WO2001005922A1 - Cleansing composition for hard surfaces - Google Patents

Abstract

The invention concerns a cleansing composition for hard surfaces comprising at least a surfactant and a water soluble or water dispersible copolymer comprising, in the form of polymerised units: (a) at least a monomer compound of general formula (I); (b) at least a hydrophilic monomer selected among monoethylenically unsaturated C3-C8 carboxylic acids, their anhydrides and their water soluble salts; (c) optionally at least an ethylenically unsaturated hydrophilic monomer compound of neutral charge bearing one or several hydrophilic groups, copolymerisable with (a) and (b).

Description

 CLEANING COMPOSITION FOR HARD SURFACES

The subject of the present invention is a cleaning composition intended for the treatment of hard industrial domestic or collective surfaces, in particular of the ceramic, tiling or glass type, aiming to confer on them hydrophilic properties.

The invention more particularly relates to a cleaning composition intended for the treatment of such a surface which is capable of imparting thereto retentive hydrophilic properties so as to avoid the subsequent presence of traces due in particular to the drying of the drops of water deposited on said surface.

Commercial detergent formulations allow effective cleaning of hard industrial, domestic or community surfaces. They generally consist of an aqueous solution of surfactants, in particular nonionic and anionic surfactants, alcohol (s) to facilitate drying, and optionally sequestering agents and bases to adjust the pH. A major shortcoming of these detergent formulations is that the subsequent contact of the hard surface with water can lead to the presence of traces during drying. This contact with water after applying detergent can come, for example, from rainwater in the case of windows, mains water on a bathroom tile, or rinse water when cleaning requires rinsing. They can also come from drying dishes in the open air in the case of detergent formulas for cleaning dishes by hand, or from drying dishes automatically in the case of detergents for dishwashers . In the case of automatic dishwashing, said formula can either be used in the cleaning cycle (detergent formula) or during rinsing (rinsing liquid).

The presence of traces or stains left on hard surfaces by water coming into contact with them is due to the phenomenon of contraction of water drops in contact with the hard surface which, during subsequent drying, leave on the surface traces reproducing the original shapes and dimensions of the drops. So far, there is no satisfactory solution to this problem.

To solve the problem posed by the retraction and drying of the water drops, the solution consists in increasing the hydrophilicity of the surface in order to obtain a contact angle as small as possible between the hard surface to be treated and the drop d 'water.

The work of the inventors having led to the present invention made it possible to determine that this problem could be resolved effectively and lastingly by incorporating into conventional cleaning compositions for hard surfaces, a water-soluble or water-dispersible organic polymer compound having both a function of interaction with the surface to be treated and a function giving this surface a hydrophilic character and having certain particular properties.

A first subject of the invention consists of a cleaning composition for hard surfaces comprising at least one surfactant and at least one 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

- Ri is a hydrogen atom or a methyl group, preferably a methyl group;

- R ₂ , R ₃ and R ₄ are linear or branched C ₁ -C ₄ alkyl groups;

- n represents an integer from 1 to 4, in particular the number 3;

- X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer; (b) at least one hydrophilic monomer chosen from monoethylenically unsaturated C ₃ -C ₈ carboxylic acids, their anhydrides and their water-soluble salts;

(c) optionally at least one hydrophilic monomeric compound with ethylenic unsaturation of neutral charge carrying one or more hydrophilic groups, copolymerizable with (a) and (b);

the average charge Q of the copolymer defined by the equation:

Q = f] - fbir

[at]

- in which [a] represents the molar concentration of monomer (a);

- in which [b] represents the molar concentration of monomer (b); and

- and r represents the neutralization rate of the monomers (b) defined by: r = [COO1

[COOH] + [COO1 where [COOH] and [COO ^" ] respectively represent the molar concentrations of monomers (b) in the form of carboxylic acid and carboxylate at the pH of use of the cleaning composition, being greater than 0 and capable of go up to 0.4, advantageously up to 0.2 Advantageously, the molar ratio (a) / (b) is between 25/75 and 70/30

The molar ratio c / (a + b + c) is advantageously between 0 and 40/100, preferably between 10/100 and 30/100.

The copolymer according to the invention is preferably random.

The average charge Q of said copolymer at the pH of the cleaning composition can be determined by any known means, in particular by assay using a polyvinyl sulfate solution or by zetametry. The monomer (a) gives the copolymer interaction characteristics with the surface to be treated, in particular allowing the copolymer to be anchored on this surface.

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

By "anti-fingerprint or residual anti-stain properties", it is meant that the treated surface retains these properties over time, including after subsequent contact with water, whether it is rainwater , water from the distribution network or rinse water with or without rinse aid added.

This hydrophilization property of the surface also makes it possible to reduce the formation of fogging on the surface; this benefit can be exploited in cleaning formulas for windows and mirrors, in particular in bathrooms.

In addition, when a surface is treated with the copolymer according to the invention, the drying speed thereof, immediately after the application of the polymer but also after subsequent and repeated contacts with an aqueous medium is improved so very significant.

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

Unless otherwise indicated, when we speak of molecular mass, it will be the molecular mass by weight, expressed in g / mol. This can be determined by aqueous gel permeation chromatography (GPC) or measurement of the intrinsic viscosity in a 1 N solution of NaNO ₃ at 30 ° C.

The preferred monomer (a) is MAPTAC of the following formula:

Among the preferred monomers (b), there may be mentioned acrylic acid, methacrylic acid, α-ethacrylic acid, β.β-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, acid allylacetic, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacroyl-alanine, N-acryloyl-hydroxy-glycine, anhydrides, and the alkali metal and ammonium salts thereof.

Among the monomers (c), there may be mentioned acrylamide, vinyl alcohol, C1-C6 alkyl esters of acrylic acid and methacrylic acid, C1-C4 hydroxyalkyl esters of acrylic acid and methacrylic acid, especially pacrylate and methacrylate of ethylene glycol and propylene glycol, polyalkoxylated esters of acrylic acid and methacrylic acid, especially esters of polyethylene glycol and polypropylene glycol.

X is any suitable counter-anion compatible with the water-soluble or water-dispersible nature of the copolymer, in particular an anion of halogen, sulphate, hydrogen sulphate, phosphate, citrate, formate and acetate.

The copolymers of the invention can be obtained according to known techniques for the radical polymerization of ethylenically unsaturated monomers.

The cleaning compositions according to the invention advantageously have a weight ratio of water-soluble or water-dispersible copolymer / surfactant of between 1/2 and 1/100, preferably between 1/5 and 1/50.

