyl N- (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamine containing - <2% by weight of polyglycerols - <0.5% by weight of laurylamidoamine - <2% by weight of sodium chloride

and exhibiting a cloud point> 90 ° C. (measured at 1% in distilled water).

Example 4

To 286 g of N-lauroyl N '- (2-hydroxyethyl) ethylene diamine, heated to 130 ° C., is added simultaneously over the space of 2 hours, 369 g of 1,2-chlorohydrin of glycerol (prepared from glycerol and of epichlorohydrin) on the one hand and 160 g of a solution

50% by weight aqueous NaOH on the other hand, while removing water.

The mixture obtained is taken up in 500 g of isopropanol.

After filtration and evaporation of the solvent, a viscous liquid is obtained consisting of N-

laurylamidoethyl N- (trihydroxy-2,6,7 oxa-4 heptyl) ethanolamine containing - <5% by weight of polyglycerols - <0.5% by weight of laurylamidoamine - <1% by weight of sodium chloride

and exhibiting a cloud point> 90 ° C. (measured at 1% in distilled water).

Example 5

To 286g of N-alkyl C1 6-C18 N '- (2-hydroxyethyl) ethylene diamine, heated to C, is added simultaneously over 2 hours, 369 g of 1,2-chlorohydrin of glycerol (prepared from of glycerol and epichlorohydrin) on the one hand and 160 g of

50% by weight aqueous solution of NaOH on the other hand, while removing water.

The mixture obtained is taken up in 500 g of isopropanol.

After filtration and evaporation of the solvent, a viscous liquid is obtained consisting of N-

cocoylamidoethyl N- (2,6,7-trihydroxy-4-oxa-heptyl) ethanolamine containing - <5% by weight of polyglycerols - <0.5% by weight of cocoylamidoamine - <1% by weight of sodium chloride

and exhibiting a cloud point> 90 ° C. (measured at 1% in distilled water).

Example 6

Simplified formulation of a C12-C14 sodium ether sulphate shamoeing containing 2 30% oxyethylenated units With polyglycerolated lauramidoamine of Example 1 3% 100% complementary water The formulation is obtained by simply mixing the constituents in a beaker using of a pale frame. The pH is brought to 6 by adding hydrochloric acid. The formulation remains clear although the polyglycerolated lauramidoamine is

cationic at this pH.

The foaming power is 0.3% (Standard NFT 73-404); the volume of foam is

300ml; the foam remains stable for more than 5 minutes.

The adjustment of the viscosity of this formulation is carried out by adding NaCl.

The variation in the viscosity of the formulation depending on the rate of added NaCl is as follows: NaCl (%) viscosity (mPa.s) *

0 10

1,500

1.1 1000

1.5 4000

* dynamic viscosity measured at 25 C, using a Brookfield viscometer, according to

AFNOR NFT 76 102 standard.

Example 7

Formulation of a pearlescent shampoo At C12-C1 4 Na ether sulfate containing 2 oxyethylenated units 30% polyglycerolated lauramidoamide of example 1 4% 30. glycol distearate 1% With monoisopropanolamine cocamide 1% preservative GERMADEN ll 0, 5% Perfume 0.1% water complement to 100% 35. citric acid to reach pH 6 NaCl to reach a viscosity of 2000 mPa.s The C1 2- C1 4 Na ether sulfate and the polyglycerolated lauramidoamide are mixed with stirring in the water; after heating to 65 ° C., the glycol distearate and the monoisopropanolamine cocamide are added with stirring; when all the ingredients are

properly dispersed, the preparation is cooled to 25 ° C. with stirring.

The preservative, the perfume are added, then the pH and the viscosity are adjusted.

Example 8

3% silicone oil emulsion of high viscosity SILBIONE 71834, marketed by RHONE-POULENC, and 10% are added with stirring to the shampoo of Example 6.

by weight of a 2% by weight solution of xanthan gum.

A hair conditioner shampoo is thus obtained.

Example 9

Formulation for toothpaste Silicas: TIXOSIL 73 (abrasive silica) 11.0 g TIXOSIL 43 (thickening silica) 10.0 g Titanium dioxide (opacifier) 1.0 g Glycerol or sorbitol (humectant) 18.0 g Product of the example 1 (foaming and cleaning agent) 1.5 g RHODICARE xanthan gum (thickener) 0.8 g Sodium monofluorophosphate (anti-caries agent) 0.7 g Sodium benzoate: 0.2 g Sodium saccharin 0.2 g Perfume Complementary water to 100 g

