WO1996020994A1

WO1996020994A1 - Detergent compositions based on glycerol or polyglycerol amides, novel polyglycerol amides, and use thereof in detergent formulations

Info

Publication number: WO1996020994A1
Application number: PCT/FR1995/001757
Authority: WO
Inventors: Paul-Joël DERIAN; Véronique Guillou; Jean-Marc Ricca
Original assignee: Rhone-Poulenc Chimie
Priority date: 1994-12-30
Filing date: 1995-12-29
Publication date: 1996-07-11
Also published as: FR2728910B1; AU4452996A; FR2728910A1

Abstract

A detergent composition based on a glycerol or polyglycerol amide of formula (I), wherein R is a straight or branched C4-22 alkenyl or alkyl group; R' is a unit (a); and n is an integer or decimal of at least 1. Novel polyglycerol amides of formula (I), where n is greater than 1, are also disclosed. Furthermore, the use of the glycerol or polyglycerol amides of formula (I), particularly in liquid formulations for washing dishes by hand, is disclosed.

Description

DETERGENT COMPOSITIONS BASED ON GLYCEROLIC AMIDES OR

POLYGLYCEROLES, NOVEL POLYGLYCEROLES AMIDES AND USE THEREOF

IN DETERGENT FORMULATIONS

The subject of the present invention is a detergent composition, in particular a> detergent composition capable of being in contact with biological systems, based on glycerolated or polyglycerolated amides, as well as as new products of the polyglycerolated amides derived from the N, N diglycerolamine.

According to the invention it is a detergent composition based on at least one glycerolated or polyglycerolated amide of formula (I)

R 'OH

, -Jt i

R-CO - N- (CH ₂ - CH-CH -O) _n H (I)

formula in which. R represents a linear or branched C4-C22 alkyl or alkenyl group. preferably C ₈ -C22

OH j. R 'represents a motif (CH2 - CH-CH2-0) _n H

. n represents an integer or decimal number equal to or greater than 1, preferably of the order of 1 to 50 and very particularly of 2 to 5.

The polyglycerolated amides can be obtained by condensation or polycondensation of an activated derivative of glycerol, such as an epoxidized derivative of glycerol

(gl cidol, epichlorohydrin), on a glycerolamide of formula (II)

R 'OH

R-CO - r! J-CH2 - 6H-CH ₂ -OH (II)

formula in which R and R 'have the definition given above, in a proportion of the order of at least 1 molar equivalent, preferably of the order of 1 to 50 molar equivalents, and very particularly of the order from 2 to 5 molar equivalents of activated derivative of glycerol relative to the glycerolamide of formula (II).

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 activated derivative of glycerol. If desired, this operation can be carried out in the presence of a third solvent which is inert with respect to the activated derivative of glycerol; as an example of a solvent, mention may be made of saturated aliphatic hydrocarbons (heptane, octane, etc.), aromatic hydrocarbons (toluene, cυmène ...), ketones (octanone-2 ...), secondary or tertiary alcohols (isopropanol, tertiobutanol ...).

This reaction can be carried out in the absence of a catalyst, or if desired in the presence of an acid catalyst (preferably a Lewis acid of the boron trifluoride type, tin tetrachloride, antimony pentachloride, etc.) or d '' a basic catalyst (alkali metal hydroxide such as NaOH, KOH, alkali metal alcoholate such as sodium methylate, potassium tert-butoxide, alkali metal amides such as sodium amide ...), and in an amount corresponding to approximately 0.05 to 10%, preferably about 0.1 to 1% by weight relative to the reaction mass. When the activated derivative of glycerol used is epichlohydrin, it is necessary to neutralize the halogen formed continuously with the aid of a base such as alkaline or alkaline 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.

The glycerolamide of formula (II) can be prepared by condensation of an activated derivative of glycerol, such as an epoxidized derivative of glycerol (glycidol, epichlorohydrin), on an amine of formula R'-NH, formula in which R 'has the same definition as above, according to the methods known to those skilled in the art, then amidation using a fatty acid derivative of the RC (O) OCH3 type where R has the definition given above above.

The glycerolated or polyglycerolated amides of formula (I) are easily biodegradable surfactants, very well tolerated by biological systems, and in particular having good foaming, dispersing and detergent power.