A particularly preferred copolymer is the following:

- in which the sum of x + y + z is equal to 4- 100%, x, y and z representing the molar% of units derived respectively from acrylamide, acrylic acid and MAPTAC in the copolymer

- the ratio y / z is from 25/75 to 70/30, and

- x is between 0 and 40%, preferably between 10 and 30%.

Said copolymer can be introduced into a formulation intended to treat hard surfaces at a content of between 0.001% and 10% by weight relative to the total weight of the formulation, depending on the concentration of active ingredients in the composition.

The composition according to the invention comprises at least one surfactant. This is advantageously anionic and / or nonionic. It can also be cationic, amphoteric or zwitterionic.

Among the anionic surfactants, mention may be made in particular of soaps such as the C ₈ -C ₂₄ fatty acid salts, for example the salts of fatty acids derived from copra and tallow; alkylbenzenesulfonates, including linear alkylbenzenesulfonates C8 latter _3, wherein the alkyl group comprises from 10 to 16 carbon atoms, alcohol-sulfates, the ethoxylated alcohol sufates, the hydroxyalkylsulfonates; alkyl sulfates and sulfonates, in particular Cι ₂ -C-i6, monoglycerides-sulfates, and fatty acid chloride condensates with hydroxyalkylsulfonates.

Advantageous anionic surfactants are in particular: - the alkyl esters sulfonates of formula R-CH (SO ₃ M) -COOR ', where R represents a C _8-2 o, preferably C10-C16 alkyl radical, R' a radical C1-Cβ alkyl, preferably C1-C ₃ and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...). Mention may very particularly be made of methyl ester sulfonates whose radicals R is C-14-C16;

- the alkyl sulfates of formula ROSOsM, where R represents a C ₅ -C ₂ alkyl or hydroxyalkyl radical, preferably C-10-C-iβ, 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 30 units, preferably from 0.5 to 10 OE and / or OP units;

the alkylamide sulfates of formula RCONHR'OSO ₃ M where R represents an alkyl radical in C ₂ -C ₂₂ , preferably in C6-C ₂₀ , R 'an alkyl radical in C ₂ -C ₃ , M representing an atom of hydrogen 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 60 OE and / or OP units;

- the salts of saturated or unsaturated fatty acids with Cβ-C ₂₄ , preferably with Cι ₄ -C ₂ o, C ₉ -C ₂₀ alkylbenzenesulfonates, primary or secondary Cs-C ₂₂ alkylsulfonates, alkylglycerol sulfonates , 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-acyls sarcosinates, alkyl glycoside sulfates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...);

- alkylated or alkylarylated ester phosphates such as RHODAFAC RA600, RHODAFAC PA15 or RHODAFAC PA23 marketed by the company RHODIA. Among the nonionic surfactants, there may be mentioned in particular the condensates of alkylene oxide, in particular of ethylene oxide with alcohols, polyols, alkylphenols, esters of fatty acids, acid amides fatty and fatty amines; amine oxides, sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, in particular sucrose monopalmitate; long chain tertiary phosphine oxides; dialkyisulfoxides; polyoxyethylene and polyoxypropylene block copolymers; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly (ethylene oxide) and fatty acid amides modified to give them a hydrophobic character (for example, mono- and diethanolamides of fatty acids containing from 10 to 18 carbon atoms ).

Mention may in particular be made of polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the 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 Cs-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 sold by Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by Shell Chemical Cy., RHODASURF IDO60, RHODASURF LA90, RHODASURF IT070 marketed by the company RHODIA.

. amine oxides such as alkyl oxides C-io-Ciβ dimethylamines, alkoxy oxides C _δ -C ₂ 2 ethyl dihydroxy ethylamines;

. the alkylpolyglycosides described in US-A-4,565,647;

. amides of C8-C20 fatty acids;

. ethoxylated fatty acids;

. ethoxylated amines

Cationic surfactants are in particular alkylammonium salts of formula R ¹ R ² R ³ R ⁴ N ⁺ X ^" where

. X ^" represents a halogen ion, CH ₃ SO ₄ ^" or C ₂ H ₅ SO ₄ ^" . R ¹ and R ² are similar or different and represent an alkyl radical in CC ₂ o, an aryl or benzyl radical

. R ³ and R ⁴ are similar or different and represent a C ₁ -C ₂₀ alkyl radical. an aryl or benzyl radical or an ethylene and / or propylene oxide condensate (CH ₂ CH ₂ O) _x - (CH ₂ CHCH ₃ O) yH, where x and y go from 0 to 30 and are never zero together , like cetylthmethylammonium bromide, RHODAQUAT® TFR sold by the company RHODIA.

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

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

The following surfactants are preferred: alkyldimethylbetaines, alkylamidopropyldimethyl betaines, alkyldimethylsulfobetaines or alkylamidopropyldimethylsulfobetaines such as MIRATAINE CBS sold by the company RHODIA, condensation products of fatty acids and protein hydrolysates;

. alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms the 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 surfactants designated in the well known manuals "Surface Active Agents", volume I by Schwartz and Perry and "Surface Active Agents and Detergents", volume II by Schwartz, Perry and Berch.

The surfactants can be present in an amount of 0.005 to 60%, especially from 0.5 to 40% by weight depending on the nature of the surfactant (s) and the destination of the cleaning composition.

Among the other usual additives used in the formulation of detergent compositions, there may be mentioned: * in particular for washing in a dishwashing machine

- organic "builders" (detergency builders improving the surface properties of surfactants) of the type: organic phosphonates like those in the range

DEQUEST® from MONSANTO, (at a rate of 0 to 2% of the total weight of detergent composition expressed as dry matter in the case of a dishwasher composition);

. polycarboxylic acids or their water-soluble salts and the water-soluble salts of carboxylic polymers or copolymers such as

. polycarboxylate or hydroxypolycarboxylate ethers. polyacetic acids or their salts (nithloacetic acid, N acid, N- dicarboxymethyl-2-aminopentane dioic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetates, nitrilotriacetates such as NERVANAID NTA Na ₃ hydroxy marketed by the company N 2 hydroxyethyl N 3 -nitrilodiacetates), (at a rate of 0 to 10% of the total weight of detergent composition expressed as dry matter in the case of a dishwasher composition);

