EP1049761A1

EP1049761A1 - Use of copolymers on the basis of unsaturated acids or their derivatives as foam-protecting agent

Info

Publication number: EP1049761A1
Application number: EP99900950A
Authority: EP
Inventors: Vance Bergeron; Harold Schoonbrood
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 1998-01-19
Filing date: 1999-01-19
Publication date: 2000-11-08
Also published as: JP3486172B2; JP2002509183A; FR2774694A1; WO1999036496A1; FR2774694B1; BR9907038A; US6706679B1

Abstract

The invention relates to the use of a copolymer or a mixture of copolymers as foam-protecting agents in detergent or cosmetic formulations, comprising at least one monomer (I) selected from the acids, diacids or unsaturated C3-C5 anhydrides; or at least one monomer (II) selected from ethylene oxide and propylene oxide; or at least one monomer (III) selected from the linear or branched C4-C8 hydrocarbons, comprising at least one ethenoid unsaturation; or at least one monomer (IV) of formula R?1-COO-R2¿, where R1 is a possibly substituted linear or branched C¿1?-C3 hydrocarbonic radical; R?2¿ is a linear or branched C¿1?-C4 hydrocarbonic radical which is possibly substituted by an anionic radical or a hydroxyl group; and the monomer (IV) further comprises at least one ethenoid unsaturation.

Description

USE OF COPOLYMERS BASED ON UNSATURATED ACIDS OR DERIVATIVES THEREOF AS FOAM PROTECTIVE AGENTS

The subject of the present invention is copolymers of which one of the monomers is an unsaturated acid or a diacid, or a foam, as a foam-protecting agent in detergent or cosmetic formulations.

The appantation of a large and lasting foam is a phenomenon which it is very important to have in detergent or cosmetic formulations, more particularly those which are implemented by hand. Indeed, it is clearly recognized that this foaming phenomenon is synonymous, for the user, with cleaning efficiency between companies. Consequently, and even if this phenomenon does not really affect the quality of cleaning, the formulators have in particular for objective to prepare formulations allowing to have a significant quantity of foam

However, the appantion and especially the durability of the foam are highly dependent on the other compounds present in the bath, and mainly on fats. In other words, as soon as the washing bath contains fatty substances, the foam is more or less rapidly eliminated.

The object of the present invention is to provide detergent and cosmetic formulations which develop large amounts of foam, and above all which retain this foam, in particular under unfavorable conditions, such as in the presence of grease, and optionally of divalent cations such as calcium.

Thus, the subject of the present invention is the use as a foam-protecting agent in detergent or cosmetic formulations, of a copolymer or of a mixture of copolymers comprising. - at least one monomer (I) chosen from acids, diacids or unsaturated C ₃ -C ₅ anhydrides, or

- at least one monomer (II) chosen from ethylene oxide, propylene oxide, or

- at least one monomer (III) chosen from hydrocarbons, comprising at least one ethylenic unsaturation, linear or branched in C-i-Cβ, or

- at least one monomer (IV) of the following formula

R1-COO-R2, in which ^• R ¹ represents a C ₁ -C ₄ hydrocarbon radical, linear or branched, optionally substituted; R ² represents a linear or branched C ₁ -C ₄ hydrocarbon radical, optionally substituted by an anionic group which may be in the form of an acid or an alkali metal or ammonium salt of type -N ( R3) ₃ ⁺ , with R3, identical or different, representing hydrogen atoms, or C1-C4 hydrocarbon radicals, or optionally substituted by a hydroxyl group; the monomer (IV) comprising at least one ethylenic unsaturation. It should be noted that by foam protective agent is meant a compound making it possible to preserve, at least partially this foam, under unfavorable conditions, such as in the presence of fats, or of divalent cations. It should be noted that the foamability of the polymer used as a foam protective agent in the present invention is not a criterion considered to be truly essential. On the other hand, the compound used must not exert a harmful effect on the ability of the foaming agents otherwise present in the formulation.

The term “fats” is understood to mean more particularly any liquid and / or solid hydrophobic hydrocarbon medium, having for example a water solubility of less than 5 g / l, preferably less than 1 g / l. This fat can be provided by the external environment and / or be a constituent of the detergent or cosmetic formulation. Thus, it can be both a hydrophobic soil and a hydrophobic active compound of said formulation, for example. As an example of grease, we can cite:

- aliphatic, aromatic hydrocarbons (alkanes (such as hexadecane for example), paraffins, mineral oils, paraffinic oils, kerosene, petroleum, fuel, perhydrosqualane, squalene, etc.);

- alkylmonoglycerides, alkyldiglycerides, triglycerides, such as oils extracted from plants and plants (palm oil, copra, cottonseed, soybeans, sunflower, olive, grape seed, sesame, d (peanut, castor, hazelnut, etc.) or oils of animal origin - tallow, fish oils), derivatives of these oils such as hydrogenated oils, lanolin derivatives;