They can represent from 0.1 to 40% of the weight of said detergent compositions which are the subject of the invention.

The term “detergent composition” is understood here to mean any formulation which can be applied in the field of household cleaning (washing powder or household formulations in powder or liquid form, intended for use in machines, washing machines or dishwashers for example, by hand or other means) or industrial (cleaning of metals for example) or in that of personal hygiene (cosmetic).

Among the glycerolated or polyglycerolated amides favorably present in said detergent compositions, mention may be made of

. N-lauroyl N, N-di (2,3-dihydroxy-propyl) amine, prepared from N, N-di (2,3-dihydroxy-propyl) amine,. N-lauroyl N, N-di (trihydroxy-2,6,7 oxa-4 heptyl) amine, prepared from lauroyldiglycerolamine,

. N-palmitoyl N, N-di (trihydroxy-2,6,7 oxa-4 heptyl) amino, prepared from palmitoyldiglycerolamine . N-stearoyl N, N-di (trihydroxy-2,6,7 oxa-4 heptyl) amine, prepared from stearoyldiglycerolamine

. the N-oleoyl

oxa-4 heptyl) amino, prepared from oleoyldiglycerolamine. N-behenoyl N, N-di (trihydroxy-2,6,7 oxa-4 heptyl) amino, prepared from behenoyldiglycerolamine

In the detergent compositions for household or industrial use which are the subject of the invention, there may be present, alongside said glycerolated or polyglycerolated amides, other additives of the type of those described below. - SURFACTANTS AGENTS other, in amounts corresponding to approximately 3-40% by weight relative to the detergent composition, surfactants such as anionic surfactants

. the alkyl esters sulfonates of formula R-CH (Sθ3M) -COOR ', where R represents a C8-rj alkyl radical. preferably at C-jo-C-iβ- ^ ' ^a C- | -C6 alkyl radical, preferably at C1-C3 and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl- , dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...). Mention may very particularly be made of methyl ester sulfonates whose radicals R is C14-C15; . the alkyl sulphates of formula ROSO3M, where R represents a C10-C24 alkyl or hydroxyalkyl radical, preferably in CJ -C ₂ Q and very particularly in C- | ₂ - C18. representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and or propoxylenated (OP) derivatives, having on average from 0.5 to 6 units, preferably from 0.5 to 3 OE and / or OP patterns; . alkyiamide sulfates of formula RCONHROSO3M where R represents an alkyl radical in C ₂ -C ₂ , preferably in C6-C o. R ′ a C ₂ -C ₃ alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and or propoxylenated (OP) derivatives, having an average of 0, 5 to 60 OE and / or OP patterns; . salts of C8-C24 saturated or unsaturated fatty acids. preferably in C14-C20. alkylbenzenesulfonates Cg-C ₂ Q, primary or secondary C ₂ alkylsurfonates in Cβ- 2. alkylgiycérol sulphonates, sulphonated polycarboxylic acids described in GB-A-1,082,179, paraffin sulphonates, N-acyl N- alkyltaurates, alkylphosphates, alkylisethionates, alkylsuccinamates alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, sulfates of alkyl glycosides, polyethoxycarboxylates the cation being an alkali metal (sodium, potassium, lithium), a residue substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanoiamine derivative (monoethanolamine, diethanolamine, triethanolamine ...); nonionic surfactants polyoxyoxyalkylated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is Cg-C- | 2 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 marketed by Rohm & Haas Cy. ;

. glucosamide, glucamide;

. glycerolamides derived from N-alkylamines (US-A-5,223,179 and FR-A-1, 585.966). polyoxyalkylenated Cg-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene); by way of example, mention may be made of

TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed 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 with a hydrophobic compound resulting from the condensation of propylene oxide with propyiene glycol, such as the Pluronic 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 alkyl oxides C10-C18 dimethylamines, alkoxy oxides C8-C22 ethyl dihydroxy ethylamines;

. the alkylpolyglycosides described in US-A-4565647;

. amides of fatty acids C8-C ₂ rj. ethoxylated fatty acids

. ethoxylated fatty amides

. ethoxylated amines cationic surfactants

. alkyldimethylammonium halides amphoteric surfactants and zwitterioniαues alkyldiméthylbétaines. alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, Iles condensation products of fatty acids and protein hydrolysates.

