EP1196527B1 - Use of an amphoteric polymer for treating selected hard surface - Google Patents

Abstract

This invention relates to the use of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:(a) at least one monomer compound of general formula I:(b) at least one hydrophilic monomer bearing a function of acidic nature which is copolymerizable with (a) and capable of ionizing in the application medium,(c) optionally, at least one hydrophilic monomer compound containing ethylenic unsaturation and of neutral charge, bearing one or more hydrophilic groups, which is copolymerizable with (a) and (b),the a/b molar ratio being between 60/40 and 5/95,to give a hard surface hydrophilic properties.

Description

The present invention relates to the cleaning of hard surfaces, dishes, shower screens and outer surfaces of motor vehicles, to give these surfaces hydrophilic.

The subject of the invention is more particularly the use of polymers with both hard surface interaction properties and hydrophilic properties to impart to it properties residual hydrophilization in order to avoid the subsequent presence of traces due in particular to the drying of drops of water deposited on the said area.

Commercial detergent formulations help to effectively clean hard industrial, domestic or community. They generally consist of an aqueous solution of surfactants, especially nonionic and anionic surfactants, alcohol (s) to facilitate drying, and optionally sequestering agents and bases to adjust the pH. An important defect of these detergent formulations is the subsequent contact of the hard surface with water can lead to drying in the presence of traces. This contact with water after application of detergent can come for example from rainwater in the case of windows, network water on a bathroom tile, or rinsing water when cleaning requires rinsing. They can also come from drying dishes in the open air in the case of detergent formulas for clean dishes by hand, or machine dish drying automatic when it comes to detergent for dishwasher machine. In the automatic cleaning of the crockery, the said formula may be used in the cleaning cycle (detergent formula) or during rinsing (rinsing liquid).

The presence of traces or stains left on hard surfaces by the water coming into contact with them is due to the phenomenon of contraction drops of water in contact with the hard surface which, during the subsequent drying, leave traces on the surface reproducing shapes and dimensions original drops.

To solve the problem of shrinkage and drying drops of water on hard surfaces, dishes, shower screens and exterior surfaces of motor vehicles, the solution is to increase the hydrophilicity of the surface in order to obtain the most weak possible between the hard surface to be treated and the drop of water.

The work of the inventors having led to the present invention determined that this problem could be solved effective and durable by incorporating into cleansing compositions of these hard surfaces, an organic polymeric compound water-soluble or water-dispersible having both an interaction function with the surface. to be treated and a function conferring on this surface a character hydrophilic.

• un monomère cationique notamment le chlorure de diméthyldialfytammonium (DADMAC pour diallyldiméthylammonium chloride);
• un monomère anionique, notamment l'acide acrylique ;
• un monomère non ionique, notamment l'acrylamide.

EP 522 756 discloses ampholytic terpolymers comprising as polymeric units:

• a cationic monomer, especially dimethyldialfytammonium chloride (DADMAC for diallyldimethylammonium chloride);
• an anionic monomer, especially acrylic acid;
• a nonionic monomer, especially acrylamide.

These terpolymers have hydration and protection of the skin and nails and are proposed in compositions intended to be applied to the skin such as aftershave, screens solar, hand lotions, liquid soaps, bath products, shaving foams. The document further discloses a composition for washing from the tableware to the hand, this composition being particularly adapted to the protection and hydration of the skin.

WO 97/22 640 discloses aqueous polymer dispersions having surfactant properties and more particularly properties foaming.

The polymers are prepared by polymerization of monomers vinyl compounds (a) having at least one quaternary nitrogen atom with vinyl monomers (b) having at least one amide group and monomers (c) having both hydrophilic and hydrophobic groups, so conferring on the terpolymer detergent properties.

As monomers (a), DADMAC is mentioned in particular.

As monomers (b), mention is especially made of (meth) acrylamide.

The monomers (c) are polyethoxylated derivatives and polypropoxylated carboxylic acid, such as acrylic acid.

EP 835 925 discloses a detergent composition for the washing of automatic dishwasher ware including a lipolytic enzyme and a copolymer obtained by polymerization of from 50 to 99 mol% of units anionic monomers, in particular acrylic acid, with 1 to 50% by weight moles of cationic monomers, in particular DADMAC and 0 to 25% moles of anionic, cationic, amphoteric, nonionic or mixture thereof, especially acrylic acid esters.

The combination of the lipolytic enzyme with the polymer avoids the deposit of limestone soap on the dishes without having a detrimental effect on the action fat removal by lipases.

WO 99/05248 discloses a detergent composition for dishwashers, comprising a builder agent and a cationic polymer or amphoteric, in particular based on DADMAC, to prevent corrosion of the washing up.

It has been proposed (JP 09169995-A-) to use in compositions for the treatment against soiling of toilet bowls, a polymer cationic to increase the hydrophilicity of the surface to be treated. Are As examples of cationic polymers, the homopolymers of DADMAC and copolymers of DADMAC and acrytamide, as well as copolymers of DADMAC and acrylic acid; the polymers cited as preferential are copolymers of DADMAC and acrylic acid having a weight ratio DADMAC / acrylic acid of 8/2 and all preferentially homopolymers of DADMAC.

The work of the inventors having led to the present invention have determined that the use, in compositions for the cleaning the dishes by hand, external cleaning or rinsing motor vehicles and rinsing shower enclosures, copolymers obtained by copolymerization of monomers having a function quaternary ammonium and two ethylenically unsaturated groups with monomers having a group capable of ionizing in the medium application to form anionic units, presenting a report of first monomers to the second monomers within a given range, allowed hard surfaces treated in this way to have properties outstanding hydrophilization.