. salts of succinic C ₅ -C ₂ o acids

. polyacetal carboxylic esters

. salts of polyaspartic or polyglutamic acids. citric acid, gluconic acid or tartaric acid or their salts (at a rate of 0 to 10% of the total weight of detergent composition expressed as dry matter in the case of a composition for dishwasher);

- mineral "builders" (detergency builders improving the surface properties of surfactants) of the type: polyphosphates of alkali metals, ammonium or alkanolamines such as RHODIAPHOS HPA3.5 sold by the company RHODIA, (at a rate of 0 to 70% of the total weight of detergent composition expressed as dry matter in the case of a composition for dishwashers);

. alkali metal pyrophosphates. zeolites;

. silicates (in an amount which can range up to approximately 50% of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition);

. borates, carbonates, bicarbonates, alkali or alkaline earth sesquicarbonates (in an amount which can range up to approximately 50% of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition);

. cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) described in EP-A-488 868, such as NABION 15 sold by the company RHODIA (in an amount which can range up to approximately 50% by weight total of said detergent composition expressed as dry matter in the case of a dishwasher composition);

(the total amount of organic and / or mineral "builders", which may represent up to 90% of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition);

- bleaching agents of the perborate type, percarbonates associated or not with acetylated bleaching activators such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED) or chlorinated products of the chloroisocyanurate type, or chlorinated products of the alkali metal hypochlorites type, (at a rate of 0 to 30% of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition);

- auxiliary cleaning agents of the acrylic acid and maleic anhydride copolymer type or homopolymers of acrylic acid (at a rate of 0 to 10%, of the total weight of said detergent composition expressed as dry matter in the case of a composition for a dishwasher); - fillers of the sodium sulfate, sodium chloride type at a rate of 0 to 50% of the total weight of the said composition expressed as dry matter;

- other various additives such as agents influencing the pH of the detergent composition, in particular alkalizing additives soluble in the washing medium (alkali metal phosphates, carbonates, perborates, hydroxides or acidifying additives soluble in the washing medium (carboxylic acids or polycarboxylic, bicarbonates and sesquicarbonates of alkali metals, phosphoric and polyphosphoric acids, sulfonic acids, etc.) or enzymes or perfumes, dyes, metal corrosion inhibiting agents;

* especially for hand washing dishes

- synthetic cationic polymers such as MIRAPOL A550®, MIRAPOL A15® marketed by RHODIA, MERQUAT 550® marketed by CALGON ..

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

- hydrotropic agents, such as C ₂ -C ₈ short alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol, ...

- moisturizing or humectants for the skin such as glycerol, urea or skin protective agents, such as proteins or protein hydrolysates, cationic polymers such as cationic guar derivatives (JAGUAR C13S®, JAGUAR C162®, HICARE 1000® marketed by RHODIA,

The compositions according to the invention can be diluted (in water) from 1 to 10,000 times, preferably from 1 to 1,000 times before use.

The cleaning composition according to the invention is applied to the surface to be treated in an amount such that it allows, after rinsing if necessary, and after drying, a deposit of copolymer according to the invention from 0.0001 to 1g / m ² , of preferably 0.001 to 0.1 g / m ² of surface to be treated. According to a particularly advantageous mode, the cleaning composition according to the invention is used for the treatment of glass surfaces, in particular of panes. This treatment can be carried out by various known techniques. Mention may in particular be made of window cleaning techniques by spraying with a water jet using Karcher® type devices.

The amount of polymer introduced will generally be such that, when using the cleaning composition, after possible dilution, the concentration is between 0.001 g / l and 2 g / l, preferably 0.005 g / l and 0, 5 g / l.

Unless otherwise indicated, the proportions are given by weight.

The window cleaning composition according to the invention comprises:

- from 0.001 to 10%, preferably 0.005 to 3% by weight of at least one water-soluble or water-dispersible copolymer as defined above;

- from 0.005 to 20%, preferably from 0.5 to 10% by weight of at least one nonionic surfactant (for example an amine oxide) and / or anionic; and

- the rest being formed of water and / or various additives customary in the field.

The window cleaning formulations comprising said polymer may also contain:

- from 0 to 10%, advantageously from 0.5 to 5% of amphoteric surfactant,

- From 0 to 30%, advantageously from 0.5 to 15% of solvent such as alcohols, and the rest being constituted by water and usual additives (perfumes in particular).

The pH of the composition is advantageously between 6 and 11. The a / b ratio is preferably between 40/60 and 60/40. The composition of the invention is also advantageous for cleaning the dishes by hand or in an automatic machine. In the latter case, said copolymer may be present, either in the detergent formula used in the washing cycle, or in the rinsing liquid.

Detergent formulations for washing dishes in automatic dishwashers advantageously comprise from 0.1 to 5%, preferably 0.2 to 3% by weight of water-soluble or water-dispersible copolymer relative to the total weight of dry matter of the composition .

The detergent compositions for dishwashers also comprise at least one surfactant, preferably nonionic in an amount ranging from 0.2 to 10%, preferably from 0.5 to 5% by weight of said detergent composition expressed as dry matter, the remainder being constituted by various additives and fillers, as already mentioned above.

The pH is advantageously between 8 and 12. The a / b ratio is preferably between 40/60 and 60/40.

Formulations for rinsing dishes in an automatic dishwasher advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5% by weight of copolymer relative to the total weight of the composition.

They also comprise from 0.5 to 20%, preferably 0.5 to 15% by weight relative to the total weight of said composition of a surfactant, preferably nonionic or a mixture of nonionic and anionic surfactant.

Among the preferred nonionic surfactants, mention may be made of polyoxyethylenated C ₆ -C ₁₂ alkylphenol type surfactants, polyoxyethylenated and / or polyoxypropylenated C ₈ -C ₂₂ aliphatic alcohols, ethylene oxide-oxide block copolymers propylene, optionally polyoxyethylenated carboxylic amides ....

They also comprise from 0 to 10%, preferably from 0.5 to 5% by weight relative to the total weight of the composition of an organic acid sequestering with calcium, preferably citric acid.

They can also include an auxiliary agent of the copolymer type of acrylic acid and maleic anhydride or homopolymers of acrylic acid in an amount of 0 to 15%, preferably 0.5 to 10% by weight relative to the total weight of said composition.

The pH is advantageously between 4 and 7. The a / b ratio is preferably between 30/70 and 55/45.

The invention also relates to a cleaning composition for washing dishes by hand.