- ADJUVANTS IMPROVING THE PROPERTIES OF SURFACTANTS ("builders"), in amounts corresponding to about 5-50%, preferably about 5-

30% by weight for liquid detergent formulas, or about 10-80%, preferably 15-50% by weight for powder detergent formulas, builders such as inorganic adjuvants ("builders") the polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines. tetraborates or borate precursors. silicates, in particular those having an Si0 ₂ / Na ₂ O ratio of the order of 1.6 / 3.2 to 3.2 1 and the lamellar silicates described in US-A-4664839. alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates). cogranules of hydrated alkali metal silicates 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 zeolites A, P, X ...; zeolite A with a particle size of the order of 0.1-10 micrometers is preferred as organic builders. water-soluble polyphosphonates (1-hydroxy-1 ethane, 1-diphosphonates, methylene salts diphosphonates ...)

. water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as

. polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic tartrate acid and its salts, distrucic tartrate acid and its salts. hydroxypolycarboxyla.es ethers

. citric acid and its salts, mellitic acid, succinic acid and their salts. the salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2 hydroxyethyl) -nitrilodiacetates). C5-C20 succinic alkyl 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 glutamic acid

. polycarboxymethylated derivatives of glutamic acid or other amino acids - WHITENING AGENTS, in amounts of about 0.1-20%. preferably about 1-10% by weight, optionally combined with WHITENING ACTIVATORS, in amounts of about 0.1-60%, preferably about 0.5-40% by weight, agents and activators such as aoents whitening. perborates such as sodium perborate monohydrate or tetrahydrate . peroxygenated 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 peroxyacid carboxylic acid; among these activators, there may be mentioned, tetraacetylethylene diamine, tetraacetyl methylene diamine, 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-4-oxopθroxybutyriquθ acid, 6-nonylamino-6-oxoperoxycaproic acid, acid diperoxydodecanedioic acid, nonylamide peroxysuccinic acid, decyldiperoxysuccinic acid.

These agents can be combined with at least one of the anti-fouling or anti-redeposition agents 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-FOULING AGENTS, in amounts of the order of 0.01-10%, preferably about 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, ethylcellulose, hydroxypropyl methylcelluiose, hydroxybutyl methylcelluiose. polyvinyl esters grafted on polyalkylene trunks such as polyvinyl acetates grafted on polyoxyethylene trunks (EP-A-219 048). polyvinyl alcohols. polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, 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-4702,857. US-A-4770666); . sulfonated polyester oligomers obtained by suffonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1,2 propylene diol, having from 1 to 4 sulfonated groups (US-A-4968451). polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl or methyl units (US-A-4,711,730) or polyester oligomers terminated with alkylpolyethoxy groups (US-A-4,702,857) or anionic groups sutfopolyethoxy (US-A-4,721,580), sulfoaroyl (US-A-4877896)

. polyesters-polyurethanes obtained by reaction of a polyesters with a molecular mass of 300-4000 in number obtained from adipic acid and / or tereptalic acid and / or sulfoisophthalic acid and a diol of mass less than 300, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular mass of 600-4000 and a diisocyanate ((FR-A-2 334698)

- ANTI-REDEPOSITION AGENTS, in amounts of about 0.01-10% by weight for a powdered detergent composition, about 0.01-5% by weight for a liquid detergent composition, agents such as

. ethoxylated monoamines or polyamines, polymers of ethoxylated amines (US-A-4,597,898, EP-A-11,984). carboxymethylcellulose. the sulfonated polyester oligomers obtained by condensation of isophthalic acid, of dimethyl sulfosuccinate and of 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). polyfunctional aromatic compounds such as dihydroxydisulfobenzenes

- POLYMERIC DISPERSING AGENTS, in an amount of the order of 0.1-7% by weight, to control the hardness of calcium and magnesium, agents such as

. the 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, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), copolymers of arylic acid and maleic anhydride of mass molecular of the order of 5,000 to 75,000 (EP-A-66915). polyethylene glycols of molecular mass of the order of 1000 to 50,000 - FLUORESCENCE AGENTS (BRIGHTENERS), in an amount of about 0.05-1, 2% by weight, agents such as derivatives of stilbene, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanins, thiophenes ... ("The production and application of fluorescent brightening agents" - M. Zahradnik, published by John Wiley & Sons, New York-1982 -)

