EP1196528B1 - 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

The subject of the present invention is a cleaning composition intended for the treatment of domestic industrial or community hard surfaces, in particular of the ceramic, tile or glass type, aimed at imparting to these properties hydrophilic properties.

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

Commercial detergent formulations can effectively clean industrial, domestic or community hard surfaces. 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. A major deficiency of these detergent formulations is that subsequent contact of the hard surface with water may lead to drying in the presence of traces. This contact with water after the application of detergent may come for example rain water in the case of windows, water network 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 to clean dishes by hand, or drying dishes in the automatic machine when it comes to dishwashing machine detergent . 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 the hard surfaces by the water coming into contact with them is due to the phenomenon of contraction of the drops of water in contact with the hard surface which, during the 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 of retracting and drying water drops, the solution is to increase the hydrophilicity of the surface to obtain the lowest possible contact angle between the hard surface to be treated and the drop of water. 'water.

The work of the inventors having led to the present invention made it possible to determine that this problem could be solved in an efficient and durable manner by incorporating into the conventional hard surface cleaning compositions, a water-soluble or water-dispersible organic polymer compound having both a water-soluble and a water-soluble function. interaction with the surface to be treated and a function conferring on this surface a hydrophilic character and having certain particular properties.

1. (a) au moins un composé monomère de formule générale I :
   
   dans laquelle
   • R₁ est un atome d'hydrogène ou un groupe méthyle, de préférence un groupe méthyle ;
   • R₂, R₃ et R₄ sont des groupes alkyle linéaire ou ramifié en C₁-C₄;
   • n représente un nombre entier de 1 à 4, notamment le nombre 3;
   • X représente un contre-ion compatible avec le caractère hydrosoluble ou hydrodispersible du polymère ;
2. (b) au moins un monomère hydrophile choisi parmi les acides carboxyliques en C₃-C₈ à insaturation monoéthylénique, leurs anhydrides et leurs sels hydrosolubles ;
3. (c) au moins un composé monomère hydrophile à insaturation éthylénique de charge neutre portant un ou plusieurs groupes hydrophiles, copolymérisable avec (a) et (b) ;
   la charge moyenne Q du copolymère définie par l'équation : $$\mathrm{Q}\mathrm{=}\frac{\left[\mathrm{a}\right]\mathrm{-}\left[\mathrm{b}\right]\mathrm{\Gamma }}{\left[\mathrm{a}\right]}$$
   
   • dans laquelle [a] représente la concentration molaire de monomère (a) ;
   • dans laquelle [b] représente la concentration molaire de monomère (b) ; et
   • et r représente le taux de neutralisation des monomères (b) défini par:
   $$\mathrm{\Gamma }\mathrm{=}\frac{\left[{\mathrm{COO}}^{\mathrm{-}}\right]}{\left[\mathrm{COOH}\right]\mathrm{+}\left[{\mathrm{COO}}^{\mathrm{-}}\right]}$$
   
   
   où [COOH] et [COO^-] représentent respectivement les concentrations molaires en monomères (b) sous forme d'acide carboxylique et de carboxylate au pH d'utilisation de la composition nettoyante,
   étant supérieure à 0 et pouvant aller jusqu'à 0,4 , avantageusement jusqu'à 0,2. Avantageusement, le rapport molaire (a)/(b) est compris entre 25/75 et 70/30

A first subject of the invention consists of a hard surface cleaning composition comprising at least one surfactant and at least one water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:

1. (a) at least one monomeric compound of general formula I:
   
   in which
   • R ₁ 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, especially the number 3;
   • X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer;
2. (b) at least one hydrophilic monomer selected from monoethylenically unsaturated C ₃ -C ₈ carboxylic acids, their anhydrides and their water-soluble salts;
3. (c) at least one neutral charge ethylenically unsaturated hydrophilic monomeric compound bearing one or more hydrophilic groups, copolymerizable with (a) and (b);
   the average charge Q of the copolymer defined by the equation: $$\mathrm{Q}\mathrm{=}\frac{\left[\mathrm{at}\right]\mathrm{-}\left[\mathrm{b}\right]\mathrm{\Gamma }}{\left[\mathrm{at}\right]}$$
   
   • wherein [a] represents the molar concentration of monomer (a);
   • wherein [b] represents the molar concentration of monomer (b); and
   • and r represents the degree of neutralization of the monomers (b) defined by:
   $$\mathrm{\Gamma }\mathrm{=}\frac{\left[{\mathrm{COO}}^{\mathrm{-}}\right]}{\left[\mathrm{COOH}\right]\mathrm{+}\left[{\mathrm{COO}}^{\mathrm{-}}\right]}$$
   
   
   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. 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 assaying with a polyvinyl sulphate 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 on the copolymer hydrophilic characteristics which, after anchoring the copolymer to the surface to be treated, are transmitted thereto.