(a) au moins un composé monomère de formule générale 1 :

   dans laquelle :

• R₁ et R₄ représentent indépendamment l'un de l'autre un atome d'hydrogène ou un groupe alkyle en C₁-C₆ linéaire ou ramifié ;
• R₂ et R₃ représentent indépendamment l'un de l'autre un groupe alkyle, hydroxyalkyle, ou aminoalkyle dans lesquelles le groupe alkyle est une chaíne en C₁-C₆, linéaire ou ramifiée, de préférence un groupe méthyle ;
• n et m sont des nombres entiers compris entre 1 et 3 ;
• X identiques ou différents représentent des contre-ions compatibles avec le caractère hydrosoluble ou hydrodispersible du polymère ;

(b) au moins un monomère hydrophile portant une fonction à caractère acide copolymérisable avec (a) et susceptible de s'ioniser dans le milieu d'application,

(c) éventuellement au moins un composé monomère hydrophile à insaturation éthylénique de charge neutre portant un ou plusieurs groupes hydrophiles, copolymérisable avec (a) et (b),

   dans lequel le rapport molaire a/b est compris entre 60/40 et 5/95, pour conférer à ladite surface dure traitée des propriétés d'hydrophilisation.A first object of the invention is to use, in a composition for treating hard surfaces, chosen from compositions for cleaning dishes by hand, external cleaning or rinsing of motor vehicles and rinsing walls. shower, a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:

(a) at least one monomeric compound of general formula 1:

in which :

• R ₁ and R ₄ represent independently of each other a hydrogen atom or a linear or branched C ₁ -C ₆ alkyl group;
• R ₂ and R ₃ represent, independently of one another, an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C ₁ -C ₆ chain, preferably a methyl group;
• n and m are integers between 1 and 3;
• X identical or different represent counter ions compatible with the water-soluble or water-dispersible nature of the polymer;

(b) at least one hydrophilic monomer carrying a function of acid character copolymerizable with (a) and capable of ionizing in the application medium,

(c) optionally at least one neutral charge ethylenically unsaturated hydrophilic monomer compound bearing one or more hydrophilic groups, copolymerizable with (a) and (b),

wherein the molar ratio a / b is from 60/40 to 5/95 to impart hydrophilic properties to said treated hard surface.

• R₁ représente hydrogène,
• R₂ représente méthyle,
• R₃ représente méthyle,
• R₄ représente hydrogène, et
• m et n sont égaux à 1.

Preferably,

• R ₁ represents hydrogen,
• R ₂ represents methyl,
• R ₃ represents methyl,
• R ₄ represents hydrogen, and
• m and n are 1.

The X ^- ion is advantageously chosen from the anions halogen (chloride), sulfate, hydrosutfate, phosphate, citrate, formate and acetate.

The monomer (a) imparts to the copolymer interaction with the surface to be treated, in particular allowing anchoring of the copolymer on this surface.

The monomer (b) and optionally the monomer (c) give the copolymer of hydrophilic characteristics which, after anchoring of the copolymer on the surface to be treated, are transmitted to it.

The copolymer according to the invention advantageously has a molecular weight of at least 1000, preferably at least 10,000; it can be up to 20 000 000, advantageously up to 10 000 000.

Unless otherwise indicated, when speaking of mass molecular, it will be the molecular weight by weight, expressed in g / mol.

This can be determined by aqueous gel permeation chromatography (GPC) or measurement of the intrinsic viscosity in a 1N solution of NaNO ₃ at 30 ° C.

The copolymer is preferably random.

   X^- étant est tel que défini précédemment.Preferably, the monomer (a) has the following structure:

X ^- being is as defined above.

A particularly preferred monomer is that of the above formula wherein X ^- represents Cl ^- , referred to as DADMAC.

The monomers (b) are advantageously water-soluble monoethylenic unsaturated C ₃ -C ₈ carboxylic, sulphonic, sulfuric, phosphonic or phosphoric acids, their anhydrides and their water-soluble salts.

Among the preferred monomers (b), mention may be made of acrylic acid, methacrylic acid, α-ethacrylic acid, β, β-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, acid ethylidineacetic acid, propylidineacetic acid, crotonic acid, acid maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic, N-methacrylalanine, N-acryloyl-hydroxy-glycine, acrylate sulfoethyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, phosphoethyl acrylate, acrylate, phophonoethyl, phosphopropyl acrylate, phophonopropyl acrylate, phosphoethyl methacrylate, phophonoethyl methacrylate, phosphopropyl methacrylate, phophonopropyl methacrylate, and alkali metal and ammonium salts thereof.

Among the monomers (c), mention may be made of acrylamide, vinyl alcohol, C ₁ -C ₄ alkyl esters of acrylic acid and of methacrylic acid, hydroxyalkyl esters of C ₁ -C ₄ acrylic acid and methacrylic acid, in particular acrylate and methacrylate ethylene glycol and propylene glycol, polyalkoxylated esters of acrylic acid and methacrylic acid, including the esters of polyethylene glycol and polypropylene glycol.

The level of monomers (a) is advantageously between 5 and 60%, preferably 20 to 50 mol%.

The level of monomers (b) is advantageously between 10 and 95%, preferably 20 to 80 mol%.

The level of monomers (c) is advantageously between 0 and 50%, preferably 5 to 30 mol%.

The molar ratio a / b is preferably between 50/50 and 10/90.

The copolymers of the invention can be obtained according to known techniques for preparing the copolymers, in particular by radical polymerization of the ethylenically starting monomers unsaturated compounds which are known or easily by the person skilled in the art using synthetic methods classical organic chemistry.

The radical polymerization is preferably conducted in a oxygen-free environment, for example in the presence of an inert gas (helium, argon, etc.) or nitrogen. The reaction is carried out in a solvent inert, preferably methanol or ethanol, and more preferably in the water.

The polymerization is initiated by the addition of an initiator of polymerization. The initiators used are the initiators of free radicals usually used in the art. Examples include organic peresters (t-butylperoxypivalate, t-amylperoxypivalate, t-butylperoxy-ac-ethylhexanoate, etc); organic compounds of the azo type, for example, azo-bis-amidino-propane hydrochloride, azobis-isobutyronitrile, azo-bis-2,4-dimethylvaleronitrile, etc.); peroxides inorganic and organic, eg hydrogen peroxide, peroxide benzyl and butyl peroxide, etc .; redox initiator systems, by examples those comprising oxidizing agents, such as persulfates (especially ammonium or alkali persulfates, etc.); the chlorates and bromates (including chlorates and / or bromates inorganic or organic); reducing agents such as sulphites and bisulphites (including inorganic and / or organic sulphites or bisulfites); oxalic acid and ascorbic acid as well as mixtures of two or several of these compounds.

Preferred initiators are water soluble initiators. Especially preferred is sodium persulfate and azo-bis-amidinopropane hydrochloride.

Alternatively, the polymerization can be initiated by irradiation at using ultraviolet light. The quantity of initiators used is in general a sufficient quantity can carry out the initiation of the polymerization. Of preferably, the initiators are present in an amount ranging from 0.001 to 10% by weight relative to the total weight of the monomers, and preferably less than 0.5% by weight per relative to the total weight of the monomers, a preferred amount being the range of 0.005 to 0.5% by weight relative to the total weight of the monomers. The initiator is added to the polymerization mixture, in a continuous manner either discontinuously.