- FOAM SUPPRESSANTS, in amounts up to 5% by weight, agents such as

. C- | o * 24 monocarboxylic fatty acids or their alkali, ammonium or alkanolamine salts, fatty acid triglycerides

. aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons, such as paraffins, waxes. N-alkylaminotriazines

. monostearylphosphates, monostearyl alcohol phosphates

. polyorganosiloxane oils or resins optionally combined with silica particles

- SOFTENING AGENTS, in amounts of about 0.5-10% by weight, agents such as clays

- ENZYMES in quantities of up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, enzymes such as

. proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139,

US-A-4 101 457, US-A-4507219. US-A-4261 868 - OTHER ADDITIVES such as

. alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin)

. buffering agents

. perfumes . pigments

In the field of household detergents, the present invention relates more particularly to compositions for hand dishwashing liquids.

Said compositions contain on the order of 0.1 to 20%, preferably on the order of 0.5 to 10% of their weight of glycerolated or polyglycerolated amide of formula (I) and of the order of 0, 5 to 40%, preferably of the order of 1 to 20% of their weight of at least one anionic or nonionic surfactant.

The preferred glycerolated or polyglycerolated amides are those already mentioned above.

Mention may in particular be made, among the anionic surfactants which may be present, of alkyl sulphates, alkyl ether sulphates, alkyl sulphonates, alkyl benzenes sulphonates, soaps, alkyl ethercarboxylates, N-acyl sarcosinates, alkylisethionates, N-acyl N-alkyltaurates, alkylphosphates, alkylsulfosuccinates, alkylsulfosuccinamates, sulfonated fatty acid derivatives ... Among the nonionic surfactants which may be present, there may be mentioned in particular amine oxides, alkylglucamides, alkylpolyglycosides, oxyalkylene derivatives of fatty alcohols such as PLANTAREN® sold by HENKEL ...

Besides glycerolated or polyglycerolated amides and anionic surfactants may be present in the compositions for hand dishwashing liquids, other additives such as amphoteric and zwitterionic surfactants such as alkyldimethylbetaines, alkylamidopropylbétaines, alkylsultaines, condensation products of fatty acids on proteins or protein hydrolysates, amphoteric derivatives of alkylpolyamines such as AMPHIONIC XL® marketed by RHONE-POULENC, AMPHOLAC 7T / X® and AMPHOLAC 7C / X® marketed by BEROL NOBEL

. bactericidal or disinfectant agents such as triclosan. synthetic cationic polymers such as MIRAPOL A550®, MIRAPOL A15® marketed by RHONE-POULENC, MERQUAT 550® marketed by CALGON ...

. polymers used to control the viscosity of the mixture and / or the stability of the foams formed in use, such as cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar ...)

. hydrotropic agents, such as C2-C8 short alcohols. in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol, .... skin moisturizers or humectants such as glycerol, urea or skin protective agents, such as proteins or protein hydrolysates, cationic polymers such as cationic guar derivatives (JAGUAR C13S®, JAGUAR C162®, HICARE 1000® marketed by RHONE-POULENC,. Dyes, perfumes, preservatives ...

The term cosmetic composition or formulation means all cosmetic products or preparations such as those described in Annex I ("illustrative list by category of cosmetic products") of European Directive No. 76/768 / EEC of July 27, 1976 known as "cosmetic directive".

The glycerolated or polyglycerolated amides of formula (I) can be used more particularly in formulations of lotions, toilet milks, cleansing 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 of hair, shampoos for hair or the body, face or body cleaning gels, liquid soaps, foaming bath compositions, formulations used for cleaning teeth or of the oral cavity such as mouthwashes or toothpaste. Said glycerolated or polyglycerolated amides can also be used alone or in combination in the formulation of soaps or toilet bars.

Cosmetic compositions generally contain surfactants which serve to disperse, emulsify, dissolve and stabilize various compounds used for their emollient or humectant properties. Surfactants are used in these compositions at concentrations varying from 0.05 to 10% by weight of the preparation. Among the humectants, there may be mentioned glycerol, sorbitol, urea, collagen, gelatin, aloe vera, hyaluronic acid, etc.