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

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

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

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

Unless otherwise indicated, when reference is made to molecular weight, it will be the molecular weight in 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), mention may be made of acrylic acid, methacrylic acid, α-ethacrylic acid, β, β-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid and the like. allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacrylalanine, N-acryloyl-hydroxy-glycine, the anhydrides, and the 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.

X is any suitable counteranion compatible with the water-soluble or water-dispersible nature of the copolymer, especially an anion of halogen, sulfate, hydrogen sulfate, phosphate, citrate, formate and acetate.

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

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

• dans lequel la somme de x+y+z est égale à 4 100%, x, y et z représentant les % molaires de motifs dérivés respectivement d'acrylamide, d'acide acrylique et de MAPTAC dans le copolymère
• le rapport y/z est de 25/75 à 70/30, et
• x est compris entre 10 et 40%, de préférence entre 10 et 30 %.

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 mol% of units respectively derived from acrylamide, acrylic acid and MAPTAC in the copolymer
• the ratio y / z is 25/75 to 70/30, and
• x is between 10 and 40%, preferably between 10 and 30%.

The said copolymer may be introduced into a formulation intended to treat the 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, 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; alkylbenzenesulfonates, especially C ₈ -C 13 linear alkyl-benzene _sulphonates , in which the alkyl group comprises from 10 to 16 carbon atoms, alcohol sulphates, ethoxylated alcohol-sulphonates, hydroxyalkyl sulphonates; alkyl sulphates and sulphonates, especially 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 alkylarylés comme les RHODAFAC RA600, RHODAFAC PA15 ou RHODAFAC PA23 commercialisés par la société RHODIA.

Advantageous anionic surfactants include:

• the alkyl ester sulfonates of formula R-CH (SO ₃ M) -COOR ', in which R represents a C _8-20 alkyl radical, preferably a C ₁₀ -C ₁₆ alkyl radical, R' a radical; C ₁ -C ₆ alkyl, preferably C ₁ -C ₃ alkyl, and M an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium, etc.). ) 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 ;
• the alkyl sulphates of formula ROSO ₃ M, in which R represents a C ₅ -C ₂₄ or 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 in which R represents a C ₂ -C ₂₂ , preferably C ₆ -C ₂₀ , alkyl radical, R 'represents a C ₂ -C ₃ alkyl radical, M represents a C 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 and preferably C ₁₄ -C ₂₀ fatty acid salts, C ₉ -C ₂₀ alkylbenzenesulphonates, primary or secondary C ₈ -C ₂₂ alkylsulfonates, and alkylglycerol sulphonates; , the sulfonated polycarboxylic acids described in GB-A-1,082,179 , paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, sulfosuccinates monoesters or diesters, N-acyl sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates, the cation being a 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 alkylaryl phosphate esters such as RHODAFAC RA600, RHODAFAC PA15 or RHODAFAC PA23 marketed by RHODIA.

Among the nonionic surfactants, mention may in particular be made of alkylene oxide condensates, especially of ethylene oxide with alcohols, polyols, alkylphenols, fatty acid esters, acid amides, fatty and fatty amines; amine oxides, sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, especially sucrose monopalmitate; long-chain tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and polyoxypropylene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly (ethylene oxide) and amides of fatty acids modified so as to confer a hydrophobic character (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 ID060, 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-C₂₀ ;
• 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 ID060, 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 aryl ou benzyl
• 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 ^- where

• 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 derivatives, especially 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.

• 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 ^® sold by Berol Nobel

Additional examples of suitable surfactants are compounds generally used as surfactants referred to 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.