When we want to obtain molecular weight copolymers high, it is desirable to add fresh initiator during the reaction of polymerization. Gradual or discontinuous addition also allows more efficient polymerization and a shorter reaction time. The polymerization is carried out under effective reaction conditions for polymerize the monomers (a), the monomers (b) and optionally the monomers (c) in an oxygen-free atmosphere. Preferably, the reaction is conducted at a temperature of 30 ° to 100 ° and preferably between 60 ° and 90 ° C. The oxygen-free atmosphere is maintained throughout the duration of the reaction, for example by maintaining a purge of nitrogen throughout the reaction.

• copolymère DADMAC/acide acrytique/acrylamide ;
• copolymère DADMAC/acide matéique ;
• copolymère DADMAC/acide sutfonique ; le rapport molaire DADMAC/monomère acide étant compris entre 60/40 et 5195, de préférence entre 50/50 et 10/90.

The following copolymers are very particularly preferred:

• DADMAC / acrylic acid / acrylamide copolymer;
• DADMAC / maleic acid copolymer;
• DADMAC / sutfonic acid copolymer; the molar ratio DADMAC / acidic monomer being between 60/40 and 5195, preferably between 50/50 and 10/90.

The copolymers described above are useful for to give surfaces on which it is applied properties hydrophilization, in particular for imparting properties to surfaces. anti-stain or anti-stick marks, as well as anti-fogging properties.

By "anti-trace or anti-persistent stain properties" is meant that the treated surface retains these properties over time, including after further contact with water, whether it is rainwater, water of the distribution network or of the rinsing water with or without added rinsing.

The copolymer as described above can be implemented in the treatment composition to a content between 0.001% and 10% by weight relative to the total weight of the composition, depending on the concentration of active ingredients thereof.

The copolymers described above are intended for be incorporated in dishwashing compositions by hand, car bodies, walls of showers.

The composition in which said copolymer is used, generally comprises at least one surfactant. It is advantageously anionic and / or nonionic. It can also be cationic, amphoteric or zwitterionic.

Among the anionic surfactants, particular mention may be made of soaps such as C ₈ -C ₂₄ fatty acid salts, for example the salts of fatty acids derived from coconut and tallow; alkylbenzenesulphonates, especially C ₈ -C ₁₃ linear alkyl-benzenesulphonates, in which the alkyl group comprises from 10 to 16 carbon atoms, alcohol-sulphates, ethoxylated alcohol-sulphonates, hydroxyalkylsulphonates; alkyl sulphates and sulphonates, especially of C ₁₂ -C ₁₆ , monoglyceride sulphates, and condensates of fatty acid chloride with hydroxyalkyl sulphonates.

• les alkylesters sulfonates de formule R-CH(SO₃M)-COOR', où R représente un radical alkyle en C_8-20, de préférence en C₁₀-C₁₆, R' un radical alkyle en C₁-C₆, de préférence en C₁-C₃ et M un cation alcalin (sodium, potassium, lithium), ammonium substitué ou non substitué (méthyl-, diméthyl-, triméthyl-, tetraméthylammonium, diméthylpiperidinium
  
  ) ou dérivé d'une alcanolamine (monoéthanolamine, diéthanolamine, triéthanolamine ). On peut citer tout particulièrement les méthyl ester sulfonates dont les radical R est en C₁₄-C₁₆ ;
• les alkylsulfates de formule ROSO₃M, où R représente un radical alkyle ou hydroxyalkyle en C₅-C₂₄, de préférence en C₁₀-C₁₈, M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés éthoxylénés (OE) et/ou propoxylénés (OP), présentant en moyenne de 0.5 à 30 motifs, de préférence de 0,5 à 10 motifs OE et/ou OP ;
• les alkylamides sulfates de formule RCONHR'OSO₃M où R représente un radical alkyle en C₂-C₂₂, de préférence en C₆-C₂₀, R' un radical alkyle en C₂-C₃, M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés éthoxylénés (OE) et/ou propoxylénés (OP), présentant en moyenne de 0,5 à 60 motifs OE et/ou OP ;
• les sels d'acides gras saturés ou insaturés en C₈-C₂₄, de préférence en C₁₄-C₂₀, les alkylbenzènesulfonates en C₉-C₂₀, les alkylsulfonates primaires ou secondaires en C₈-C₂₂, les alkylglycérol sulfonates, les acides polycarboxyliques sulfonés décrits dans GB-A-1 082 179, les sulfonates de paraffine, les N-acyl N-alkyltaurates, les alkylphosphates, les iséthionates, les alkylsuccinamates les alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les sulfates d'alkylglycosides, les polyéthoxycarboxylates le cation étant un métal alcalin (sodium, potassium, lithium), un reste ammonium substitué ou non substitué (méthyl-, diméthyl-, triméthyl-, tetraméthylammonium, diméthylpiperidinium ) ou dérivé d'une alcanolamine (monoéthanolamine, diéthanolamine, triéthanolamine ) ;
• les phosphates esters alkylés ou alkytarytés comme les RHODAFAC RA600, RHODAFAC PA15 ou RHODAFAC PA23 commercialisés par la société RHODIA.

Advantageous anionic surfactants include:

• alkyl ester sulphonates of formula R-CH (SO ₃ M) -COOR ', where R is an alkyl radical C _8-20, preferably C ₁₀ -C _16, R' an alkyl radical in C ₁ -C _6, preferably C ₁ -C ₃ and M an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium)
  
  ) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ). Mention may in particular be made of methyl ester sulphonates whose R radical is C ₁₄ -C ₁₆ ;
• alkyl sulphates of formula ROSO ₃ M, in which R represents a C ₅ -C ₂₄ , preferably C ₁₀ -C ₁₈ , alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 30 units, preferably from 0.5 to 10 EO and / or OP units;
• the alkylamide sulphates of formula RCONHR'OSO ₃ M where R represents a C ₂ -C ₂₂ alkyl radical, preferably C ₆ -C ₂₀ radical, R 'represents a C ₂ -C ₃ alkyl radical, M represents an atom of hydrogen or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 60 EO and / or OP units;
• saturated or unsaturated C ₈ -C ₂₄ , preferably C ₁₄ -C ₂₀ fatty acid salts, C ₉ -C ₂₀ alkylbenzenesulfonates, primary or secondary C ₈ -C ₂₂ alkylsulfonates, alkylglycerol sulphonates, the sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates , the alkyl glycoside sulphates, the 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 );
• alkylated or alkylarytituted phosphate esters such as RHODAFAC RA600, RHODAFAC PA15 or RHODAFAC PA23 marketed by RHODIA.