The emollients are generally chosen from alkylmonoglycerides, alkyldiglycerides and triglycerides such as oils extracted from plants and plants (palm, copra, cottonseed, soybean, sunflower, olive and grape seed oils. , sesame, peanut, castor oil ...) or oils of animal origin (tallow, fish oils, ...), derivatives of these oils such as hydrogenated oils, lanolin derivatives, mineral oils or paraffinic oils, perhydrosqualane, squalene, diols like 1-2-propanediol, 1 -3-butanediol, cetyl alcohol, stearyl alcohol, oleic alcohol, polyethylene glycols or polypropylene glycols, fatty esters such as isopropyl palmitate, ethyl-2-hexyl cocoate, myristyl myristate, esters of lactic acid, stearic acid, behennic acid, isostearic acid, silicone oils grouping cyclic polydimethylsiloxanes, pol α-ω hydroxylated ydimethylsiloxanes, α-ω trimethylsilylated polydimethylsiloxanes, polyorganosiloxanes such as polyalkylmethylsiloxanes, polymethylphenylsiloxanes, polydiphenylsiloxanes, amino derivatives of silicones, commercial wax SILIONs, silicone oils, etc. RHONE-POULENC or DC 190® sold by DOW CORNING) or mixed silicone derivatives such as polyalkylmethylsiloxane-silicone copolyether copolymers. To these compounds, it is possible to add 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 one micrometer, sometimes of some 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-hydroxybenzolque acid, sodium benzoate, GERMABEN® or any chemical agent preventing bacterial proliferation or molds and traditionally used in cosmetic compositions are generally introduced into these compositions in an amount of 0.01 to 3% by weight.

As an alternative to these chemical agents, it is sometimes possible to use agents modifying the activity of water and greatly increasing 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 strongly absorbing UV radiation like the compounds authorized in the European directive N ° 76/768 / EEC, its annexes and subsequent amendments to this directive, either titanium dioxide or cerium oxides in the form of powder or colloidal particles.

Perfumes, dyes or pigments can also be added. May also be present viscous or gelling polymers (such as crosslinked polyacrylates CARBOPOL® marketed by GOODRICH-, cellulose derivatives such as hydroxypropylcellulose, carboxymethylcellulose, guars and their derivatives, carob, tara gum 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 of the composition), from 0.1 to 5% by weight of said glycerolated or polyglycerolated amides of formula (I ), taken alone or in mixture with the usual surfactants such as anionic, nonionic or zwitterionic surfactants such as alkylbetaines or alkylamidopropylbétaines or amphoterics or combinations of these compounds. These surfactants 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 alkyl sarcosinates which protect the teeth by inhibiting the enzymatic activity of the 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-spinning nature of the paste is controlled by thickening agents such as certain silica used for this purpose (TIXOSIL 43® 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 from 0.1 to 15% by weight of the composition of a toothpaste.

We also generally find associated with these various constituents therapeutic agents such as certain fluorine or potassium salts, flavors, sweetening agents and water.

The glycerolated or polyglycerolated amides of formula (I) can also be present in formulations of toilet rolls called soaps or soaps. Conventional toilet bar compositions generally comprise fatty acid salts used in combination with glycerolated or polyglycerolated amides of formula (I) and optionally surfactants other than the fatty acid salts 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, C8-C2 sodium alkyl isethionates or C8-C22 sodium alkylsulfates. we can also add different constituents useful to reduce irritation or aggression of the skin such as alkali metal salts or isethionates or to promote hydration of the skin like 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 vegetable proteins (hydrolysates of wheat proteins for example), natural hydrocolloids (guar, carob, tara gum ...) or from fermentation processes such as xanthan gum e and derivatives of these polycarbohydrates such as modified celluloses (for example Hydroxyethylcellulose, carboxymethylcellulose, cationic celluloses such as POLYMER JR® sold by the company UNION CARBIDE), guar or carob derivatives such as their cationic derivatives (JAGUAR C13S®, JAGUAR C162® sold by RHONE-POULENC) or non-ionic derivatives (for example hydroxypropylguar), anionic derivatives (carboxymethylguar) or mixed nonionic / anionic derivatives such as carboxy-hydroxypropyl-guar or nonionic / cationic. It is also possible to add, alternatively or in combination, synthetic polymers such as polyacrylates or synthetic cationic polymers, known under the generic name CTFA of "Polyquaternium", for example the polymers MIRAPOL A15® or MIRAPOL 550® from the company RHONE-POULENC. One can also advantageously add to these compositions 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. About in the cosmetic industry (mineral oils, fatty acid esters, triglycerides, silicones).