Preferred detergent formulations of this type comprise from 0.1 to 5 parts by weight of copolymer of the invention 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 at least one surfactant, preferably anionic, chosen in particular from sulphates of aliphatic alcohols saturated with C ₅ -C ₂₄ , preferably with C ₁₀ -C ₁₆ , optionally condensed with approximately 0.5 to 30, preferably 0.5 to 5, very particularly 0.5 to 3 moles of ethylene oxide, in acid form or in the form of a salt, in particular alkaline (sodium), alkaline earth (calcium, magnesium) ...

The present invention relates more particularly to aqueous detergent foaming liquid formulations for washing dishes by hand.

Said formulations may also contain other additives, in particular other surfactants, such as:

. nonionic surfactants such as amine oxides, alkylglucamides, oxyalkylene derivatives of fatty alcohols, alkylamides, alkanolamides, amphoteric or zwitterionic surfactants.

. non-cationic bactericidal agents or disinfectants such as triclosan

. synthetic cationic polymers

. polymers to control the viscosity of the mixture and / or the stability of the foams formed in use

. hydrotropic agents

. moisturizing or moisturizing or protective agents for the skin

. dyes, perfumes, preservatives ... as already mentioned above

The pH of the composition is advantageously between 6 and 8. The a / b ratio is preferably between 40/60 and 60/40.

Another subject of the invention consists of a cleaning composition for the external cleaning, in particular of the bodywork, of motor vehicles.

In this case also, the copolymer according to the invention can be present either in a detergent formula used for the washing operation, or in a rinsing product.

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

- nonionic surfactants (at a rate of 0 to 30%, preferably 0.5 to 15% of the formulation),

- amphoteric and / or zwitterionic surfactants (at a rate of 0 to 30%, preferably 0.5 to 15% of the formulation)

- cationic surfactants (at a rate of 0 to 30%, preferably 0.5 to 15% of the formulation);

- anionic surfactants (at a rate of 0 to 30%, preferably 0.5 to 15% of the formulation);

. organic or mineral detergency builders

. hydrotropic agents

. fillers, pH regulating agents ...

The minimum amount of surfactant present in type of composition can be at least 1% of the formulation)

The pH is advantageously between 8 and 12. The a / b ratio is preferably between 40/60 and 60/40. The composition of the invention is also particularly suitable for cleaning hard surfaces other than those described above, in particular of ceramics (tiles, baths, sinks, etc.).

In this case, the cleaning formulation advantageously comprises from 0.02 to 5% by weight of copolymer relative to the total weight of said composition as well as at least one surfactant.

As surfactants, nonionic surfactants are preferred, in particular the compounds produced by condensation of alkylene oxide groups as described above which are of hydrophilic nature with a hydrophobic organic compound which may be of aliphatic or alkyl-aromatic nature.

The length of the hydrophilic chain or of the polyoxyalkylene radical condensed with any hydrophobic group can be easily adjusted to obtain a water-soluble compound having the desired degree of hydrophilic / hydrophobic balance (HBL).

The amount of nonionic surfactants in the composition of the invention is generally from 40 to 30% by weight, preferably from 0 to 20% by weight

An anionic surfactant can optionally be present in an amount of 0 to 30%, advantageously 0 to 20% by weight.

It is also possible but not compulsory to add amphoteric, cationic or zwitterionic detergents in the composition of the present invention for cleaning hard surfaces.

The total amount of surfactant compounds used in this type of composition is generally between 1.5 and 50%, preferably between 5 and 30% by weight, and more particularly between 10 and 20% by weight relative to the total weight of the composition.

The hard surface cleaning composition of the present invention may also contain other minority ingredients which are cleaning additives.

For example, the composition can contain organic or inorganic detergency builders as mentioned above. In general, the detergency builder is used in an amount between 0.1 and 25% by weight relative to the total weight of the composition.

Another optional ingredient of the hard surface cleaning compositions of the invention is a foam control agent, which can be used in compositions having a tendency to produce excess foam when in use. An example of these materials are soaps. The soaps are salts of fatty acids and include the soaps of alkali metals, in particular the sodium, potassium, ammonium and alkanol ammonium salts of higher fatty acids containing about 8 to 24 carbon atoms, and preferably d '' about 10 to about 20 carbon atoms. Particularly useful are the sodium, potassium and mono-, di- and triethanolamine salts or mixtures of fatty acids derived from coconut oil and ground nut oil. The amount of soap can be at least 0.005% by weight, preferably from 0.5% to 2% by weight relative to the total weight of the composition. Additional examples of foam control materials are organic solvents, hydrophobic silica, silicone oil and hydrocarbons.

The hard surface cleaning compositions of the present invention may also contain in addition to the above-mentioned ingredients, other optional ingredients such as pH regulating agents, dyes, optical brighteners, soil suspending agents, detergent enzymes, compatible bleaches, gel formation regulators, freeze-thaw stabilizers, bactericides, preservatives, solvents, fungicides, insect repellents, hydrotropic agents, fragrances and opacifiers or pearlescent.

The pH of the composition is advantageously between 3 and 11. The a / b ratio is preferably between 30/70 and 60/40.

The composition of the invention can also be implemented by cleaning the toilet bowls. A composition particularly suitable for this purpose comprises from 0.05 to 5% by weight of copolymer according to the invention, having an a / b ratio of between 25/75 and 50/50.

The composition for cleaning toilet bowls according to the invention also comprises an acid cleaner which can consist of a mineral acid such as phosphoric, sulfamic, hydrochloric, hydrofluoric, sulfuric, nitric, chromic acid and mixtures thereof or an organic acid, in particular acetic, hydroxyacetic, adipic, citric, formic, fumaric, gluconic, glutaric, glycolic, malic, maleic, lactic, malonic, oxalic, succinic and tartaric acid as well as mixtures thereof, salts of acids such as sodium bisulfate and mixtures thereof.

The amount of acidic ingredients is preferably between 0.1 to about 40%, and preferably between 0.5 and about 15% by weight relative to the total weight of the composition.

The preferred amount depends on the type of acid cleaner used: for example with sulfamic acid. It is between approximately 0.2 and approximately 1%, with hydrochloric acid between approximately 1 and approximately 5%, with citric acid between approximately 2 and approximately 10%, with formic acid, between approximately 5 and approximately 15% and with phosphoric acid, between about 5 and about 30% by weight.

The amount of acid agent is generally such that the final pH of the composition is from about 0.5 to about 4, preferably 1 to 3.