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

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

* especially for washing in the dishwasher

• - "builders" (detergency builders improving the surface properties of surfactants) organic type:
  • organic phosphonates such as those of the range DEQUEST ^® from Monsanto (in a proportion of 0 to 2% of the total weight of detergent composition expressed as solids in the case of a composition for dishwasher);
  • polycarboxylic acids or their water-soluble salts and the 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), (at 0 to 10% of the total weight of detergent composition expressed as dry matter in the case of a dishwashing composition);
    • . 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 (in a proportion of 0 to 10% of the total weight of detergent composition expressed as dry matter in the case of a dishwashing composition);
• - "builders" (adjuvants of detergency improving the surface properties of surfactants) mineral type:
  • polyphosphates of alkali metals, ammonium or alkanolamines, such as RHODIAPHOS HPA3.5 sold by the company RHODIA, (in a proportion of 0 to 70% of the total weight of detergent composition expressed as dry matter in the case of a composition for dishwashers);
  • pyrophosphates of alkali metals
  • zeolites;
  • silicates (in an amount of up to about 50% of the total weight of said detergent composition expressed as dry matter in the case of a dishwashing composition);
  • alkali or alkaline earth borates, carbonates, bicarbonates, sesquicarbonates (in an amount of up to about 50% of the total weight of said detergent composition expressed as dry matter in the case of a dishwashing composition);
  • cogranulates 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 of up to about 50% of the total weight of said detergent composition expressed as dry matter in the case of a dishwashing composition);
    (the total amount of "builders", organic and / or inorganic, may represent up to 90% of the total weight of said detergent composition expressed as dry matter in the case of a dishwashing composition);
• bleaching agents of the perborate or percarbonate type, whether or not associated with acetylated bleaching activators such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED) or chloroisocyanurate-type chlorinated products, or chlorinated products of the alkali metal hypochlorite type, (in a proportion of 0 to 30% of the total weight of said detergent composition expressed as dry matter in the case of a dishwashing composition);
• auxiliary cleaning agents of the copolymer type of acrylic acid and of maleic anhydride or homopolymers of acrylic acid (in a proportion of 0 to 10%, of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition);
• fillers of the sodium sulphate, sodium chloride type in a proportion of 0 to 50% of the total weight of the said composition, expressed as dry matter;
• other various additives such as agents affecting 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, sulphonic acids, etc.) or enzymes or perfumes, dyes, corrosion inhibitors of metals;

* 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 the 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, etc.
• hydrating or moisturizing agents for the skin such as glycerol, urea or protective agents to the skin, such as proteins or protein hydrolyzates, cationic polymers such as cationic derivatives of guar (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, after rinsing, it is possible, and after drying, a copolymer deposit according to the invention of 0.0001 to 1 g / m ² , preferably 0.001 to 0.1g / m ² of surface to be treated.

According to a particularly advantageous embodiment, the cleaning composition according to the invention is used for the treatment of glass surfaces, in particular glass panes. This treatment can be performed by the various known techniques. In particular, techniques for cleaning windows by spraying a jet of water using devices of the Karcher® type can be mentioned.

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

Unless otherwise indicated, the proportions are given by weight.

• de 0,001 à 10 %, de préférence 0,005 à 3 % en poids d'au moins un copolymère hydrosoluble ou hydrodispersable tel que défini précédemment ;
• de 0,005 à 20 %, de préférence de 0,5 à 10 % en poids d'au moins un agent tensioactif non-ionique (par exemple un amine oxyde) et/ou anionique ; et
• le reste étant formé d'eau et/ou d'additifs divers usuels dans le domaine.

The cleaning composition of the windows according to the invention comprises:

• from 0.001 to 10%, preferably from 0.005 to 3% by weight of at least one water-soluble or water-dispersible copolymer as defined previously;
• 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 surfactant; and
• the remainder being water and / or various additives customary in the field.

• de 0 à 10%, avantageusement de 0,5 à 5 % de tensioactif amphotère,
• de 0 à 30 %, avantageusement de 0,5 à 15 % de solvant tels que des alcools, et

le reste étant constitué par de l'eau et des additifs usuels (parfums notamment).The glass 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 water and usual additives (especially perfumes).

The pH of the composition is advantageously between 6 and 11. The ratio a / b is preferably between 40/60 and 60/40.

The composition of the invention is also interesting for cleaning the dishes by hand or automatic machine. In the latter case, said copolymer may be present either in the detergent formula used in the wash cycle or in the rinse liquid.