- essential oils, natural or not, such as eucalyptus, lavender, iavandin, vetiver, lemon, orange, sandalwood, rosemary, chamomile, savory, nutmeg, cinnamon oils , bergamot, cade, geraniol, etc. - fatty alcohols such as cetyl alcohol, stearyl alcohol, oleic alcohol;

- fatty esters such as isopropyl palmitate, ethyl-2-hexyl cocoate, myristyl myristate, esters of lactic acid, stearic acid, behennic acid, isostearic acid ;

- oils, gums or resins such as polyorganosiloxanes or cyclic linear polydimethylsiloxanes, polydimethylsiloxanes α-ω hydroxylated polydimethylsiloxanes α-ω trimethylsilyl, polyalkylmethylsiloxanes, the polyméthylphénylsiioxanes, polydiphenylsiloxanes, amino derivatives of silicones, silicone waxes; - organic soiling (sebum, etc.).

Thus, the use of these copolymers in detergent or cosmetic formulations makes it possible to have initial foaming properties at least as good as those of conventional formulations. In addition, and this constitutes a remarkable advantage of these copolymers, the use of the latter in detergent and cosmetic formulations makes it possible to maintain a volume of foam of 10%, preferably 15%, or even up to 30% greater than that of formulations which are devoid of it, and this in the presence of greases possibly combined with divalent cations. However, other objects and advantages of the present invention will appear more clearly on reading the description and the examples which follow.

As has just been said, the foam protective agent used in the present invention is a copolymer or a mixture of several copolymers comprising at least one of the monomers (I) to (IV) mentioned above. More specifically, the copolymer or mixture of copolymers comprises at least one monomer of at least two monomers of types (I) to (IV), of at least two monomers of type (IV) and optionally of at least one monomer of type (I) to (III), or mixtures thereof.

It should be noted that the copolymer used as a foam protective agent is more particularly soluble at the time of the use of the formulation into which it is introduced, that is to say soluble in aqueous media.

More particularly, the copolymer is such that it is soluble in an aqueous solution whose pH is basic. Such conditions are conventional in particular in the cleaning of dishes and linen. In addition, the copolymer used according to the invention advantageously has both a hydrophilic part and a hydrophobic part. Thus, it makes it possible to lower the interfacial tension between the aqueous solution and the fats, which improves the dispersion of the latter in the aqueous solution.

Generally, the copolymers used according to the invention have a molar mass by weight of between 103 and 10 ⁷ g / mol, more particularly between 104 and 106 g / mol, and preferably between 10 _e and 5.105 g / mol. According to an even more advantageous embodiment, the copolymers have a molar mass by weight of between 1.5.10 and 5.105 g / mol. The molar mass is determined by steric exclusion chromatography in aqueous phase. As an example of a method for measuring the molar mass of the copolymers used in the context of the invention, a TSK - gel column, with an eluent comprising water, 0.1 mol / l of NaO ₃ and 200 ppm NaN ₃ , was used. Molecular mass detection is based on the refractive index, using polyethylene oxide as a standard. As regards more particularly the monomer (I), the latter is chosen from acids, diacids or unsaturated C3-C5 anhydrides.

The most suitable representatives of this monomer are acrylic acid, methacrylic acid. As regards the diacids and anhydrides, mention may be made, inter alia, of maleic acid, fumaric acid, itaconic acid, maleic anhydride, fumaric anhydride, itaconic anhydride.

The monomer (II) is chosen from ethylene oxide, propylene oxide. The monomer (III) is chosen from hydrocarbons, linear or branched comprising at least one ethylenic unsaturation, in C4-C8. As an example of this type of monomer, mention may very particularly be made of isobutylene and diisobutylene. Finally, the monomer (IV) corresponds to the following formula: R1-COO-R2, in which: R1 represents a hydrocarbon radical in C1-C4, linear or branched, optionally substituted; R2 represents a linear or branched C1-C4 hydrocarbon radical, optionally substituted by an anionic radical which may be in the form of an acid or an alkali metal or ammonium salt of type -N (R3) 3 ⁺ , with R3, identical or different, representing hydrogen atoms, or C1-C4 hydrocarbon radicals, or optionally substituted by a hydroxyl group; the monomer (IV) comprising at least one ethylenic unsaturation.

More particularly, said monomer (IV) is such that R1 is derived from acrylic acid, methacrylic acid or even acetic acid.

It is also conceivable to use a monomer (IV) in which the radical Rf is substituted. Note that by substituent, is meant a radical during or else a group interrupting the hydrocarbon chain. Thus, as a suitable substituent, mention may be made of the radicals -OH, -O-, -C (O) -, -C (O) -N-, -C (O) OR, with R representing an atom of hydrogen, an alkali metal, hydrocarbon radical, preferably saturated, C1-C4. The term “anionic radical” is intended to denote the sulphonated, sulphated, phosphated, phosphonate or carboxylic radicals. Preferably, a sulfonated monomer is used.