The toilet bowl cleaning composition also comprises from 0.5 to 10% by weight of a surfactant so as to contribute to the removal of soiling or so as to provide foaming or wetting characteristics or to increase the cleaning effectiveness of the composition. The surfactant is preferably an anionic or nonionic surfactant.

Cationic surfactants can also be added to the composition for cleaning toilet bowls according to the invention to provide germicidal properties. Those skilled in the art will see that agents amphoteric surfactants can also be used. Mixtures of various surfactants can be used if desired.

The toilet bowl cleaning composition according to the invention can also comprise a gum type thickener, in particular a xanthan gum introduced at a concentration of 0.1 to 3%, as well as one or more of the following minority ingredients: a preservative intended to prevent the growth of microorganisms in the product, a dye, a perfume, and / or an abrasive.

The composition according to the invention is also suitable for rinsing the walls of the showers.

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

The other main active components of the aqueous shower rinse compositions of the present invention are at least one surfactant present in an amount ranging from 0.5 to 5% by weight and optionally a metal chelating agent present in an amount ranging from 0 , 01 to 5% by weight.

Preferred metal chelating agents are ethylenediaminetetraacetic acid (EDTA) and its analogs.

The aqueous rinsing compositions for showers advantageously contain water with optionally at least a lower alcohol in the majority proportion and additives in the minority proportion (between approximately 0.1 and approximately 5% by weight, more advantageously between approximately 0.5% and about 3% by weight, and even more preferably between about 1% and about 2% by weight).

Certain surfactants which can be used in this type of application are described in US Patents 5,536,452 and 5,587,022, the content of which is incorporated by reference in the present description.

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

The pH of the composition is advantageously between 7 and 11. The a / b ratio is preferably between 40/60 and 60/40.

The composition according to the invention can also be used for cleaning ceramic hobs.

Advantageously, the formulations for cleaning ceramic hobs of the invention include:

- 0.1 to 5% by weight of the copolymer of the invention;

- 0.1 to 1% by weight of a thickener such as a xanthan gum;

- 10 to 40% by weight of an abrasive agent such as calcium carbonate or silica;

- 0 to 7% by weight of a glycol such as butyldiglycol;

- 1 to 10% by weight of a nonionic surfactant;

- 0.1 to 3% by weight of a silicone type copolymer; and

- possibly alkalizing agents or sequestrants. The pH of the composition is advantageously between 7 and

12 44. The a / b ratio is preferably between 40/60 and 60/40.

A subject of the invention is also the use, in a cleaning composition for a hard surface, of at least one 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

- Ri is a hydrogen atom or a methyl group, preferably a methyl group;

- R ₂ , R ₃ and R ₄ are linear or branched C1-C4 alkyl groups;

- n represents an integer from 1 to 4, in particular the number 3;

- X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer;

(b) at least one hydrophilic monomer chosen from monoethylenically unsaturated C ₃ -C ₈ carboxylic acids, their anhydrides and their water-soluble salts;

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

the average charge Q of the polymer defined by the equation:

Q = fal - fb] r [a]

- in which [a] represents the molar concentration of monomer (a);

- in which [b] represents the molar concentration of monomer (b); and

- and r represents the neutralization rate of the monomers (b) defined by: r = fCOOl

[COOH] + [COQ-] where [COOH] and [COO ^" ] represent respectively the molar concentrations of monomers (b) in the form of carboxylic acid and carboxylate at the pH of use of the cleaning composition, being greater than 0 and possibly ranging up to 0, 4, advantageously up to 0.2 to give the hard surface to which it has been applied, hydrophilization properties.

Advantageously, the molar ratio (a) / (b) is between 25/75 and 70/30.

The molar ratio (c) / (a + b + c) is advantageously between 0 and 40/100, preferably between 10/100 and 30/100. j

The hydrophilization properties imparted by the copolymer of the invention are in particular "anti-flow", "anti-fog" properties and "anti-stain" and / or "anti-trace" properties.

The subject of the invention is also the use, in a liquid cleaning composition for hard surfaces, of at least one water-soluble or water-dispersible copolymer of general formula I given above, as an agent making it possible to reduce the drying speed of the surface on which said liquid composition has been applied.

It likewise relates to a process for improving the hydrophilicity of a hard surface, by treatment of said surface with the aid of a cleaning composition comprising at least one copolymer of general formula I given above.

It also relates to a method for improving the drying speed of a hard surface after cleaning thereof using a cleaning composition, by incorporating into said composition at least one copolymer of general formula I given above. The examples below are intended to illustrate the invention.

EXAMPLE 1:

An acrylic acid / MAPTAC / acrylamide copolymer having a 40/40/20 molar ratio is prepared in a manner known per se. Its weight average molecular mass is of the order of 2,000,000.

Two detergent solutions are prepared, each containing a concentration of 50 ppm of polymer, 0.2 g / l of non-ionic surfactant Symperonic A7 from BASF and the pH of which is adjusted by adding 0.01 molar soda. The transmittance of the solution is measured using a photometer. The charge of the polymer is determined by assay with a solution of potassium polyvinyl sulfate.

Each aqueous solution is sprayed onto a black ceramic tile, arranged vertically. After the ceramic tile has dried, pure water is sprayed onto the surface. The flow of water on the surface of the ceramic is observed visually.

The results obtained are recorded in the table below:

This result shows that the polymer solution 1 having a low pH and consequently a high average charge does not allow an effective hydrophilization benefit to be obtained on the surface. On the other hand, the polymer having a very low charge (solution 2) as defined in the invention leads to effective hydrophilization of the surface. EXAMPLES 2 to 4:

Assessment method

A glass surface is used made up of microscopy slides of dimension 2.5 x 7.5 cm, previously cleaned with ethanol, the composition of which is given below:

If: 21-43% by weight

Ca: 2.8-5.8% by weight

Mg: 1.6-3.4% by weight

Na: 6.8-14.2% by weight

Al: 0.3-0.7% by weight

Detergent solutions are prepared, each containing a concentration of 50 ppm of polymer of Example 1 (acrylic acid / MAPTAC / acrylamide copolymer with 40/40/20 molar ratio), 0.2 g / l of nonperionic surfactant Symperonic A7 of BASF and 1 mol / l of KCI salt and whose pH is adjusted by adding 0.01 molar soda.