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 disinfection of the skin.

In a toilet roll whose formulation consists mainly of soaps of monocarboxylic fatty acids (sodium, potassium, mono-, di- or tri-ethanolammonium salts); the fatty acid soap contents are generally more than 25% by weight of the formulation, generally 30 to 95% by weight.

In a toilet roll whose formulation is based on other main constituents than fatty acid soaps, the formulation contains from 0 to 50% by weight, preferably from 1 to 40% by weight of these acid soaps. bold. These toilet roll compositions can also contain from 0 to 95%, preferably from 0 to 60% of surfactants other than soaps, in particular Cβ-C22 alkyl or alkenyl isethionates.de as well as alkyl ether sulfates, alkyl betaines, alkylamidopropylbetaines, alkylamphoacetates, -diacetates, -propionates or - dipropionates used to reduce the irritation that can be caused by other surfactants, mainly anionic surfactants. From 1 to 15% of free fatty acids in C8-G22 can also be introduced into the compositions of soaps as superfatting agents or to modify the appearance and the creamy character of the foam during washing.

We can also find in these compositions waxes such as paraffinic waxes, natural waxes such as beeswax or ozokeritθ or silicone waxes. These waxes are advantageously used to improve the appearance, behavior, processability and storage conservation of toilet rolls.

Shampoos, shower gels and more generally detergent compositions for personal use may contain, in addition to the glycerol or polyglycerol amides of formula (I), the usual compounds present in these types of formulation.

We can cite in particular:

- anionic surfactants, such as the water-soluble salts of alkylsulphates, of alkylethersulphates, the alkylisethionates and the alkyftaurates or their salts, the alkylcarboxylates, the alkylsulphosuccinates or the alkylsuccinamates, the alkylsarcosinates, the alkyl derivatives of protein hydrolysates , acylaspartates

zwitterionic or amphoteric surfactants, such as alkylbetaines, alkylamidopropylbétaines, imidazoline derivatives such as alkyiamphoacetates, alkylamphodiacetates, alkylamphopropionates, alkylamphodipropionates, alkylsultaines or alkylamidopropylhydroxysultaines

- non-ionic surfactants agents, such as polyoxyethylene derivatives of aliphatic or arylaliphatic C8 C22 _*> ^{alkylpolysaccharides} having a hydrophobic group in C6-C30, preferably C10-C16 and a polysaccharide moiety, e.g. polyglycoside , as a hydrophilic group as well as from 1 to 3 sugar units, the alkylated derivatives of sugars, such as the aikylglucamides produced by the amidification reaction of a fatty acid on N-methylglucamine

- amides derived from fatty acids generally used for their ability to improve the foaming of the compositions or to increase the viscosity of said compositions; these amides are generally chosen

- cationic conditioners (improving combability, styling, feel and volume of the hair) such as synthetic cationic polymers of the MIRAPOL AD1®, MIRAPOL A550® or MIRAPOL A15® type marketed by RHONE-POULENC, cationic polymers natural like cationic derivatives of guar (JAGUAR C13S®, JAGUAR C162® marketed by RHONE-POULENC) or cationic derivatives of cellulose (POLYMER JR400® marketed by UNION CARBIDE).

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

- dandruff agents, such as pyridinesthiones, more particularly zinc pyridinethione, selenium-based compounds such as selenium sulfide or OCTOPYROX®. marketed by HOECHST

- anti-parasite agents (anti-lice), such as LINDANE or various pyrethrins used in this connection.