According to a particular embodiment of the invention, the monomer (IV) comprises at least one ethylenic unsaturation. If there is only one unsaturation, it can be found either on the radical R1 or on the radical R2. If there are several unsaturations, they can be located on the radical R1, on the radical R2, or even on the two radicals R1 and R2. Preferably, a monomer comprising only an ethylenic unsaturation is used.

Consequently, if the monomer (IV) derives from an unsaturated acid, then the radical R2 does not carry ethylenic unsaturation. On the other hand, in the opposite case, the radical R2 comprises ethylenic unsaturation.

A first embodiment of the invention consists of the use of a copolymer comprising at least one monomer (I) and at least one monomer (III).

Preferably, this copolymer comprises maleic acid or maleic anhydride as the monomer (I), and isobutylene or diisobutylene as the monomer (III).

The copolymer can be in the acid form or else in the form of an alkali metal or ammonium salt of type -N (R3) ₃ ⁺ , with R3, identical or different, representing hydrogen atoms, or radicals C1-C4 hydrocarbons. Preferably, the copolymer is in the form of sodium salts. The distribution of the monomers is alternated in the molecule.

The proportion of the monomer (I) relative to the monomer (III) is 50/50. These copolymers are well known compounds and are sold in particular under the name GEROPON® T 36 (Rhodia Chimie).

A second embodiment of the invention consists of the use of a copolymer comprising at least one monomer (I) and at least one monomer (II).

More particularly, this copolymer comprises a polymer chain consisting of the monomer (s) (II) on which are grafted polymer chains derived from the monomer (s) (I).

According to a particularly advantageous variant of the invention, said copolymer comprises, as monomer (I), acrylic acid, and as monomer (II), ethylene oxide, or a mixture of ethylene oxide / propylene oxide . In the case of an ethylene oxide / propylene oxide mixture, preferably a chain is used having an ordered distribution corresponding to a diblock of the two abovementioned monomers. The copolymer according to this variant has a proportion by weight of monomer (II) varying from 1 to 50% relative to the weight of the copolymer. Preferably, it is between 1 and 30% relative to the weight of the copolymer.

These copolymers can be obtained by any means known to those skilled in the art.

For example, they are obtained by carrying out a polymerization, in an appropriate solvent, of the monomer (I) and of the polymer chain consisting either of ethylene oxide alone, or of an ethylene oxide / propylene oxide mixture, in the presence of an initiator producing free radicals. Generally, the reaction is carried out using water or an alcohol / water mixture. In addition, the reaction of polymerization is carried out in the presence of a base, so that, if present, the monomer (I) is partially neutralized.

According to a third embodiment of the invention, the copolymer used as protective agent for foam, optionally comprises at least one monomer (I) and at least one monomer (IV).

The monomer (IV) can be more particularly chosen from the following monomers: vinyl acetate; alkyl acrylate; alkyl methacrylate; alkyl methacrylate or acrylate carrying, as an anionic group, a sulfonated (sulfoalkyl) group, in the form of an acid or an alkali metal or ammonium salt of type -N (R3) ₃ ⁺ ; hydroxyalkyl acrylate or methacrylate; monomers in which the alkyl radical corresponds to the methyl, ethyl, propyl and isomer radicals, butyl and isomers.

As regards the sulfonated monomers, use is more particularly made of monomers in the form of a salt, preferably in the form of an alkali metal salt. By way of example of a monomer of the sulfoalkyl type, mention may be made of sodium sulfoethyl acrylate, sodium sulfoethyl methacrylate.

As regards the monomer comprising a hydroxyalkyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate are advantageous examples thereof. It should be noted that the copolymer can comprise one or more monomers (IV), with or without monomer (I).

A first type of particularly advantageous copolymer has the following composition: monomer (I) 0-50% by weight monomer (IV) vinyl acetate 0-92% by weight

CC ₄ alkyl (meth) acrylate

(preferably butyl) 0-50% by weight

(meth) sodium sulfoalkyl acrylate CC ₄ (preferably ethyl) 0-10% by weight the sum of each of the monomers used being equal to 100% by weight of the copolymer.

More particularly, this copolymer comprises 1-15% of monomer (I); 50-85% vinyl acetate; 5-20% alkyl acrylate or methacrylate; 0.5-5% sodium sulfoalkyl acrylate or methacrylate; the sum of each of the monomers used being equal to 100% by weight of the copolymer.

In the case where the copolymer comprises at least one monomer (I), the latter is more particularly chosen from acrylic acid, methacrylic acid. A second type of very advantageous copolymer consists in using a monomer (I), and preferably (meth) acrylic acid, and at least one monomer

(IV) comprising a hydroxyl substituent, which is preferably 2-hydroxyalkyl acrylate or 2-hydroxyalkyl methacrylate, in which the alkyl radical is C ₁ -C ₄ , preferably C 2.

More particularly, the proportion of monomer (I) in this second type of copolymer is 0.1-50% by weight relative to the weight of the copolymer, preferably between 20-60% by weight.