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

- depositing the polymer solution on the glass slide;

- rotation of the glass slide at 1500 rpm for 30 seconds. A contact angle measurement can then be performed on the treated slide to obtain a so-called "no-rinse" result. The so-called "rinsing" result requires the following additional steps: immersion of the glass slide in purified water for 15 seconds; blade drying by rotation with the rotary applicator, for 30 seconds at 1,500 rpm. The contact angle between water and treated glass is measured on a Ramé-Hart assembly and is expressed in degrees. Eight to ten measurements are made per glass slide. Two to three glass slides are prepared for each polymer and the results therefore correspond to the average of 20 to 30 measurements.

The contact angle obtained on a blade having undergone the treatment described with an aqueous solution (demineralized water) without polymer gives a contact angle of 31.7 + -1 °.

The values before rinsing give information on the hydrophilic or hydrophobic nature of the polymer. But the most interesting data corresponds to the contact angle after rinsing, which characterizes both the hydrophilicity and the strength of the polymer / glass interactions. For the hard surface cleaning application, a low value of this rinsing contact angle is sought. A polymer having a contact angle of less than 20 ° and more particularly of 15 ° will give good performance in application.

The polymers studied and the results obtained are reported in the following table:

EXAMPLES 5 and 6

The method of Examples 2 to 4 is used with solutions of polymers in demineralized water at a concentration of 0.5 g / l and on ceramic tiles having a surface similar to toilet bowls. The pH of these solutions is 3.8. At this pH, the deprotonation rate of acrylic acid in the polymer is 30%. This value makes it possible to calculate the charge Q of the polymers studied. With these higher polymer concentrations, it is considered that a good result in application corresponds to a contact angle of less than 15 °.

Polymers with the following general structure are evaluated:

The table below gives the results obtained

These results show that significant hydrophilization of ceramic tiles is obtained only when the polymer load is low.

EXAMPLE 7:

An aqueous solution is prepared containing 0.5 g / l of nonionic surfactant Symperonic A7 from BASF and 0.2 g / l of acrylic acid / MAPTAC / acrylamide copolymer with a 40/40/20 molar ratio in hard water containing 300 ppm. of CaCO ₃ . This solution has a pH of 7.

This solution is used to treat a ceramic tile. This tile is arranged vertically and the treatment is done as follows: spraying the detergent solution in order to wet the entire tile; drying for 2 minutes; rinsing by spraying with hard water at 300 ppm in CaCO ₃ drying for two hours.

The tile thus treated is placed on a precise scale at 10 ^"2 g and 24 drops of water of 3 μl each are placed on the tile using a multichannel micropipette.

The drying time of the tile is evaluated by the change in mass, and in particular the time required for 90% of the water to evaporate is noted.

Tiles treated with a simple surfactant solution require a 90% drying time of 17 minutes.

The tile treated with the polymer and surfactant solution requires a 90% drying time of 12 minutes.

This result shows that the polymer provides rapid drying of hard surfaces.

EXAMPLES 8 to 10:

Cleaning formulations for window cleaning

The table below reports the composition of three cleaning formulations used for cleaning windows; the glass hydrophilization test by contact angle described for examples 2 to 4 is used directly with the detergent formula without dilution. As in examples 2 to 4, the glass slide is rinsed with pure water after application of the detergent solution.

The contact angle results obtained on formulas A and B (in comparison with formula (C) show that this polymer provides in the formula a persistent hydrophilization of the glass surface.

Formulations A and B are used as such by spraying onto 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 11 and 12: Cleaning formulations for hard surfaces such as tiles

The table below gives cleaning formulations for cleaning hard surfaces. The glass hydrophilization test by contact angle described for Examples 2 to 4 is used with the detergent formula after dilution. As in examples 2 to 4, the glass slide is rinsed with pure water after application of the detergent solution.

Formulations D and E are diluted before use, at a rate of 10 g of formulation in 1 liter of water.

Example D is given for comparison. The contact angle results obtained on formulas D and E show that the polymer provides in the formula a persistent hydrophilization of the glass surface.

EXAMPLES 13 to 16:

Detergent formulas for automatic dishwashers

A glass hydrophilization test by contact angle is used under the following conditions:

The glass slides are placed in an automatic dishwasher and the powdered detergent formula is placed in the tank provided for this purpose, with a dosage of 32 g. No rinsing liquid is used in this test. These glass slides are washed with the "normal" program which gives a maximum washing temperature of 65 ° C. At the end of washing, the dishwasher is kept closed for 3 hours.

The hydrophilicity of the glass slides thus treated is then characterized by the technique of contact angles, described in Examples 2 to 4.

** ethylene diamine tetraacetate

Examples 16 and 17 are given by way of comparison The contact angle results obtained on formulations 14 and 15 show that the polymer provides in the formula a persistent hydrophilization of the glass surface in the dishwasher, which is not found with the comparative examples.

EXAMPLES 17 to 19:

Formulations for rinsing dishes in an automatic dishwasher

An evaluation similar to that given in Examples 13 to 16 is carried out for the rinsing liquid. This test is carried out with the detergent powder of Example 15 and with the rinsing liquids mentioned below.

Example 17 is given for comparison.

The contact angle results obtained on formulas 18 and 19 show that the polymer provides in the formula a persistent hydrophilization of the glass surface in a dishwasher, which is not found with the formulation of Example 17.

EXAMPLES 20 to 22:

Hand dishwashing formulation

The glass hydrophilization test by contact angle described for Examples 2 to 4 is used with the detergent formula after dilution to 1 g / l. As in Examples 2 to 4, the glass slide is rinsed with pure water after application of the detergent solution.

Example 20 is given for comparison. The contact angle results obtained on formulas 21 and 22 show that the polymer provides a residual hydrophilization of the glass surface in the dishwasher in the formulation, a property which is not found with the formulation of Example 20 .

EXAMPLES 23 to 25:

Detergent formulations for cleaning hard surfaces (tiles, sinks, baths)

The hydrophilization test of the glass by contact angle described for examples 2 to 4 is used with the detergent formula after dilution to 1 g / l but it is carried out on black ceramic tiles. As in examples 2 to 4 , the support is rinsed with pure water after application of the detergent solution.

The contact angle results obtained on formulas 24 and 25 show that the polymer provides a residual hydrophilization of hard surfaces in the formulation, a property which is not found with the formulation of Example 23.