These compositions can also contain agents modifying the appearance or the viscosity of the formulations such as pearlescent compounds based on polyethylene glycol stearate or polymers improving viscosity or stability such as 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 glycerol amidoamines of the invention) can consist of (percentages by weight)

. glycerolated or polyglycerolated amide 0.1 -15%

. anionic surfactant 0-15%

. amphoteric surfactant 0-10% . 0-5% fatty acid alkanolamide

. thickening agent 0-5%

. conditioning agent 0-3%

. perfume 0-2% i. preservative 0-2%

. anti-dandruff agent 0-2%

. water 100% complement

The present invention also relates, as new industrial products, to the polyglycerolated amides of formula (D

R 'OH

R-CO - N- (CH ₂ - CH-CH ₂ -O) _n H d ')

. α represents an integer or decimal number greater than 1, preferably more than 1 to

50 and especially from 2 to 5.

OH . R "represents a unit (CH2 - CH-CH2-O) _n H (unit M).

These polyglycerolated amides can be obtained by condensation or polycondensation of an activated derivative of glycerol, such as an epoxidized derivative of glycerol

(glycidol, epichlorohydrin), on a glycerolamide of formula (II ')

R 'OH

R-CO - N-CH ₂ - CH-CH -OH (II ')

formula in which R and R 'have the definition given above, in a proportion of more than 1 molar equivalent, preferably of more than 1 to 50 molar equivalents, and very particularly of the order of 2 to 5 molar equivalents of activated derivative of glycerol relative to the glycerolamide of formula (II ').

These polyglycerolated amides can be prepared according to the procedure developed above.

The present invention also relates to the use of glycerolated or polyglycerolated amides of formula (I) or d ') as surface-active agents, in particular in household or industrial detergent formulations or in cosmetic formulations; it particularly relates to the use of glycerolated or polyglycerolated amides of formula (I) or (D in formulations entering or susceptible to come into contact with biological systems, such as in cosmetics or in hand dishwashing liquids.

In addition, these glycerolated or polyglycerolated amides of formula (I) or (D can function as viscosifying agents in association with anionic surfactants, as activator, enhancer or stabilizer of foaming properties of surfactant solutions.

Furthermore, when the total carbon number of the radicals R and R 'of formulas (I) and (D exceeds 14, preferably is 18, these products can be used as pearlescent agents, opacifiers or periescent agents in liquid detergent compositions.

The following examples are given as an indication.

Example 1

Preparation of the NN-di (dihvdroxv-2.3 propyl) amino or diglvcerolamine To a solution of 3-amino propanediol-1, 2 (149.2 g, 1.63 mole) in methanol (320 ml) is added at room temperature glycidol ( 60.5 g, 0.82 mole). The residual mixture is stirred for 18 hours at room temperature and the solvent is evaporated under reduced pressure.

The residual oil is purified by distillation under reduced pressure. The volatile fraction (125 ° C / 667Pa) mainly containing the residual glycerolamine is recovered.

N, N-di (2,3-dihydroxy propyl) amine is obtained in the form of a very viscous oil.

Preparation of N-lauroyl N.N-di (dihvdroxv-2.3 propyl) amino or laurovldiglvcéroamine

A mixture of methyl laurate (214 g, 1 mole) and diglverceramine (165 g, 1 mole) in methanol (350 ml) is heated to 50 ° C, and sodium methylate (1.35 g, 2, 5

% molar) is added.

The residual solution is heated for 24 hours at 70-75 ° C. After distillation of the theoretical amount of methanol, the analysis by chromatography in aqueous phase shows a complete conversion of the methyl laurate. The solvent is then evaporated under reduced pressure and the lauroyldiglycerolamine is obtained in the form of a pale yellow oil.

Example 2

Preparation of the N laurovl NN-di (trihvdroxv-2.6.7 oxa-4 heptvl) amino The N lauroyl N, N- (2,3-dihydroxypropyl) amine obtained in Example 1 is heated to 145 ° C., then added in 3 hours, 148 g (or 2 moles) of glycidol. The medium is maintained at this temperature for another 2 hours. A viscous, yellow-colored oil is obtained, consisting of N lauroyl NN- (trihydroxy-2,6,7 oxa-4 heptyl) amino and containing less than 5% by weight of residual polyglycerols (measurement by high performance chromatography, with using an evaporative light scattering detector).

Example 3

Dishwashing liquid by hand

The foaming and wetting power of the product of Example 2 in a formulation for washing dishes by hand is tested as follows.