The copolymers used in this third embodiment of the invention are preferably copolymers having a statistical distribution of the various aforementioned monomers.

These copolymers can again be obtained by using conventional means for those skilled in the art.

Thus, the polymerization can take place in solution, or in emulsion, by introducing the various monomers, in the presence of a compound producing free radicals. Generally, the reaction is carried out using water or an alcohol / water mixture. It is possible to carry out the polymerization reaction in solution or in emulsion, in which case the use of a surfactant is necessary. In addition, conventional compounds can be used, if necessary, such as buffering agents, bases for neutralizing acids, if such monomers are present, transfer agents (limiting the growth of chains).

The foam protective agent is therefore used in detergent or cosmetic formulations, and it represents more particularly 0.05 to 10% by weight of the formulation, more particularly between 0.05 and 2% by weight. Advantageously, the amount of foam protective agent represents 0.5 to 2% by weight of the formulation.

The detergent formulations in which the foam protective agent can be used, are more particularly household detergent formulations intended for washing by hand the dishes or the linen. In the field of household detergents, the present invention relates more particularly to compositions for hand dishwashing liquids.

Said compositions, in addition to the foam protective agent according to the invention, can contain of the order of 0.5 to 40%, by weight of anionic surfactants, of the order of 0.5 to 10% by weight of surfactants non-ionic, and 0 to 20% by weight of zwitterionic or amphoteric surfactants.

ANIONIC SURFACTANTS:. the alkyl sulphates of formula ROSO3M, where R represents a C ₁ 0-C 24 alkyl or hydroxyalkyl radical, preferably C ₁ 2-C ₂ 0 and very particularly C ₁ 2- C- | 8, 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 on average from 0.5 to 6 units, preferably from 0.5 to 3 OE and / or OP units; . alkylethersulfates; . alkyl glycoside sulfates;

. the alkylamide sulfates of formula RCONHROSO3M where R represents an alkyl radical in C2-C22- preferably in C6-C20. 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 (OE) and / or propoxylenated (OP) derivatives, having an average of 0, 5 to 60 OE and / or OP patterns;

. C9-C-20 alkylarylsulfonates - primary or secondary C% - C22 alkylsulfonates, alkyl glycerol sulfonates, sulfonated polycarboxylic acids described in GB-1082179, sulfonated fatty acid derivatives; paraffin sulfonates; . alkyl sulfonate esters of formula R-CH (Sθ3M) -COOR ', where R represents a Cβ-20 alkyl radical. preferably in Cιo-C-i6 _> R 'an alkyl radical in Ci-Cβ, preferably in 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-C-16;

. alkylphosphates;

. polyethoxycarboxylates; the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...);

. the salts of C8-C20, preferably C12-C16 saturated or unsaturated fatty acids, N-acyl N-alkyltaurates, alkylisethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates. NON-IONIC SURFACTANTS: polyoxyalkylenated (polyoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols 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; . glucosamide, glucamide; . glycerolamides derived from N-alkylamines (US 5,223,179 and FR 1,585,966);

. polyoxyalkylenated C8-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, NEODOL 45-9, NEODOL 23-65,

NEODOL 45-7, NEODOL 45-4, KYRO EOB;

. products resulting from the condensation of ethylene oxide with a hydrophobic compound resulting from the condensation of propylene oxide with propylene glycol, such as PLURONIC;

. products resulting from the condensation of ethylene oxide the compound resulting from the condensation of propylene oxide with ethylenediamine, such as TETRONIC;

. amine oxides such as alkyl oxides C-10-C-iβ dimethylamines, alkoxy oxides C8-C22 ethyl dihydroxy ethylamines; . the alkylpolyglycosides described in US 4,565,647;

. oxyalkylene derivatives of fatty alcohols such as PLANTAREN®;

. amides of C8-C20 fatty acids;

. ethoxylated fatty acids;

. ethoxylated fatty amides; . ethoxylated amines.

AMPHOTERIC AND ZWITTERIONIC SURFACTANTS:

. alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethyl sulfobetaines;

.alkylamphoacetates or alkylamphodiacetates, such as the products of the Miranol® range;

. fatty acid condensation products on proteins or protein hydrolysates;

. amphoteric derivatives of alkyl polyamines such as AMPHIONIC XL®, AMPHOLAC

7T / X® and AMPHOl-ΛC 7C / X®. The formulations may contain other additives such as:

VISCOSITY AGENTS, such as:

. cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose; guar derivatives such as hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar. HYDROTROPIC AGENTS:

. C2-C8 short alcohols, in particular ethanol, but also methanol, propanol, isopropanol;

. diols and glycols such as propanediol, ethylene glycol, diethylene glycol, dipropylene glycol; It should be noted that amphoteric surfactants can also play the role of hydrotropic agent, as can toluene sulfonate, xylene sulfonate, urea.