Claims

1. Cleaning composition for hard surfaces comprising at least one surfactant and at least one 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

- Ri is a hydrogen atom or a methyl group, preferably a methyl group;

- R ₂ , R ₃ and R ₄ are linear or branched C ₁ -C ₄ alkyl groups;

- n represents an integer from 1 to 4, in particular the number 3;

- X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer;

(b) at least one hydrophilic monomer chosen from monoethylenically unsaturated C ₃ -C ₈ carboxylic acids, their anhydrides and their water-soluble salts;

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

the average charge Q of the polymer defined by the equation: Q = fa] - [b] r

[at]

- in which [a] represents the molar concentration of monomer (a);

- in which [b] represents the molar concentration of monomer (b); and

- and r represents the neutralization rate of the monomers (b) defined by: r = ΓCOQ

[COOH] + [COU ^" ] where [COOH] and [COO ^" ] represent respectively the molar concentrations of monomers (b) in the form of carboxylic acid and carboxylate at the pH of use of the cleaning composition, being greater than 0 and up to 0.4, advantageously up to 0.2.

2. A detergent composition according to claim 1, in which the monomer (a) is represented by the following formula:

3. Cleaning composition according to any one of the preceding claims, in which the monomer is chosen from acrylic acid, methacrylic acid, α-ethacrylic acid, β, β-dimethylacrylic acid, methylenemalonic acid , vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, acid citraconic, mesaconic acid, N-methacroyl-alanine, N-acryloyl-hydroxy-glycine, anhydrides, and the alkali metal and ammonium salts thereof.

4. Cleaning composition 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, C ₁ -C ₄ hydroxyalkyl esters of acrylic acid and methacrylic acid, in particular ethylene glycol and propylene glycol acrylate and methacrylate, polyalkoxylated esters of acrylic acid and methacrylic acid, in particular the esters of polyethylene glycol and polypropylene glycol.

5. Cleaning composition according to any one of the preceding claims, in which X is chosen from halogen, sulphate, hydrogen sulphate, phosphate, citrate, formate and acetate anions.

6. Cleaning composition according to any one of the preceding claims, characterized in that the molar ratio (a) / (b) is between 25/75 and 70/30.

7. Cleaning composition according to any one of the preceding claims, characterized in that the molar ratio (c) / (a + b + c) is between 0 and 40/100, preferably 10/100 and 30/100.

8. Cleaning composition according to any one of the preceding claims, in which the copolymer is

- in which the sum of x + y + z is equal to 100%, x, y and z representing the molar% of units derived respectively from acrylamide, acrylic acid and MAPTAC in the copolymer

- the ratio y / z is from 25/75 to 70/30, and

- x is between 0 and 40%, preferably between 10 and 30%.

9. Cleaning composition according to any one of the preceding claims, characterized in that the molecular weight of the copolymer is at least 1,000, advantageously at least 10,000 and at most 20,000,000, advantageously at least plus 10,000,000.

10. Cleaning composition 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. Cleaning composition according to one of claims 1 to 10, characterized in that the copolymer weight ratio of formula I / surfactant is between 1/2 and 1/100, advantageously between 1/5 and 1/50.

12. Cleaning composition according to one of claims 1 to 11 for cleaning windows, said composition comprising:

- from 0.001 to 10%, preferably 0.005 to 3% by weight of at least one water-soluble or water-dispersible copolymer as defined in one of claims 1 to 9 - from 0.005 to 20%, preferably from 0.5 to 10% by weight of at least one nonionic and / or anionic surfactant;

- the remainder being formed of water, solvents such as alcohols and / or various additives. and having a pH of between 6 and 11 and a molar ratio a / b of between 40/60 and 60/40.

13. A cleaning composition according to claim 12 for cleaning windows, said composition comprising as non-ionic surfactant an amine oxide.

14. Cleaning composition according to one of claims 1 to 11 for washing dishes in an automatic dishwasher, characterized in that the composition comprises:

- from 0.1 to 5%, advantageously from 0.2 to 3% by weight of the water-soluble or water-dispersible copolymer defined in one of claims 1 to 9, relative to the total weight of dry matter of the composition;

- from 0.2 to 10%, advantageously from 0.5 to 5%, by weight relative to the total weight of dry matter of a preferably nonionic surfactant and optionally

- up to 90% of the total weight of detergent composition expressed in dry matter of detergency builders ("builders")

- Up to 30% of the total weight of said detergent composition expressed as dry matter of a bleaching agent of the perborate type, percarbonate associated or not with a bleaching activator;

- Up to 10% of the total weight of said detergent composition expressed as dry matter of cleaning agents;

- Up to 50% of the total weight of said composition expressed as dry matter of fillers of the sodium sulfate or sodium chloride type;

- Up to 10% of the total weight of said composition expressed as dry matter, or of perfumes, dyes, and corrosion inhibiting agents of metals of various additives, in particular of agents influencing the pH of the detergent composition, enzymes in the case of solid compositions, said composition having a pH between 8 and 12, and a molar ratio a / b between 40/60 and 60/40.

15. Cleaning composition according to one of claims 1 to 11 for rinsing dishes in an automatic dishwasher, characterized in that the composition comprises:

- from 0.02 to 10%, preferably from 0.1 to 5% by weight of water-soluble or water-dispersible copolymer defined in one of claims 1 to 9 relative to the total weight of the composition;

- from 0.5 to 20%, preferably 0.5 to 15% by weight relative to the total weight of said composition of a nonionic surfactant or a mixture of nonionic and anionic surfactants;

- from 0 to 10%, preferably from 0.5 to 5% by weight relative to the total weight of dry matter of an organic acid sequestering with calcium, preferably citric acid;

- from 0 to 15%, preferably 0.5 to 10% by weight relative to the total weight of said composition expressed as dry matter of an auxiliary detergency agent such as a copolymer of acrylic acid and maleic anhydride or homo acrylic acid polymers, said composition having a pH of between 4 and 7 and a a / b molar ratio of between 30/70 and 55/45.

16. Cleaning composition according to one of claims 1 to 11 for washing dishes by hand, characterized in that the composition comprises:

- from 0.1 to 5 parts by weight relative to the total weight of said composition of water-soluble or water-dispersible copolymer in one of claims 1 to 9;

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

. at least one non-cationic bactericidal or disinfectant agent; . at least one synthetic cationic polymer agent;

. a polymer used to control the viscosity of the mixture and / or the stability of the foams

. a hydrotropic agent;

. a moisturizing or moistening agent or a skin protection agent;

. a dye, perfume, and a preservative, said composition having a pH of between 6 and 8, and a molar ratio a / b of 40/60 and 60/40.