Among the nonionic surfactants, mention may be made of in particular alkylene oxide condensates, especially ethylene oxide condensates with alcohols, polyols, alkylphenols, fatty acid esters, amides of fatty acids and fatty amines; amine-oxides, derivatives of sugar such as alkylpolyglycosides or esters of fatty acids and sugars, especially sucrose monopalmitate; phosphine oxides tertiary long chain; dialkyl sulfoxides; block copolymers of polyoxyethylene and polyoxypropylene; polyalkoxylated sorbitan esters ; sorbitan fatty esters, poly (ethylene oxide) and acid amides modified to give them a hydrophobic character (eg for example, mono- and diethanolamides of fatty acids containing from 10 to 18 carbon atoms).

• les alkylphénols polyoxyalkylénés (polyéthoxyéthylénés, polyoxypropylénés, polyoxybutylénés) dont le substituant alkyle est en C₆-C₁₂ et contenant de 5 à 25 motifs oxyalkylènes ; à titre d'exemple, on peut citer les TRITON X-45, X-114, X-100 ou X-102 commercialisés par Rohm & Haas Cy. ;
• les glucosamides, glucamides, glycérolamides ;
• les alcools aliphatiques en C₈-C₂₂ polyoxyalkylénés contenant de 1 à 25 motifs oxyalkylènes (oxyéthylène, oxypropylène). A titre d'exemple, on peut citer les TERGITOL 15-S-9, TERGITOL 24-L-6 NMW commercialisés par Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 commercialisés par Shell Chemical Cy., les RHODASURF IDO60, RHODASURF LA90, RHODASURF IT070 commercialisés par la société RHODIA.
• les oxydes d'amines tels que les oxydes d'alkyl C₁₀-C₁₈ diméthylamines, les oxydes d'alkoxy C₈-C₂₂ éthyl dihydroxy éthylamines ;
• les alkylpolyglycosides décrits dans US-A-4 565 647 ;
• les amides d'acides gras en C₈-C_{20 ;}
• les acides gras éthoxylés ;
• les amines éthoxylées

We can mention everything especially

• polyoxyalkylenated alkylphenols (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) whose alkyl substituent is C ₆ -C ₁₂ 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. ;
• glucosamides, glucamides, glycerolamides;
• polyoxyalkylenated C ₈ -C ₂₂ 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 sold by Shell Chemical Cy., RHODASURF IDO60, RHODASURF LA90, RHODASURF IT070 marketed by Rhodia.
• amine oxides such as C ₁₀ -C ₁₈ alkyl dimethylamine oxides, C ₈ -C ₂₂ alkoxy ethyl dihydroxy ethylamine oxides;
• the alkylpolyglycosides described in US-A-4,565,647;
• C ₈ -C ₂₀ fatty acid amides _;
• ethoxylated fatty acids;
• ethoxylated amines

• X^- représente un ion halogène, CH₃SO₄ ^- ou C₂H₅SO₄ ^-
• R¹ et R² sont semblables ou différents et représentent un radical alkyl en C₁-C₂₀, un radical aryle ou benzyle
• R³ et R⁴ sont semblables ou différents et représentent un radical alkyl en C₁-C₂₀, un radical aryl ou benzyl ou un condensat oxyde d'éthylène et/ou de propylène (CH₂CH₂O)_x-(CH₂CHCH₃O)y-H, où x et y vont de 0 à 30 et ne sont jamais nuls ensemble,

comme le bromure de cétyltrimethylammonium, le RHODAQUAT® TFR commercialisé par la société RHODIA. Cationic surfactants include alkylammonium salts of the formula R ¹ R ² R ³ R ⁴ N ⁺ X ^- or

• X ^- represents a halogen ion, CH ₃ SO ₄ ^- or C ₂ H ₅ SO ₄ ^-
• R ¹ and R ² are the same or different and represent a C ₁ -C ₂₀ alkyl radical, an aryl or benzyl radical
• R ³ and R ⁴ are the same or different and represent a C ₁ -C ₂₀ alkyl radical, an aryl or benzyl radical or a condensate ethylene oxide and / or propylene oxide (CH ₂ CH ₂ O) _x - (CH ₂ CHCH ₃ O) yH, where x and y range from 0 to 30 and are never zero together,

such as cetyltrimethylammonium bromide, RHODAQUAT® TFR sold by Rhodia.

Examples of zwitterionic surfactants include aliphatic quaternary ammonium compounds, especially 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-sulphonate and 3- (N, N-dimethyl-N-hexadecyl-ammonio) 2-hydroxypropane 1-sulfonate.

Examples of amphoteric surfactants include betaines, sulfobetaines and carboxylates and fatty acid sulfonates and imidazole.

• les alkyldiméthylbétaïnes, les alkylamidopropyldiméthylbétaïnes, les alkyldiméthylsulfobétaïnes ou les alkylamidopropyldiméthylsulfobétaïnes comme le MIRATAINE CBS commercialisé par la société RHODIA, les produits de condensation d'acides gras et d'hydrolysats de protéines ;
• les alkylamphoacétates ou alkylamphodiacétates dont le groupe alkyle contient de 6 à 20 atomes de carbone
• les dérivés amphotères des alkylpolyamines comme l'AMPHIONIC XL® commercialisé par RHODIA, AMPHOLAC 7T/X® et AMPHOLAC 7C/X® commercialisés par BEROL NOBEL

The following surfactants are preferred:

• alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyldimethylsulphobetaines or alkylamidopropyldimethylsulphobetaines, such as the MIRATAINE CBS sold by the company Rhodia, the condensation products of fatty acids and of protein hydrolysates;
• alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms
• amphoteric derivatives of alkylpolyamines, such as AMPHIONIC XL® marketed by RHODIA, AMPHOLAC 7T / X® and AMPHOLAC 7C / X® marketed by BEROL NOBEL

Additional examples of suitable surfactants are compounds generally used as designated surfactants in the well-known "Surface Active Agents" manuals, volume I by Schwartz and Perry and Surface Active Agents and Detergents, Volume II by Schwartz, Perry and Berch.

Surfactants may be present at a rate of 0.005 to 60%, especially 0.5 to 40% by weight depending on the nature of the agent (s) surfactant (s) and the destination of the cleaning composition.

Advantageously, the weight ratio copolymer of formula general I, surfactant, is between 1/2 and 1/100, advantageously 1/5 and 1/50.

In what follows, unless otherwise stated, the proportions are indicated by weight.