MOISTURIZING OR PROTECTIVE AGENTS FOR THE SKIN, such as:. glycerol; urea,

. proteins or protein hydrolysates;

. cationic polymers such as cationic guar derivatives (JAGUAR C13S®, JAGUAR C162®, HICARE 1000®. OTHER ADDITIVES such as:

. bactericidal or disinfectant agents such as triclosan; . buffering agents; . perfumes ;

. pigments, dyes; . conservatives.

With regard more particularly to the formulations intended for washing linen by hand (liquid or solid), these may comprise, in addition to the foam protective agent according to the invention, the following elements:

SURFACTANTS, in an amount corresponding to about 3-40% by weight relative to the detergent composition. The lists of surfactants that have been given for household detergency formulations remain valid and will not be repeated here. We can therefore refer to it.

BUILDERS, in an amount 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 detergent formulas in powders, such as: inorganic builders: polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines; . tetraborates; . silicates, in particular those having an Siθ2 / Na2θ ratio of the order of 1.6 / 1 to 3.2 / 1 and the lamellar silicates described in US 4,646,839; . alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates); . the 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 488 868;

. crystalline or amorphous aluminosilicates 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. organic builders:. water-soluble polyphosphonates (1-hydroxy-1, 1-diphosphonate ethane, methylene diphosphonate salts, etc.);

. the water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as: . polycarboxylate ethers (oxidisuccinic acid and its salts, tartic acid and its salts, succinic acid and its salts, or their co-products);

. hydroxypolycarboxyla.es ethers;

. citric acid and its salts, mellitic acid, succinic acid and their salts; . polyacetic acid salts (ethylenediaminetetraacetates, nitrilotriacetates,

N- (2 hydroxyethyl) -nitrilodiacetates);

. succinic C5-C20 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.

ANTI-FOULING AGENTS, in an amount of the order of 0.01-10%, preferably about 0.1-5%, and very particularly of the order of 0.2-3% by weight, such as:

. cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose; . polyvinyl ethers grafted on polyalkylenated trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP 219048); . 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 3959230, US 3893929, US 4116896, US 4702857, US 477066); . sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethylterephthalate and 1,2 propylene diol, having from 1 to 4 sulfonated groups (US 4968451);

. polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated by ethyl or methyl units (US 4711730) or polyester oligomers terminated by alkylpolyethoxy groups (US 4702857) or anionic sulfopolyethoxy groups (US 4721580), sulfoaroyles 4,877,896); . polyesters-polyurethanes obtained by reaction of a polyesters with a molecular mass of 300-4000 in number obtained from adipic acid and / or terephthalic 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 weight of 600-4000 and a diisocyanate

(FR 2334698).

ANTI-REDEPOSITION AGENTS, more particularly in formulations intended for washing clothes, in an amount of approximately 0.01-10% by weight for a powdered detergent composition, of approximately 0.01-5% by weight for a composition liquid detergent, such as:

. ethoxylated monoamines or polyamines, polymers of ethoxylated amines

(US 4597898, EP 11984);

. carboxymethylcellulose; . polyester sulfonated oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol (FR 2236926);

. polyvinylpyrrolidones.

CHELATING AGENTS of calcium, magnesium, and iron, in an amount of the order of 0.1-10%, preferably of the order of 0.1-3% by weight, 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, for controlling the hardness of calcium and magnesium, such as:

. 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 very particularly polyacrylates of molecular weight of the order of 2000 to 10000 (US 3308067), the copolymers of acrylic acid and maleic anhydride of molecular weight of the order of 5,000 to 75,000

(EP 66915);

FLUORESCENCE AGENTS, in an amount of about 0.05-1.2% by weight, 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-). SOFTENING AGENTS, in an amount of about 0.5-10% by weight, such as clays.

ENZYMES in amounts up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, such as: . proteases, a ylases, lipases, cellulases, peroxidases (US 3553139, US 4101457, US 4507219, US 4261868).

OTHER ADDITIVES such as:. alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin);

. buffering agents; . perfumes ; . pigments.

The foam protective agent according to the invention can likewise enter into the composition of cosmetic formulations such as, inter alia, formulations for shampoos for hair or the body, face or body cleansing gels, liquid soaps, foaming compositions for the bath.

In addition to the agent according to the invention, said formulations can comprise at least one of the following elements: SURFACTANTS, anionic type, if necessary combined with nonionic, zwitterionic and amphoteric surfactants, in an amount varying from 0.05 to 20 % by weight of the preparation. Again, reference may be made to the lists of surfactants given previously.