Example 10

Use of the product of example 3 in a compact detergent formulation for linear sodium alkylbenzene sulfonate: 3% Product of example 3: 8% NABION 15 (carbonate silicate cogranule marketed by RHONE-POULENC) 40% Perborate tetrahydrate 16% Sodium carboxyMethylcellulose 0.6% Enzymes (Savinase / alkalase) 0.6% Mixed optical brighteners 0.14% TetraAcetylEthyleneDiamine (perborate activator) 4.3% Sodium salt of hydroxyethylene 1-1 diphosphonate 1.6% SOKALAN CP5 (acrylic / maleic copolymer marketed by BASF) 5% light sodium carbonate absorbent 6% Antifoam 8% solid silicone 2.5% silicone Perfume 0.12% Sodium sulphate to make up to 100%

Example 1 1

Use of the product of exemole 2 in a detergent formulation for the laundry Linear sodium alkylbenzene sulfonate 7.5% Product of example 2 4.5% Zeolite TEL 24% Disilicate ALNA 2.5% Perborate tetrahydrate 14% Sadistic carboxyMethylcellulose 0.6% Enzymes (Esperase) 0.3% Optical brighteners in mixture 0.11% TetraAcetylEthyleneDiamine (perborate activator) 2% Sodium salt of hydroxyethylene 1-1 diphosphonate 1.6% SOKALAN CP5 (acrylic / maleic copolymer sold by BASF) 4% Sodium carbonate 14% Defoamer 1.5% Repell-O-Tex '(anti-fouling agent marketed by RHONE-POULENC) 0-1% Perfume 0.1% Sodium sulphate to make up to 100%

Example 12

Formulation of washing-up liquid by hand Product of example 1 10% Sodium Lauryl Ethersulfate RHODAPEX ESY (RHONE-POULENC): 5% NERVANAID B30 '(EDTA sequestrant from RHONE-POULENC) 1% GLOKILL 77 (bactericide from RHONE-POULENC) 0.1% Water 83.9% The components of the formulation are mixed in cold. The pH of the solution is adjusted to 8 by adding citric acid and the viscosity of the formulation is adjusted to 1500 mPa.s

by adding NaCl.

Example 13

The product of Example 1 is used to lower the critical micellar concentration and

the surface tension of solutions of anionic surfactants.

The critical miceilar concentration of sodium dodecyl sulfate (ALDRICH) is

2.3 g / l and the surface tension above this concentration is 34 mN / m.

The critical micellar concentration of the product of Example 1 is 0.10 g / l and the voltage

surface area above this concentration is 31 mN / m.

The critical micellar concentration of the 50/50 mixture by weight of sodium dodecylsulfate and of the product of Example 1 is 0.03 g / l and the surface tension above

of this concentration is 27 mN / m.

Example 14

The compounds which are the subject of this invention are mildly irritating surfactants.

to non-irritants.

For example, the level of ocular irritation of the product of Example 1 was evaluated by in-vitro test in comparison with surfactants known to be non-irritating or mildly irritating such as cocoamphodiacetates (for example MIRANOL C2M, marketed by RHONE- POULENC) (irritation data published in Journal of

the American College of Toxicology, Volume 9, Number 2, 1990, p1 21 et seq).

The in vitro test used is the erythrocyte hemolysis test.

The procedure used is that described by R.W. LEWIS in the article A comparison of two cytotoxicity tests for predicting the ocular irritancy of surfactants', published in Toxicology in Vitro, Vol. 7, No.2, pp 155-158 (1993), Pergamon Press Ltd. The hemolyzing surfactant concentrations for 50% of the erythrocyte population (denoted TC50 in the publication referenced above) are: 350 mg / I for MIRANOL C2M)

485 mg / l for the product of Example 1.

This concentration measured for the product of Example 1 shows that a higher concentration of the product of Example 1 is needed with respect to that of MIRANOL C2M to hemolyze 50% of the red blood cells; the product of example 1 is therefore

less irritating than MIRANOL C2M, itself slightly irritating to the eye.

The classification established by the publication referenced above shows that the product of

Example 1 belongs to the category of minimally irritant products.

The product of Example 1 can be used to reduce the irritation of solutions of anionic surfactants generally used in shampoo formulations,

bubble baths or washing up liquid in hand.

For example, the TC50 concentration for sodium laurylethersulfate (2 moles

ethylene oxide) is 295 mg / l.

In a 25% mixture of this surfactant with 75% of the product of Example 1, the

TC50 concentration increases to 514 mg / I.

Example 15

Formulation of toilet bar (bar of soap) The use of the product of Example 1 improves foaming in hard water, loaded with calcium ions and reduces the aggression on the skin which would be caused by the soap alone (acid salt bold). Soaps: C16-C18 sodium alkylate 71% Sodium cocoate 15.5% Water 7.5% Product of example 1 5% Opacifier Titanium dioxide 0.3% Colorant, perfume, preservative 100% supplement Soaps and the opacifier are mixed to give a mixture A. The product of Example 1 is added to the water with stirring at 45 C. This solution is added slowly with stirring to the mixture A. Additives such as colorants, perfume and the preservative are then added. When the mixture is homogeneous, it is ground and calendered until perfect homogeneity; the mixture is then extruded and formed into a bar.