• des "builders" (adjuvants de détergence améliorant les propriétés de surface des tensioactifs) organiques, notamment :
  • phosphonates organiques comme ceux de la gamme DEQUEST® de MONSANTO,
  • acides polycarboxyliques ou leurs sels hydrosolubles et les sels hydrosolubles de polymères ou de copolymères carboxyliques tels que . éthers polycarboxylates ou hydroxypolycarboxylates
  • acides polyacétiques ou leurs sels (acide nitriloacétique, acide N,N-dicarboxyméthyl-2-aminopentane dioïque, acide éthylènediamine tétraacétique, acide diéthylènetriamine pentaacétique, éthylènediaminetetraacétates, nitrilotriacétates comme le NERVANAID NTA Na₃ commercialisé par la société RHODIA, N-(2 hydroxyéthyl)-nitrilodiacétates),
  • sels d'acides alkyl C₅-C₂₀ succiniques
  • esters polyacétals carboxyliques
  • sels d'acides polyaspartiques ou polyglutamiques
  • acide citrique, acide gluconique ou acide tartrique ou leurs sels;
• des "builders" (adjuvants de détergence améliorant les propriétés de surface des tensioactifs) minéraux du type :
  • polyphosphates de métaux alcalins, d'ammonium ou d'alcanolamines tels que le RHODIAPHOS HPA3,5 commercialisé par la société RHODIA ,
  • pyrophosphates de métaux alcalins
  • zéolites;
  • silicates ;
  • borates, carbonates, bicarbonates, sesquicarbonates alcalins ou alcalino-terreux ;
  • cogranulés de silicates hydratés de métaux alcalins et de carbonates de métaux alcalins (sodium ou de potassium) décrits dans EP-A-488 868, comme le NABION 15 commercialisé par la société RHODIA ;
• des charges du type sulfate de sodium, chlorure de sodium à raison de 0 à 50 % du poids total de ladite composition exprimé en matière sèche;
• d'autres additifs divers comme des agents influant sur le pH de la composition détergente, notamment des additifs alcalinisants solubles dans le milieu lessiviel (phosphates de métaux alcalins, carbonates, perborates, hydroxydes

ou des additifs acidifiants solubles dans le milieu lessiviel (acides carboxyliques ou polycarboxyliques, bicarbonates et sesquicarbonates de métaux alcalins, acides phosphoriques et polyphosphoriques, acides sulfoniques) ; ou des enzymes ou des parfums, colorants, agents inhibiteurs de corrosion des métaux ;
* notamment pour le lavage à la main de la vaisselle

• des polymères cationiques synthétiques comme le MIRAPOL A550® , le MIRAPOL A15® commercialisés par RHODIA, le MERQUAT 550® commercialisé par CALGON.
• des polymères utilisés pour contrôler la viscosité du mélange et/ou la stabilité des mousses formées à l'utilisation, comme les dérivés de cellulose ou de guar (carboxyméthylcellulose, hydroxyéthylcellulose, hydroxypropylguar, carboxyméthylguar, carboxyméthylhydroxypropyl-guar )
• des agents hydrotropes, comme les alcools courts en C₂-C₈, en particulier l'éthanol, les diols et glycols comme le diéthylène glycol, dipropylène-glycol,
• des agents hydratants ou humectants pour la peau comme le glycérol, l'urée ou des agents protecteurs de la peau, comme les protéines ou hydrolysats de protéines, les polymères cationiques comme les dérivés cationiques du guar (JAGUAR C13S®, JAGUAR C162®, HICARE 1000® commercialisés par la société RHODIA,

Among the other usual additives used in the formulation of detergent compositions, mention may be made of:

• builders (detergency builders improving the surface properties of surfactants) organic, including:
  • organic phosphonates such as those from the MONSANTO DEQUEST® range,
  • polycarboxylic acids or their water-soluble salts and water-soluble salts of carboxylic polymers or copolymers such as. polycarboxylate ethers or hydroxypolycarboxylates
  • polyacetic acids or their salts (nitriloacetic acid, N, N-dicarboxymethyl-2-aminopentane dioic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetates, nitrilotriacetates such as NERVANAID NTA Na ₃ sold by Rhodia, N- (2 hydroxyethyl)) nitrilodiacetates)
  • C ₅ -C ₂₀ alkyl succinic acid salts
  • polyacetal carboxylic esters
  • salts of polyaspartic or polyglutamic acids
  • citric acid, gluconic acid or tartaric acid or their salts;
• "builders" (detergency builders improving the surface properties of surfactants) mineral type:
  • polyphosphates of alkali metals, of ammonium or of alkanolamines such as RHODIAPHOS HPA3,5 sold by Rhodia,
  • pyrophosphates of alkali metals
  • zeolites;
  • silicates;
  • alkali or alkaline earth borates, carbonates, bicarbonates, sesquicarbonates;
  • cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) described in EP-A-488 868, such as NABION® sold by RHODIA;
• fillers of sodium sulfate type, sodium chloride in a proportion of 0 to 50% of the total weight of said composition expressed as dry matter;
• other various additives such as agents affecting the pH of the detergent composition, especially alkalizing additives soluble in the washing medium (alkali metal phosphates, carbonates, perborates, hydroxides

or acidifying additives soluble in the washing medium (carboxylic or polycarboxylic acids, alkali metal bicarbonates and sesquicarbonates, phosphoric and polyphosphoric acids, sulfonic acids); or enzymes or perfumes, dyes, metal corrosion inhibitors;
* especially for hand washing dishes

• synthetic cationic polymers such as MIRAPOL A550®, MIRAPOL A15® marketed by RHODIA, MERQUAT 550® sold by Calgon.
• polymers used to control the viscosity of the mixture and / or the stability of foams formed in use, such as cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropyl-guar )
• hydrotropic agents, such as short C ₂ -C ₈ alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol,
• skin moisturizing or humectant agents such as glycerol, urea or skin-protecting agents, such as proteins or protein hydrolysates, cationic polymers such as cationic derivatives of guar (JAGUAR C13S®, JAGUAR C162®, HICARE 1000® marketed by Rhodia,

The compositions in which the copolymer described is used above, can be diluted (in water) from 1 to 10,000 times, preferably 1 to 1000 times before use.

The cleaning or rinsing composition is applied to the surface to be treated in such an amount as to allow, after rinsing, if necessary, and after drying a copolymer deposit of 0.0001 to 1 g / m ² , preferably 0.001 to 0.1 g / m ² of surface to be treated.

According to a first embodiment of the invention, the copolymer described above is used in a formulation for the cleaning the dishes by hand to give dishwashing hydrophilization properties as described above.