MOISTURIZING AGENTS, such as; . glycerol, sorbitol; . urea;

. collagen, gelatin; . the aloe vera ; . hyaluronic acid. EMOLLIENTS, such as:

. alkylmonoglycerides, alkyldiglycerides, triglycerides such as oils extracted from plants and plants (palm, copra, cottonseed, soybean, sunflower, olive, grapeseed, 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 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-2-hexyl cocoate, myristyl myristate, lactic acid esters,

. stearic acid, behennic acid, isostearic acid, silicone oils comprising cyclic polydimethylsiloxanes, α-ω hydroxylated polydimethylsiloxanes, α-ω trimethyisilyllated polydimethylsiloxanes, polyorganosiloxanes such as polyalkylmethylsiloxanes, polymethyl phenylsiloxanes, polydiphenylsiloxanes, amino derivatives of silicones, silicone waxes, copolyether silicones (such as SILBIONE 70646® or DC 190® oil) or mixed silicone derivatives such as mixed polyalkylmethyl copolymers - copolyether silicones.

MINERAL PARTICLES OR SOLAR FILTERS, such as:. calcium carbonate,

. mineral oxides in powder form or in colloidal form (particles of smaller size or of the order of one micrometer, sometimes of a few tens of nanometers) such as titanium dioxide, silica, aluminum salts, kaolin, talc, clays and their derivatives, ...

PRESERVING AGENTS, in an amount of the order of 0.01 to 3% by weight such as:

. the methyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid,. sodium benzoate, GERMABEN®.

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.

VISCOSING / GELIFYING AGENTS, such as:. CARBOPOL® crosslinked polyacrylates;

. cellulose derivatives such as hydroxypropylcellulose, carboxymethylcellulose; . guars and their derivatives, carob, tara or cassia gum; . xanthan gum; . alginates, carrageenans; . chitin derivatives like chitosan.

The foam protective agent according to the invention can likewise be used in formulations of toilet bars called soaps or soaps.

Conventional toilet bar compositions generally comprise fatty acid salts used in combination with the agent according to the invention, but also surfactants other than the fatty acid salts or the fatty acids themselves, and mentioned above. .

These compositions may not even contain any fatty acid or fatty acid salt and their formulations are then based on other surfactants, such as, for example, C8-C22 sodium alkyl isethionates or Cs-C22 sodium alkyl sulphates. SKIN IRRITA TION / HYDRA TANTS:

. alkali metal salts or isethionates; . carbohydrates (glycerol, sorbitol for example); . polyethylene 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 (wheat protein hydrolysates for example); . natural hydrocolloids (guar, carob, tara gum ...) or derived 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 ®), guar or carob derivatives such as their cationic derivatives (JAGUAR C13S®, JAGUAR C162®) or nonionic derivatives (for example hydroxypropylguar), anionic derivatives (carboxymethylguar) or mixed nonionic / anionic derivatives such as carboxy-hydroxypropyl-guars 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®. Calcium sequestering agents such as citrate ions. EMOLLIENT AGENTS such as silicones or oils or fatty substances used for this purpose in the cosmetic industry (mineral oils, fatty acid esters, triglycerides, silicones). ADDITIVES:

. perfumes,

. dyes and / or opacifying agents such as pigments (titanium oxide particles); . bactericidal or fungicidal agents. 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, as well as alkyl ether sulfates, alkyl betaines, alkylamidopropylbetaines, alkylampho-acetates, -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 C8-C22 fatty acids can also be introduced into the soap compositions as superfatting agents or to modify the appearance and the creamy character of the foam during washing.

Waxes such as paraffinic 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, behavior, processability and storage conservation of toilet rolls.

Shampoos, and more generally detergent compositions for personal use may contain, in addition to the foam protective agent according to the invention, the usual additives present in these types of formulation. We can cite in particular:

SURFACTANTS such as those indicated above, in an amount varying from 5 to 25%.

CONDITIONING AGENTS such as:. synthetic cationic polymers of the MIRAPOL AD1® or MIRAPOL A550® type, natural cationic polymers such as cationic guar derivatives (JAGUAR C135®, JAGUAR C162®) or cationic cellulose derivatives (POLYMER JR400®);

. 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.).

ANTI-DANDRUFF AGENTS, such as:. pyridinesthiones, more especially zinc pyridinethione,. selenium-based compounds such as selenium sulfide or OCTOPYROX®. AGENTS THAT MODIFY UASPECT OR VISCOSITY, such as:

. pearlescent compounds based on polyethylene glycol stearate; . CARBOPOL®,

. hydrocolloids and their derivatives such as guar or modified guars, carob, xanthan gum, cellulose derivatives (hydroxyethylcellulose, carboxymethylcellulose).

OTHER ADDITIVES, such as:. anti-parasite agents (anti-lice), such as LINDANE or various pyrethrins; . dyes, pigments; . perfumes.

Concrete but nonlimiting examples of the invention will now be presented. PC17FR99 O 99/36496

17

EXAMPLE 1

This example relates to the preparation of a copolymer based on acrylic acid and ethylene oxide.

In a 2 liter glass reactor, fitted with a double jacket and an agitator (190 rpm), 10 g of sodium hydroxide are dissolved in 680 g of water, at room temperature. The temperature is then increased to 65 ° C.