We are preparing a system consisting of

- 86.5 parts by weight of sodium lauryl ether sulfate containing 2 oxyethylene units

- And 13.5 parts by weight of oily product of Example 2, the foaming and wetting properties of which are compared with those of sodium lauryl ether sulfate containing 2 oxyethylene units, alone.

The foaming power is measured according to the "Ross Miles modified" test according to the AFNOR NFT 73404 standard. This is evaluated by "free fall" at 50 ° C., using a solution of 0.05% of material. active in synthetic hard water containing 0.5g / l of CaCl2, 2 H2O (340ppm).

The results are as follows:

Na LES * Na LES + product of Example 2 volume of foam (ml) at 1 min 400 440 at 3 min 390 430 at 5 min 370 420

* Na lauryl ether sulfate

The wetting power is measured according to AFNOR NFT 73406 standard. This is evaluated by wetting a cotton washer at 23 ° C., using a 0.05% solution of active material in hard water. synthetic containing 0.5 g / l of CaCl2. 2 H2O (340ppm). The results are as follows:

Na LES Na LES + product of Example 2 wetting time 153 107 (seconds)

Claims

1) Detergent composition based on at least one glycerolated or polyglycerolated amide of formula (I)

R 'OH

R-CO - N- (CH2 - CH-CH ₂ -0) _n H (I)

OH 1. R "represents a motif (CH2-CH-CH2-O) _n H

2) Detergent composition according to claim 1), characterized in that it contains of the order of 0.1 to 40% of its weight of at least one glycerolated or polyglycerolated amide of formula (I).

3) Detergent composition according to claim 1) or 2), for household or industrial cleaning or for personal hygiene.

4) detergent composition according to claim 3), for washing dishes by hand.

5) liquid detergent composition for washing dishes by hand according to claim 4), characterized in that it contains about 0.1 to 20%, preferably about 0.5 to 10 % of its weight of glycerolated or polyglycerolated amide of formula (I) and of the order of 0.5 to 40%, preferably of the order of 1 to 20% of its weight of at least one surfactant anionic or nonionic active.

6) Detergent composition according to any one of the preceding claims, characterized in that said glycerolated or polyglycerolated amide of formula (I) is

. N-lauroyl N, N-di (2,3-dihydroxy propyl) amino

. N-lauroyl N, N-di (trihydroxy-2,6,7 oxa-4 heptyl) amino

. N-palmitoyl N, N-di (trihydroxy-2,6,7 oxa-4 heptyl) amino . N-stearoyl N, N-di (trihydroxy-2,6,7 oxa-4 heptyl) amine. N-oleoyl N, N-di (2,6,7-trihydroxy-oxa-4 heptyl) amine. N-behenoyl N, N-di (trihydroxy-2,6,7 oxa-4 heptyl) amino

7) Polyglycerolated amides of formula (D

R 'OH

R-CO - N- (CH - CH-CH ₂ -O) _n H (D

formula in which

. R represents a linear or branched C4-C22 alkyl or alkenyl group. preferably in C8-C22

. n represents an integer or decimal number greater than 1, preferably more than 1 to

50 and especially from 2 to 5 OH

1

. R "represents a motif (CH2- CH-CH2-O) _n H.

8) Process for the preparation of glycerolated or polyglycerolated amides of formula (D forming the subject of claim 7), by condensation or polycondensation of an epoxidized derivative of glycerol on a glycerolamide of formula (II ')

R 'OH

R-CO - -CH ₂ - CH-CH ₂ -OH (II ')

formula in which R and R 'have the definition given in claim 7), in a proportion of more than 1 molar equivalent, preferably of more than 1 to 50 molar equivalents, and very particularly of the order of 2 to 5 equivalents molars, of an epoxidized derivative of glycerol relative to the glycerolamide of formula (II ′).

9) Use of the glycerolated or polyglycerolated amides mentioned in any one of claims 1), 6) or 7), as surfactants, in household or industrial detergent formulations or for personal hygiene, in particular in formulations entering or likely to come into contact with biological systems.

10) Use according to claim 9), in liquid formulations for washing dishes by hand. 11) Use according to claim 10), in an order of 0.1 to 20%. preferably of the order of 0.5 to 10% by weight relative to the weight of said formulations.