Preferred detergent formulations of this type comprise from 0.1 to 5 parts by weight of copolymer described above per 100 parts by weight of said composition and contain from 3 to 50, preferably from 10 to 40 parts by weight of at least one surfactant, preferably anionic, chosen especially from sulphates of saturated aliphatic C ₅ -C ₂₄ alcohols, preferably C ₁₀ -C ₁₆ aliphatic alcohols, optionally condensed with 0.5 to 30, preferably 0.5 to 5, in particular 0.5 to 3 moles of ethylene oxide, in acid form or in the form of a salt, especially alkaline (sodium), alkaline earth (calcium, magnesium)

The present invention aims more particularly at the use of copolymers described above in aqueous detergent formulations foaming liquids for hand washing dishes.

• des agents tensioactifs non ioniques tels que les oxydes d'amines, les alkylglucamides, les dérivés oxyalkylénés d'alcools gras, les alkylamides, les alcanolamides, des agents tensioactifs amphotères ou zwitterioniques.
• des agents bactéricides ou désinfectants non cationiques comme le triclosan
• des polymères cationiques synthétiques
• des polymères pour contrôler la viscosité du mélange et/ou la stabilité des mousses formées à l'utilisation
• des agents hydrotropes
• des agents hydratants ou humectants ou protecteurs de la peau
• des colorants, des parfums, des conservateurs comme déjà mentionné ci-dessus.

Said formulations may further contain other additives, including other surfactants, such as:

• nonionic surfactants such as amine oxides, alkylglucamides, oxyalkylenated fatty alcohol derivatives, alkylamides, alkanolamides, amphoteric or zwitterionic surfactants.
• non-cationic bactericidal or disinfectant agents such as triclosan
• synthetic cationic polymers
• polymers for controlling the viscosity of the mixture and / or the stability of foams formed upon use
• hydrotropic agents
• moisturizing or humectant or skin-protecting agents
• dyes, perfumes, preservatives as already mentioned above.

Another object of the invention is the use of a copolymer as defined above in compositions for cleaning external or rinsing, including bodywork, motor vehicles.

The copolymer can be present either in a detergent formula used for the washing operation, either in a rinsing product.

• des agents tensioactifs non ioniques (à raison de 0 à 30%, de préférence de 0.5 à 15 % de la formulation),
• des agents tensioactifs amphotères et/ou zwitterioniques (à raison de 0 à 30%, de préférence de 0.5 à 15 % de la formulation)
• des agents tensioactifs cationiques (à raison de 0 à 30%, de préférence de 0.5 à 15 % de la formulation);
• des agents tensioactifs anioniques (à raison de 0 à 30%, de préférence de 0.5 à 15 % de la formulation);
  • des adjuvants de détergence ("builders") organiques ou minéraux
  • des agents hydrotropes
  • des charges, des agents régulant le pH

The cleaning composition for motor vehicles advantageously comprises from 0.05 to 5% by weight of copolymer described above relative to the total weight of said composition, as well as:

• nonionic surfactants (from 0 to 30%, preferably from 0.5 to 15% of the formulation),
• amphoteric and / or zwitterionic surfactants (in a proportion of from 0 to 30%, preferably from 0.5 to 15% of the formulation)
• cationic surfactants (from 0 to 30%, preferably from 0.5 to 15% of the formulation);
• anionic surfactants (from 0 to 30%, preferably from 0.5 to 15% of the formulation);
  • organic or mineral builders
  • hydrotropic agents
  • fillers, pH regulating agents

The minimum amount of surfactant present may be at least 1% of the formulation)

The subject of the invention is also the use of the copolymer described above in compositions for rinsing the walls of showers.

Aqueous compositions for rinsing the walls of showers comprise from 0.02% to 5% by weight, preferably from 0.05% to 1% by weight. copolymer of the invention.

The other main active components of the compositions Aqueous shower rinses are at least one surfactant present in an amount of from 0.5 to 5% by weight and optionally a chelating agent of metals present in an amount ranging from 0.01 to 5% by weight.

The preferred metal chelating agents are the acid ethylenediaminetetraacetic acid (EDTA) and its analogues.

Aqueous shower rinse compositions contain advantageously water with possibly at least one lower alcohol in proportion and additives in a minority proportion (between approximately 0.1 and about 5% by weight, more preferably between 0.5% and 3% by weight, and even more preferably between 1% and 2% % in weight).

Certain surfactants that can be used in this type of application are described in US Patents 5,536,452 and 5,587,022.

Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan mono-oleates and castor oil polyethoxylated. Specific examples of such surfactants are the condensation products of 20 moles of ethylene oxide and mono-oleate sorbitan (marketed by RHODIA Inc. under the name ALKAMULS) PSMO-20® with an HLB of 15.0) and 30 or 40 moles of ethylene oxide and of castor oil (marketed by Rhodia Inc. under the name ALKAMULS EL-620 ® (HLB 12.0) and EL-719® (HLB 13.6) respectively). The degree of ethoxylation is preferably sufficient to obtain a surfactant having an HLB greater than 13. Other surfactants such as that alkylpolyglucosides are also well suited to these compositions.

The hydrophilic properties conferred by the copolymer described above are notably "anti-stain" and / or "anti-trace" properties.

Another object of the invention is the use, in a cleaning composition, in particular liquid, for hard surface, chosen among the compositions for cleaning the dishes by hand, cleaning external or rinsing of motor vehicles and rinsing of the walls of shower, at least one water-soluble or water-dispersible copolymer described above, as an agent to decrease the speed of drying the surface on which said liquid composition has been applied especially.

Examples 1-6, 19-20 below are intended to illustrate the invention.

Examples 7-18 are not included in the claim fields.

Examples 1 to 3 and Comparative Examples 4 to 6 Preparation of copolymers of the invention

Référence rapport a/b rapport c/b/a Polymère 1 50/50 2/4/4 Polymère 2 25/75 3/3/1 Polymère 3 50/50 1/1/1 Polymère 4 (camp) 100/0 4/0/6 Polymère 5 (comp) 80/20 0/2/8 Polymère 6 (comp) 100/0 0/0/1 Polymère 7 33/66 0/2/1 As before, copolymers of the following formula are prepared:

Reference report a / b report c / b / a Polymer 1 50/50 2/4/4 Polymer 2 25/75 3/3/1 Polymer 3 50/50 1/1/1 Polymer 4 (camp) 100/0 4/0/6 Polymer 5 (comp) 80/20 0/2/8 Polymer 6 (comp) 100/0 0/0/1 Polymer 7 33/66 0/2/1

The copolymers of Examples 1 to 3 and Examples Comparatives 4 to 6 are evaluated for their ability to confer properties hydrophilization to a glass plate.