An initiator solution comprising 0.105 g of ammonium persulfate and 30 g of water is prepared. Furthermore, a solution comprising 30 g of water and 70 g of acrylic acid and a solution comprising 10 g of sodium hydroxide and 30 g of water are mixed.

In the reactor, 14 g of polyethylene oxide (100,000 g / mol) are dissolved. Then the solution comprising acrylic acid and the initiator solution is introduced continuously. The operation is carried out over 300 minutes, keeping a constant introduction rate and the temperature at 65 ° C.

Once the introduction is complete, the reaction mixture is left under stirring for 120 minutes and at 65 ° C.

The mixture is finally cooled to room temperature.

A copolymer is obtained, the polyoxyethylenated chain of which carries grafts of the polyacrylic acid type.

The pH is 4.8.

The solids content is 12%.

EXAMPLE 2

This example relates to the preparation of a copolymer based on acrylic acid and ethylene oxide / propylene oxide.

In a 2 liter glass reactor, fitted with a double jacket and an agitator (190 rpm), 10 g of sodium hydroxide are dissolved in 630 g of water, at room temperature. The temperature is then increased to 65 ° C. An initiator solution comprising 0.46 g of ammonium persulfate and 10 g of water is prepared. Furthermore, a solution is prepared comprising 28 g of water and 92 g of acrylic acid. 18.4 g of a polyethylene oxide / propylene polyethylene block copolymer (6500 g / mol, 50% ethylene oxide) and 180 g of ethanol are introduced into the reactor.

Then the initiator solution is added once the diblock copolymer has dissolved. Continuously, the solution comprising acrylic acid is then added, over a period of 120 minutes, keeping a constant rate of introduction and the temperature at 65 ° C.

Once the introduction is complete, the reaction mixture is left under stirring for 120 minutes and at 65 ° C. The mixture is finally cooled to room temperature.

A copolymer is obtained in which the polyoxyethylenated / polyoxypropylenated chain carries grafts of the polyacid acrylic type. The pH is 4.8. The solids content is 12%.

EXAMPLE 3

This example illustrates the preparation of a copolymer comprising, as monomers, vinyl acetate, acrylic acid, butyl acrylate and sodium sulfoethyl methacrylate.

A mixture comprising 150.6 g of water is introduced with stirring into a 2 liter glass reactor, fitted with a double jacket and a stirrer (190 rpm),

1.6 g of sodium lauryl sulfate, 7.21 g of an aqueous solution of sodium sulfoethyl methacrylate at 44.35% and 1.6 g of sodium acetate, and the reactor is brought to

70 ° C.

An initiator solution comprising 1.6 g of ammonium persulfate and 6 g of water is prepared, which is introduced into the reactor at t = to. A mixture comprising 150 g of water, 246.4 g of vinyl acetate is emulsified,

51.2 g of butyl acrylate, 22.4 g of acrylic acid and 1.6 g of sodium lauryl sulfate. The emulsion is then added to the reactor, over a period of 5 hours from to.

Then we add:

- a solution of 2.176 g of sodium sulfoxide, 1.6 g of sodium bicarbonate in 48 g of water, in 7 hours from to;

- a solution of 1.83 g of tert-butyl hydroperoxide (70%) and 40 g of water in 7 hours from to. The temperature is then increased to 80 ° C and maintained for one hour before cooling.

A statistical copolymer is obtained.

EXAMPLE 4

This example illustrates the preparation of a copolymer comprising acrylic acid and 2-hydroxyethyl methacrylate.

10 g of sodium hydroxide dissolved in 252 g of water, at room temperature, are introduced into a 2-liter glass reactor, fitted with a double jacket and a stirrer (190 rpm).

The temperature is then increased to 65 ° C.

A mixture of 408 g of water, 55 g of 2-hydroxyethyl methacrylate, 55 g of acrylic acid and 0.22 g of methyl mercaptopropionate is prepared.

A solution comprising 1.1 g of ammonium persulfate is introduced into the reactor. The above mixture is then added continuously, over a period of 120 minutes, at a temperature of 65 ° C.

The mixture is finally cooled to temperature.

A copolymer is obtained having a statistical distribution of the monomers, the pH is 7.2. The solid content of 15.3%.

EXAMPLE 5

This example relates to the use of each of the copolymers previously obtained, in a detergent formulation, in the presence of grease.

The detergent formulation used includes:

° 21% by dry weight of sodium lauryl ether sulfate (EMPICOL ESB / 3M sold by Albright &Wilson);

- 3% by dry weight of ethoxylated alcohol containing on average 6 oxyethylene units (RHODASURF IDO60 marketed by Rhodia Chimie);

- 3% by dry weight of cocoamidopropyl betaine (DEHYTON K sold by Henkel);

° qs 100% by weight of water. The pH was adjusted to 7.

The copolymers obtained previously were tested separately with the formulation described above; the content of copolymer being 2% by weight relative to that of the formulation; the whole being diluted to 1%.