17. Cleaning composition according to one of claims 1 to 11 for the external cleaning of motor vehicles, characterized in that it comprises:

- from 0.1 to 5% by weight of water-soluble or water-dispersible copolymer according to one of claims 1 to 9 relative to the total weight of said composition;

- from 0 to 30%, preferably e 0.5 to 15% by weight of the formulation of at least one nonionic surfactant;

- from 0 to 30%, preferably e 0.5 to 15% by weight of the formulation of at least one anionic surfactant;

- from 0 to 30%, preferably e 0.5 to 15% by weight of an amphoteric and / or zwitterionic surfactant;

- from 0 to 30%, preferably e 0.5 to 15% by weight of a cationic surfactant; the minimum amount of surfactant being at least 1%;

- from 0 to 50%, preferably from 0.1 to 20% by weight of the formulation of a mineral and / or organic detergency builder;

- Optionally a hydrotropic agent, fillers, agents regulating the pH, said composition having a pH of between 8 and 12, and a molar ratio a / b of between 40/60 and 60/40.

18. Cleaning composition according to one of claims 1 to 11 for cleaning ceramics, in particular tiles, baths, and sinks, characterized in that it comprises:

- from 0.02 to 5% by weight relative to the total weight of said composition of water-soluble or water-dispersible copolymer according to one of claims 1 to 9;

- from 1.5 to 50%, preferably from 5 to 30%, more particularly from 10) 20% by weight of at least one surfactant, preferably nonionic

- from 0.1 to 25% by weight relative to the total weight of the composition of at least one organic or inorganic detergency builder

- optionally a foam regulating agent, in particular an alkali metal soap;

- optionally pH regulating agents, dyes, optical brighteners, soil suspending agents, detergent enzymes, compatible bleaching agents, agents for regulating gel formation, freezing-thawing stabilizers, bactericides, preservatives, solvents, fungicides, insect repellents, hydrotropic agents, perfumes, opacifiers of pearlescent agents, said composition having a pH between 3 and 1, and a molar ratio a / b between 30/70 and 60/40.

19. Cleaning composition according to one of claims 1 to 11 for cleaning toilet bowls, characterized in that it comprises:

- from 0.05 to 5% by weight of water-soluble or water-dispersible copolymer according to one of claims 1 to 9;

- from 0.1 to 40%, and preferably between 0.5 and about 15% by weight relative to the total weight of the composition of a mineral acid cleaner chosen from phosphoric, sulfamic, hydrochloric, hydrofluoric, sulfuric acid , nitric, chromic and mixtures thereof or organic selected among acetic, hydroxyacetic, adipic, citric, formic, fumaric, gluconic, glutaric, glycolic, malic, maleic, lactic, malonic, oxalic, succinic and tartaric acid as well as mixtures thereof, or an acid salt , especially sodium bisulfate, and mixtures thereof;

- from 0.5 to 10% by weight of a surfactant, preferably anionic or nonionic;

- 0.1 to 3% by weight of a thickening agent, preferably a gum, in particular a xanthan gum;

various additives, in particular a preservative intended to prevent the growth of microorganisms, a dye, a perfume and / or an abrasive, said composition having a pH of between 0.5 and 4, and a / b molar ratio of between 25 / 75 and 50/50.

20. Cleaning composition according to one of claims 1 to 11 for rinsing the walls of the showers, characterized in that it comprises:

- from 0.02 to 5% by weight, advantageously from 0.05 to 1% of water-soluble or water-dispersible copolymer one of claims 1 to 9;

- 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, said composition having a pH of between 7 and 11, and a molar ratio a / b of between 40/60 and 60/40.

21. Cleaning composition according to one of claims 1 to 11 for cleaning ceramic hobs, characterized in that it comprises:

- 0.1 to 5% by weight of the water-soluble or water-dispersible copolymer according to claim 1;

- from 1 to 10% by weight of a nonionic surfactant; - 0.1 to 1% by weight of a thickener, in particular a xanthan gum;

- from 10 to 40% by weight of an abrasive agent, in particular calcium carbonate or silica;

- from 0 to 7% by weight of a glycol, in particular butyldiglycol;

- 0.1 to 3% by weight of a silicone type copolymer; and

- Optionally an alkalizing agent or a sequestering agent, said composition having a pH of between 7 and 11 and an a / b ratio of between 40/60 and 60/40.

22. Use in a cleaning composition for a hard surface of at least one 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

- Ri is a hydrogen atom or a methyl group, preferably a methyl group;

- R ₂ , R ₃ and R ₄ are linear or branched C ₁ -C ₄ alkyl groups;

- n represents an integer from 1 to 4, in particular the number 3;

- X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer; (b) at least one hydrophilic monomer chosen from monoethylenically unsaturated C ₃ -C ₈ carboxylic acids, their anhydrides and their water-soluble salts;

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

the average charge Q of the polymer defined by the equation:

Q = fa] - fbir [a]

- in which [a] represents the molar concentration of monomer (a);

- in which [b] represents the molar concentration of monomer (b); and

- and r represents the neutralization rate of the monomers (b) defined by:

r = COOη

[COOH] + [COO] where [COOH] and [COO ^" ] respectively represent the molar concentrations of monomers (b) in the form of carboxylic acid and carboxylate at the pH of use of the cleaning composition, being greater than 0 and up to 0.4, advantageously up to 0.2 to give a hard surface to which it has been applied, hydrophilization properties.

23. Use in a liquid cleaning composition for a hard surface, of at least one copolymer as defined in one of claims 1 to 11, for decreasing the drying rate of a surface on which said composition has been applied.

24. Use according to claim 22, characterized in that the hydrophilization properties are chosen from the "anti-flow", "anti-fog" properties, and the residual "anti-stain" or "anti-trace" properties.

25. Use according to one of claims 22 to 24, characterized in that one deposits on the surface to be treated from 0.0001 to 6 g / m ² , preferably from 0.001 to 2 g / m ² of the surface of said water-soluble or water-dispersible copolymer.

26. Use according to one of claims 22 to 25, to impart hydrophilizing properties to a glass or ceramic surface, or to decrease the drying rate of such a surface.

27. Use according to claim 24 to 26, for cleaning or rinsing the dishes by hand or in an automatic dishwasher.

28. Use according to claim 24 to 26, for cleaning windows.

29. Use according to claim 24 to 26, for cleaning tiles, baths and sinks.

30. Use according to claim 24 to 26, for cleaning toilet bowls.

31. Use according to claim 24 to 26, for cleaning the shower walls.

32. Use according to claim 24 to 26, for cleaning the ceramic hobs.

33. Use according to one of claims 22 to 25, for the external cleaning of motor vehicles.