Evaluation method

Si :

21-43 % en poids

Ca :

2,8-5.8 % en poids

Mg :

1,6-3,4 % en poids

Na :

6,8-14,2 % en poids

Al :

0,3-0,7 % en poids

A glass surface made up of 2.5 × 7.5 cm microscope slides, previously cleaned with ethanol, whose composition is given below:

Yes :

21-43% by weight

Ca:

2.8-5.8% by weight

Mg:

1.6-3.4% by weight

N / A :

6.8-14.2% by weight

Al:

0.3-0.7% by weight

The polymer studied is. solubilized in deionized water containing 0.5 g / l of BASF Symperonic A7 nonionic surfactant at a concentration of 0.5 or 0.1 g / l and the pH is adjusted by adding sodium hydroxide at pH = 9.

• dépôt de la solution de polymère et d'agent tensioactif sur la lame de verre ;
• rotation de la lame de verre à 1 500 tr/min pendant 30 secondes.

The solution of polymer and surfactant is deposited on a glass slide using a centrifugal applicator with:

• depositing the polymer and surfactant solution on the glass slide;
• rotation of the glass slide at 1500 rpm for 30 seconds.

• immersion de la lame de verre dans de l'eau épurée pendant 15 secondes ;
• séchage de la lame par rotation à l'applicateur rotatif, pendant 30 secondes à 1 500 tr/min.

A contact angle measurement can then be performed on the treated blade to obtain a result called "without rinsing". The result called "with rinsing" requires the following additional steps:

• immersion of the glass slide in purified water for 15 seconds;
• drying the blade by rotation to the rotary applicator for 30 seconds at 1500 rpm.

The angle of contact between the water and the treated glass is measured on a assembly of Ramé-Hart and is expressed in degrees. Eight to ten measurements are made by glass slide. Two to three glass slides are prepared for each polymer and the results therefore correspond to the average of 20 to 30 measures.

The contact angle obtained on a blade that has undergone the treatment described with an aqueous solution (demineralized water) without polymer gives a contact angle of 16 °.

The values before rinsing give information on the hydrophilic or hydrophobic nature of the polymer. But the most interesting is the contact angle after rinsing, which characterizes the hydrophilicity and strength of polymer / glass interactions. For the application cleaning of hard surfaces, a low value of this contact angle with rinsing is sought. A polymer having a lower contact angle at 12 ° and especially at 10 ° will give good performance in applications mentioned above.

The results obtained are reported in the following table: Example Contact angle 0.1 g / l before rinsing Contact angle 0.1 g / l after rinsing Contact angle 0.5 g / l before rinsing Angle of contact 0.5 g / l after rinsing 1 16.7 ± 1.0 17 ± 0.8 10.8 ± 1.0 6.8 ± 1.1 2 13 ± 0.6 12.8 ± 1.1 7.2 ± 0.8 6.3 ± 1.0 3 15 ± 0.7 13.5 ± 0.9 7.6 ± 0.8 10.9 ± 0.9 4 (comparative) 20.9 ± 0.5 22.9 t 1.3 19.7 ± 1.1 21.4 ± 1.3 5 (comparative) 19.5 ± 0.8 20.2 ± 0.5 20.3 ± 0.8 21.4 ± 1.2 6 (comparative) 23.3 ± 1.4 20.4 ± 2.4 24.1 ± 1.4 23, ± 1.2

These examples show that the polymers of the invention provide residual hydrophilization of the surfaces when the ratio a / b is less than 60/40. This is not the case for polymers given for comparative purposes which have a ratio a / b greater than 60/40.

EXAMPLES 7 to 9: Cleaning formulations for window cleaning

The table below reports the composition of three cleaning formulations used for window cleaning: components Formulations (by weight) Example 7 Example 8 Example 9 Isopropylic alcohol 7 7 15 Fatty alcohol (C12) ethoxylated (7OE) 0 0 3 Sodium dodecylbenzene sulphonate 0.5 0.5 0 Ammonium hydroxide 0.3 0.3 0.3 Monomethyl ether of dipropylene glycol 0.25 0.25 0.5 Copolymer example n ° 1 0.05 0.5 1 Water qs 100 qs 100 qs 100

The formulations of Examples 7 to 9 are used as such by spraying on the surface of the panes to be cleaned (6 to 8 sprays, ie 3 to 5 g of formulation per m ² of surface.

EXAMPLES 10 to 11: Cleaning formulations for hard surfaces such as tiles, ceramics, sinks, bathtubs.

The table below gives cleaning formulations for cleaning hard surfaces. components Formulations (by weight) Example 10 Example 11 Fatty alcohol (C12) ethoxylated (7OE) 6 8 Alkane (C12) sodium sulfonate 3 2 Welded such that pH = 10.4 such that pH = 10.4 Copolymer example n ° 2 1 0.5 Water qs 100 qs 100

The formulations of Examples 10 and 11 are diluted before use, at the rate of 10g of formulation in 1 liter of water.

EXAMPLE 12 to 15 Detergent formula for automatic dishwashers

A basic detergent formula is prepared from the compounds given in the table below: Sample formulation Example 12 Example 13 Example 14 Example 15 Sodium tripolyphosphate 0 0 60 35 Sodium carbonate 35 30 0 20 Sodium disilicate 20 15 23 10 Sodium citrate 20 15 0 0 Sodium sulphate 0 20 0 19 Sodium polyacrylate CP5 from BASF 6 5 0 0 Plurafac LF 403 2 1 2 2 Bleach system (perborate, 1 H ₂ O + TAED **) 12 10 10 10 Other additives (including benzatriaole, enzymes, perfume) 3 3 3 3 Polymer 7 2 1 2 1

EXAMPLES 16 to 18: Formulations for rinsing dishes in the dishwasher automatic

Formulation Example 16 Example 17 Example 18 Nonionic surfactant C13-3OP-7OE (linear fatty alcohol EO / OP) 12 12 12 Citric acid 3 3 3 Polymer Polymer 1 (2%) polymer 2 (2%) polymer 7 (2%) Water qsp to 100 qsp to 100 qsp to 100

EXAMPLES 19 and 20: Hand washing dishwashing formulation

Formulation example 19 example 20 Sodium alkylsulphonate (C14) 24 12 Ethoxylated fatty alcohol C12 - 1,5 EO 5 3 Ethoxylated fatty alcohol C10 - 7OE 4 4 Polymer polymer 1 (2%) polymer 7 (2%) Water qsp to 100 qsp to 100

EXAMPLES 21 and 22: Detergent formulations for cleaning surfaces hard (tiles, washbasins, bathtubs)