The test involves doing the following:

250 ml of the formulation described above are introduced into a 500 ml bottle and 7 ml of fat are added (50/50 mixture by weight of sunflower oil and margarine).

The bottle is capped then a series of inversion of the bottle is carried out, with a frequency of 60 inversion per minute.

The results show that the volume of foam maintained in the presence of the grease used, remains approximately 15% higher in the case of formulations comprising the copolymer according to the invention, than that of a formulation which does not contain any.

Claims

nΛ ne Λne PCT / FR99 / 00091 99/3649621 CLAIMS

1. Use as a foam-protecting agent in detergent or cosmetic formulations, of a copolymer or of a mixture of copolymers comprising:

- at least one monomer (I) chosen from acids, diacids or unsaturated C3-C5 anhydrides, or

- at least one monomer (II) chosen from ethylene oxide, propylene oxide, or

- at least one monomer (III) chosen from hydrocarbons, comprising at least one ethylenic unsaturation, linear or branched in C4-C8, or

- at least one monomer (IV) of the following formula:

R1-COO-R2, in which: R ¹ represents a linear or branched C1-C3 hydrocarbon radical, optionally substituted;

R2 represents a linear or branched C1-C4 hydrocarbon radical, optionally substituted by an anionic radical which may be in the form of an acid or an alkali metal salt, or of ammonium of type -N (R3) ₃ ⁺ , with R3, identical or different, representing hydrogen atoms, or C1-C4 hydrocarbon radicals, or optionally substituted by a hydroxyl group; the monomer (IV) comprising at least one ethylenic unsaturation.

2. Use according to the preceding claim, characterized in that the monomer (I) is chosen from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, fumaric anhydride, itaconic anhydride.

3. Use according to any one of the preceding claims, characterized in that the monomer (II) is chosen from isobutylene, diisobutylene.

4. Use according to any one of the preceding claims, characterized in that the monomer (IV) has a radical R ¹ derived from acrylic acid, methacrylic acid, acetic acid.

5. Use according to claim 1, characterized in that the copolymer comprises at least one monomer (I) and at least one monomer (III).

6. Use according to the preceding claim, characterized in that the copolymer comprises the monomer (I) is maleic acid or maleic anhydride, and the type monomer (III) is isobutylene or diisobutylene.

7. Use according to claim 1, characterized in that the copolymer comprises at least one monomer (I) and at least one monomer (II).

8. Use according to the preceding claim, characterized in that the copolymer comprises a polymer chain consisting of the monomer (s) (II) on which are grafted polymer chains derived from the monomer (s) (I).

9. Use according to any one of claims 7 or 8, characterized in that the monomer (I) is acrylic acid, and the monomer (II) is either ethylene oxide or an oxide mixture ethylene / propylene oxide.

10. Use according to claim 1, characterized in that the copolymer optionally comprises at least one monomer (I) and at least one monomer (IV).

11. Use according to any one of claims 10 or 11, characterized in that the monomer (IV) is chosen from the following: vinyl acetate, alkyl acrylate, alkyl methacrylate, methacrylate or alkyl acrylate bearing a sulfonated (sulfoalkyl) group, in the form of an acid or an alkali metal or ammonium salt of -N (R3) ₃ ^{+ type} , hydroxyalkyl acrylate or methacrylate; monomers in which the alkyl radical corresponds to the methyl, ethyl, propyl and isomer radicals, butyl and isomers.

12. Use according to any one of claims 10 or 11, characterized in that the copolymer has the following composition: monomer (I) 0-50% by weight monomer (IV): vinyl acetate 0-92% by weight

(meth) C ₁ -C ₄ alkyl acrylate 0-50% by weight

(meth) sodium sulfoalkyl acrylate CC ₄ 0-10% by weight the sum of each of the monomers used being equal to 100% by weight of the copolymer.

13. Use according to the preceding claim, characterized in that the copolymer has the following composition: 1-15% of monomer (I); 50-85% vinyl acetate; 5-20% alkyl acrylate or methacrylate; 0.5-5% acrylate or sodium sulfoalkyl methacrylate; the sum of each of the monomers used being equal to 100% by weight of the copolymer.

14. Use according to any one of claims 10 to 13, characterized in that the copolymer comprises at least one monomer (I), preferably chosen from acrylic acid, methacrylic acid.

15. Use according to any one of claims 10 or 11, characterized in that the monomer (IV) is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and in that the monomer (I) is acrylic acid, methacrylic acid.

16. Use according to the preceding claim, characterized in that the proportion of monomer (I) relative to the monomer (IV) is between 0.1 and 90% by weight relative to the weight of the copolymer.

17. Use according to any one of the preceding claims, characterized in that the amount of foam-protecting agent in a detergent or cosmetic formulation represents 0.05 to 10% by weight of the formulation, preferably between 0.05 and 2% by weight.

18. Use according to any one of the preceding claims in detergent formulations intended for washing dishes or linen by hand.

19. Use according to any one of claims 1 to 17 in cosmetic formulations.