Example 16

Syndet bar formulation (synthetic detergent bar or synthetic soap bar) Sodium alkyl isethionate GEROPON AS-200 75% Product of example 3 10% Water 5% Sodium isethionate 2% Glycerol 1% Titanium dioxide 0.3% Stearic acid 5% Color, fragrance, preservative 100% supplement

Example 17

Formulation of a conditioning balm for the hair Product of example 5 4% Cetyl alcohol NF 1.5% Polyethylene glycol stearate ALKAMULS EGMS 1% JAGUAR HP60 COS 0.8% Complement water at 100% JAGUAR HP 60 COS is dispersed in water with stirring. The solution is heated to 70 ° C. The product of Example 5, cetyl alcohol, ALKAMULS EGMS is added thereto. When the dispersion is homogeneous, the pH of the formulation is adjusted to 4 per opening of citric acid. The system is cooled to 40 ° C. with stirring. Perfumes, pigments, dyes and a preservative can then be added.

Claims (12)

1) Polyglycerolated amidoamines of formula OH R1-CO-NR2 - [(CH2) n-NR3] m- (CH2- CH-CH2-O) pH formula in which - R1 represents a C2-C22, preferably C8-C22, alkyl or alkenyl hydrocarbon group linear or branched, cycloalkyl or alkylaryl - R2 and R3 are the same or different and represent a hydrogen atom, a C1-C4 alkyl group, a 2-hydroxyethyl, 2-hydroxypropyl or polyhydroxyoxaalkyl group with a number of hydroxyoxaalkyl units from 1 to 10, preferably from 2 to 5 - n is an integer which may range from 2 to 6, preferably equal to 2 or 3 - m is an integer which may range from 1 to 5, preferably equal to 1 or 2 - j is an integer or decimal greater than 1, preferably of the order of 1.1 to 50. 2) Polyglycerolated amidoamines of formula CH2-CH2-OH I R1-CO-NH-CH2-CH2- N OH (CH2 CH-CH2-O) p-H formula in which R1 represents a linear or branched alkyl or alkenyl group in C2-C22, preferably in C8-C22 and. is an integer or decimal greater than 1, preferably of the order of 1.1 to 50. 3) polyglycerolated amidoamines according to claim 1) or 2), characterized in that 1 is an integer or decimal of the order of 2 to 5. 4) Process for the preparation of polyglycerolated amidoamines forming the subject of claim 1), by polycondensation of an activated derivative of glycerol on an amidoamine of formula RI- CONR2 - [(CH2) n-NR3] m-OH formula in which - R1 represents a C2-C22, preferably C8-C22, alkyl or alkenyl linear or branched, cycloalkyl or alkylaryl group - R2 and R3 are similar or different and represent a hydrogen atom, a C1- alkyl group C4, a 2-hydroxyethyl, 2-hydroxypropyl or polyhydroxyoxaalkyl group with a number of hydroxyoxaalkyl units from 1 to 10, preferably from 2 to 5 - n is an integer ranging from 2 to 6, preferably equal to 2 or 3 - m is an integer which may range from 1 to 5, preferably equal to 1 or 2 - a is an integer or decimal greater than 1, preferably of the order of 1.1 to 50) Method according to claim 4), characterized in that 1 is an integer or decimal of the order of 2 to 5. 6) Process for the preparation of polyglycerolated amidoamines forming the subject of claim 2), according to the process of claim 4) or 5), characterized in that the amidoamine used has the formula R1 -CO-NH-CH2-CH2-NH-CH2-CH2-OH formula in which R1 represents a linear or branched C2-C22, preferably C8-C22, alkyl or alkenyl group and p is an integer or decimal greater than 1, preferably of the order of 1.1 to 50. 7) Method according to any one of claims 4) to 6), characterized in that that the polycondensation operation is carried out at a temperature of the order of 70 to C, preferably of the order of 110 to 150 C, by continuous addition of the activated derivative of glycerol in a proportion of the order of 1 , 1 to 50 molar equivalents, preferably of the order of 2 to 5 molar equivalents, of activated derivative of glycerol per compared to the amidoamine used. 8) A method according to any one of claims 4) to 7), characterized in that that the activated derivative of glycerol is epichlorohydrin or glycidol. 9) Polyglycerolated amidoamines according to any one of claims 1) to 3), characterized in that they are associated with at least one anionic surfactant. ) Use of polyglycerolated amidoamines which are the subject of any of claims 1) to 3) and 9) as surfactants or surfactant systems. 11) Use according to claim 10) in cosmetic compositions. 12) Use according to claim 10) in detergent compositions. 13) Use according to claim 10) in agrochemical formulations. 14) Use of polyglycerolated amidoamines which are the subject of any of claims 1) to 3), to reduce the irritation of solutions of surfactants anionics in the fields of cosmetics and detergents.