Formulation example 21 example 22 Sodium alkylsulphonate (C12) 24 12 Ethoxylated fatty alcohol C 12 - 6 EO 5 3 Ethanol 4 4 Polymer polymer 3 (2%) polymer 1 (2%) Water qsp to 100 qsp to 100

Claims (18)

1. Use, in a composition for treating hard surfaces, chosen from compositions for doing the washing-up by hand, for the external cleaning and rinsing of motor vehicles and for rinsing shower walls, of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:

   (a) at least one monomer compound of general formula I:

   

      in which:

   R₁ and R₄, independently of each other, represent a hydrogen atom or a linear or branched C₁-C₆ alkyl group;

   R₂ and R₃, independently of each other, represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C₁-C₆ chain;

   n and m are integers between 1 and 3;

   X, which may be identical or different, represent counterions which are compatible with the water-soluble or water-dispersible nature of the polymer;

   (b) at least one hydrophilic monomer bearing a function of acidic nature which is copolymerizable with (a) and capable of ionizing in the application medium,

   (c) optionally, at least one hydrophilic monomer compound containing ethylenic unsaturation and of neutral charge, bearing one or more hydrophilic groups, which is copolymerizable with (a) and (b);

      in which the a/b molar ratio is between 60/40 and 5/95; to give said treated hard surface hydrophilic properties.
2. Use according to claim 1, in which the monomer (a) is represented by the following formula:

   

      X^- being as defined in claim 1.
3. Use according to claim 1 or 2, in which (b) is chosen from C₃-C₈ carboxylic, sulphonic, sulphuric, phosphonic and phosphoric acids containing monoethylenic unsaturation.
4. Use according to any one of the preceding claims, in which the monomer (b) is chosen from acrylic acid, methacrylic acid, α-ethacrylic acid, β,β-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylideneacetic acid, propylideneacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacryloylalanine, N-acryloylhydroxyglycine, sulphopropyl acrylate, sulphoethyl acrylate, sulphoethyl methacrylate, sulphoethyl methacrylate, styrenesulphonic acid, vinylsulphonic acid, vinylphosphonic acid, phosphoethyl acrylate, phosphonoethyl acrylate, phosphopropyl acrylate, phosphonopropyl acrylate, phosphoethyl methacrylate, phosphonoethyl methacrylate, phosphopropyl methacrylate and phosphonopropyl methacrylate, and the ammonium and alkali metal salts of these acids.
5. Use according to any one of the preceding claims, in which the monomer (c) is chosen from acrylamide, vinyl alcohol, C₁-C₄ alkyl esters of acrylic acid and of methacrylic acid, C₁-C₄ hydroxyalkyl esters of acrylic acid and of methacrylic acid and polyalkoxylated esters of acrylic acid and of methacrylic acid.
6. Use according to any one of the preceding claims, in which X is chosen from chloride, sulphate, hydrogen sulphate, phosphate, citrate, formate and acetate anions.
7. Use according to any one of the preceding claims, characterized in that the water-soluble or water-dispersible copolymer is obtained by copolymerization:

   of 5 mol% to 60 mol%, preferably 20 mol% to 50 mol%, of the monomer (a);

   of 10 mol% to 95 mol%, preferably 20 mol% to 80 mol% of the monomer (b);

   of 0 mol% to 50 mol% of the monomer (c).
8. Use according to any one of the preceding claims, characterized in that the a/b molar ratio is between 50/50 and 10/90.
9. Use according to any one of the preceding claims, characterized in that the molecular mass of the copolymer is at least 1000 and not more than 20 000 000.
10. Use according to one of claims 1 to 9, characterized in that said copolymer of formula I represents from 0.001% to 10% of the total weight of said composition.
11. Use according to one of claims 1 to 10, characterized in that the copolymer of formula I/surfactant weight ratio is between 1/2 and 1/100.
12. Use according to one of claims 1 to 11 in a composition for doing the washing-up by hand, characterized in that said water-soluble or water-dispersible copolymer is used in proportions of from 0.1 to 5 parts by weight, relative to the total weight of said composition, and in that said composition also comprises:

    from 5 to 80 parts and preferably from 10 to 50 parts by weight of at least one surfactant, preferably an anionic surfactant;

    at least one non-cationic bactericide or disinfectant;

    at least one synthetic cationic polymer;

    a polymer used to control the viscosity of the mixture and/or the foam stability;

    a hydrotropic agent;

    a moisturizer or wetting agent or a protecting agent for the skin;

    a dye, fragrance and a preserving agent.
13. Use according to one of claims 1 to 11 in a composition for the external cleaning of motor vehicles, characterized in that said water-soluble or water-dispersible copolymer is used in proportions of from 0.1 to 5 parts by weight, relative to the total weight of said composition, and in that said composition also comprises:

    from 0% to 30%, relative to the weight of the formulation, of at least one nonionic surfactant;

    from 0% to 30%, relative to the weight of the formulation, of at least one anionic surfactant;

    from 0% to 30% by weight of an amphoteric and/or zwitterionic surfactant;

    from 0% to 30% by weight of a cationic surfactant;

    the minimum amount of surfactant being at least 1%;

    from 0% to 50%, relative to the weight of the formulation, of an inorganic and/or organic detergent adjuvant ("builder");

    optionally, a hydrotropic agent, fillers and pH regulators.
14. Use according to one of claims 1 to 11 in a composition for rinsing shower walls, characterized in that said water-soluble or water-dispersible copolymer is used in proportions of 0.05% to 5% by weight and advantageously from 0.05% to 1% by weight relative to the total weight of said composition, and in that said composition also comprises:

    from 0.5% to 5% by weight of a nonionic surfactant, in particular a polyethoxylated fatty acid ester or an alkylpolyglucoside;

    optionally, from 0.01% to 5% by weight of a metal-chelating agent.
15. Use according to one of claims 1 to 14, characterized in that the amount of water-soluble or water-dispersible copolymer to be deposited on the surface to be treated to give it hydrophilic properties is from 0.0001 g/m² to 6 g/m² and preferably from 0.001 g/m² to 2 g/m².
16. Use according to one of claims 1 to 15, characterized in that the hydrophilic properties given by said water-soluble or water-dispersible copolymer are long-lasting "stain-resistance" and "mark-resistance" properties.
17. Use according to any one of claims 1 to 16, characterized in that said water-soluble or water-dispersible copolymer also makes it possible to increase the speed of drying of the surface treated by said composition.
18. Use according to claim 17, characterized in that said composition is liquid.