Detergent formulations for dishwashing in automatic dishwashers advantageously comprise from 0.1 to 5%, preferably from 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 dishwashing detergent compositions also comprise at least one surfactant, preferably nonionic in an amount ranging from 0.2 to 10%, preferably from 0.5 to 5%, of the weight of said detergent composition expressed as dry matter. the rest being constituted by various additives and fillers, as already mentioned above.

The pH is advantageously between 8 and 12. The ratio a / b 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 from 0.5 to 15% by weight relative to the total weight of said composition of a surfactant, preferably a nonionic surfactant 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, and the like. propylene, possibly 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 calcium, preferably citric acid.

They may also comprise an auxiliary agent of copolymer type acrylic acid and maleic anhydride or homopolymers of acrylic acid in a proportion 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 ratio a / b 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 the 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 one surfactant, preferably anionic, chosen in particular from sulphates of saturated C ₅ -C ₂₄ aliphatic alcohols, preferably of C ₁₀ -C ₁₆ , optionally condensed with approximately 0.5 to 30, preferably 0.5 at 5, in particular 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 is more particularly directed to liquid foaming detergent aqueous formulations 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

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

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

In this case also, the copolymer according to the invention may be present either in a detergent formula used for the washing operation, or 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 according to the invention 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 in the composition type may be at least 1% of the formulation)

The pH is advantageously between 8 and 12. The ratio a / b 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, especially ceramics (tiles, bathtubs, washbasins, 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 surface-active agents, nonionic surfactants are preferred, in particular compounds produced by condensation of alkylene oxide groups as described above which are hydrophilic in nature with a hydrophobic organic compound which may be of aliphatic or alkylaromatic nature.

The length of the hydrophilic chain or 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 may optionally be present in an amount of 0 to 30%, advantageously 0 to 20% by weight.

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

The total amount of surfactant compounds employed 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. composition.

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

For example, the composition may contain organic or inorganic builders as mentioned above.

In general, the detergency builder is used in an amount of 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 may be employed in compositions having a tendency to produce excess foam when in use. An example of these materials are soaps. Soaps are salts of fatty acids and include alkali metal soaps, including sodium, potassium, ammonium and higher alkanol ammonium salts of fatty acids containing from about 8 to 24 carbon atoms, and preferably about 10 to about 20 carbon atoms. Particularly useful are the salts of mono-, di- and triethanolamine of sodium and potassium or mixtures of fatty acids derived from coconut oil and ground nut oil. The amount of soap may 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 aforementioned ingredients, other optional ingredients such as pH control agents, colorants, optical brighteners, soil-suspending agents, detergent enzymes, compatible bleaching agents, gel formation control agents, freeze-thaw stabilizers, bactericides, preservatives, solvents, fungicides, insect repellents, hydrotropic agents; perfumes and opacifiers or pearls.

The pH of the composition is advantageously between 3 and 11. The ratio a / b 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 a ratio a / b of between 25/75 and 50/50.

The composition for cleaning toilet bowls according to the invention also comprises an acidic cleaner which may consist of a mineral acid such as phosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, 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, acid salts such as sodium bisulfate and mixtures thereof.

The amount of acidic ingredients is preferably from 0.1 to about 40%, and preferably from 0.5 to 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 about 0.2 and about 1%, with hydrochloric acid between about 1 and about 5%, with citric acid between about 2 and about 10%, with formic acid, between about 5 and about 15% and with phosphoric acid, from about 5 to about 30% by weight.

The amount of acidic 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 dirt or to provide foaming or wetting characteristics or to increase the cleaning efficiency of the composition. The surfactant is preferably an anionic or nonionic surfactant.

Cationic surfactants may also be added to the toilet bowl cleaning composition according to the invention to provide germicidal properties. The skilled person will see that agents Amphoteric surfactants can also be used. Various surfactant mixtures may be employed if desired.

The toilet bowl cleaning composition according to the invention may also comprise a gum-type thickener, especially a xanthan gum introduced at a concentration of 0.1 to 3% and one or more of the following minority ingredients: a preserving agent 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 showers.

The aqueous rinsing compositions of the shower walls 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 of from 0.5 to 5% by weight and optionally a metal chelating agent present in an amount of from 0.1 to 5% by weight.

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

The aqueous shower rinse compositions advantageously contain water with optionally at least one lower alcohol in major proportion and additives in a minor proportion (between about 0.1 and about 5% by weight, more preferably between about 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 the patents US5,536,452 and 5587022 .

Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan mono-oleates and polyethoxylated castor oil. Specific examples of such surfactants are the condensation products of 20 moles of ethylene oxide and sorbitan mono-oleate (sold by RHODIA Inc. under the name ALKAMULS PSMO-20® with a 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 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 alkylpolyglucosides are also well suited to these compositions.

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

The composition according to the invention can also be used for cleaning vitroceramic plates.

• 0,1 à 5 % en poids du copolymère de l'invention ;
• 0,1 à 1 % en poids d'un épaississant tel qu'une gomme xanthane ;
• 10 à 40 % en poids d'un agent abrasif tel que le carbonate de calcium ou la silice ;
• 0 à 7 % en poids d'un glycol tel que le butyldiglycol ;
• 1 à 10 % en poids d'un agent tensioactif non ionique ;
• 0,1 à 3 % en poids d'un copolymère de type silicone ; et
• éventuellement des agents d'alcalinisation ou des séquestrants.

Advantageously, the formulations for the cleaning of vitroceramic plates of the invention comprise:

• 0.1 to 5% by weight of the copolymer of the invention;
• 0.1 to 1% by weight of a thickener such as 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
• optionally alkalizing agents or sequestering agents.

The pH of the composition is advantageously between 7 and 12 . The ratio a / b is preferably between 40/60 and 60/40.

1. (a) au moins un composé monomère de formule générale I :
   
   dans laquelle
   • R₁ est un atome d'hydrogène ou un groupe méthyle, de préférence un groupe méthyle ;
   • R₂, R₃ et R₄ sont des groupes alkyle linéaire ou ramifié en C₁-C₄;
   • n représente un nombre entier de 1 à 4, notamment le nombre 3;
   • X représente un contre-ion compatible avec le caractère hydrosoluble ou hydrodispersible du polymère ;
2. (b) au moins un monomère hydrophile choisi parmi les acides carboxyliques en C₃-C₈ à insaturation monoéthylénique, leurs anhydrides et leurs sels hydrosolubles ;
3. (c) au moins un composé monomère hydrophile à insaturation éthylénique de charge neutre portant un ou plusieurs groupes hydrophiles, copolymérisable avec (a) et (b),
   la charge moyenne Q du polymère définie par l'équation : $$\mathrm{Q}\mathrm{=}\frac{\left[\mathrm{a}\right]\mathrm{-}\left[\mathrm{b}\right]\mathrm{\Gamma }}{\left[\mathrm{a}\right]}$$
   
   • dans laquelle [a] représente la concentration molaire de monomère (a) ;
   • dans laquelle [b] représente la concentration molaire de monomère (b) ; et
   • et r représente le taux de neutralisation des monomères (b) défini par:

$$\mathrm{\Gamma }\mathrm{=}\frac{\left[{\mathrm{COO}}^{\mathrm{-}}\right]}{\left[\mathrm{COOH}\right]\mathrm{+}\left[{\mathrm{COO}}^{\mathrm{-}}\right]}$$

où [COOH] et [COO^-] représentent respectivement les concentrations molaires en monomères (b) sous forme d'acide carboxylique et de carboxylate au pH d'utilisation de la composition nettoyante,
étant supérieure à 0 et pouvant aller jusqu'à 0,4, avantageusement jusqu'à 0,2
pour conférer à la surface dure sur laquelle elle a été appliquée, des propriétés d'hydrophilisation.The invention also relates to the use, in a hard surface cleaning composition, of at least one water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:

1. (a) at least one monomeric compound of general formula I:
   
   in which
   • R ₁ 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, especially the number 3;
   • X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer;
2. (b) at least one hydrophilic monomer selected from monoethylenically unsaturated C ₃ -C ₈ carboxylic acids, their anhydrides and their water-soluble salts;
3. (c) at least one neutral charge ethylenically unsaturated hydrophilic monomeric compound bearing one or more hydrophilic groups, copolymerizable with (a) and (b),
   the average charge Q of the polymer defined by the equation: $$\mathrm{Q}\mathrm{=}\frac{\left[\mathrm{at}\right]\mathrm{-}\left[\mathrm{b}\right]\mathrm{\Gamma }}{\left[\mathrm{at}\right]}$$
   
   • wherein [a] represents the molar concentration of monomer (a);
   • wherein [b] represents the molar concentration of monomer (b); and
   • and r represents the degree of neutralization of the monomers (b) defined by:

$$\mathrm{\Gamma }\mathrm{=}\frac{\left[{\mathrm{COO}}^{\mathrm{-}}\right]}{\left[\mathrm{COOH}\right]\mathrm{+}\left[{\mathrm{COO}}^{\mathrm{-}}\right]}$$

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, preferably up to 0.2
to impart hydrophilic properties to the hard surface to which it has been applied.

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

Another subject of the invention is the use, in a hard surface cleaning liquid composition, 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 treating said surface with 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 with 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

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

Two detergent solutions each containing a concentration of 50 ppm of polymer, 0.2 g / l of BASF Symperonic A7 nonionic surfactant and whose pH is adjusted by the addition of 0.01 molar sodium hydroxide are prepared. The transmittance of the solution is measured using a photometer. The charge of the polymer is determined by assaying with a solution of potassium polyvinyl sulphate.

Each aqueous solution is sprayed on a black ceramic tile, arranged vertically. After drying the ceramic tile, 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: Solution 1 (eg comparative) Solution 2 pH 4 9 Polymer charge 0.6 0.05 transmittance 100 86 Visual observation Heterogeneous flow of the water film Homogeneous flow of the water film

This result shows that the polymer solution 1 having a low pH and therefore a high average load does not make it possible to obtain an effective hydrophilization benefit of the surface. On the other hand, the polymer having a very low charge (solution 2) as defined in the invention leads to an efficient hydrophilization of the surface.

EXAMPLES 2-4: Evaluation method

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

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

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

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.

• 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 contact angle between the water and the treated glass is measured on a Ramé-Hart fixture 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 treated blade 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 contact angle with rinsing is sought. A polymer having a contact angle of less than 20 ° and more particularly 15 ° will give good performance in application.

The polymers studied and the results obtained are reported in the following table: Examples pH of the polymer solution Contact angle before rinsing Contact angle after rinsing Polymer charge 2 (comparative) 4 24 25 0.60 3 7 22 20 0.17 4 9 18 16 0.05

EXAMPLES 5 and 6:

The method of Examples 2 to 4 is used with polymer solutions 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 the acrylic acid in the polymer is 30%. This value makes it possible to calculate the load 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 having the following general structure are evaluated:

The table below gives the results obtained: Examples x mol% y mol% z mol% Charge Q Angle before rinsing Angle after rinsing 5 (comparative) 20 20 60 0.9 20.45 24.1 6 20 60 20 0.1 11.2 14.5

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

EXAMPLE 7

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

• pulvérisation de la solution détergente afin de mouiller la totalité du carreau ;
• séchage pendant 2 minutes ;
• rinçage par pulvérisation d'eau dure à 300 ppm en CaCO₃
• séchage pendant deux heures.

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 to wet the entire tile;
• drying for 2 minutes;
• rinsing with hard water spray at 300 ppm 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 3μl 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.

The tile treated with a simple surfactant solution requires 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 fast 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 window cleaning; the hydrophilization test of the glass 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. formulations components A (by weight) B (by weight) C (by weight) Isopropylic alcohol 7 15 7 Fatty alcohol (C12) ethoxylated (7OE) 0 3 0 Sodium dodecylbenzene sulphonate 0.5 0 0.5 Ammonium hydroxide 0.3 0.3 0.3 Monomethyl ether of dipropylene glycol 0.25 0.5 0.25 Copolymer of Example 1 0.05 0.5 0.0 Water qs 100 qs 100 qs 100 pH of the formula 7 7 7 Polymer charge Q 0.15 0.15 / Contact angle 21 15 28

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

Formulations A and B are used as such by spraying on the surface of the windows 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 contact lens hydrophilization test 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. components formulations D (by weight) E (by weight) 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 of the example 1 0 1 Water qs 100 qs 100 Polymer charge Q / 0.05 Contact angle (°) 28 16

Formulations D and E are diluted before use, at the 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 permanent hydrophilization of the glass surface.

EXAMPLES 13-16: Detergent formulas for automatic dishwashers

• Les lames de verres sont placées dans un lave-vaisselle automatique et la formule détergente en poudre est placée dans le réservoir prévu à cet effet, avec un dosage de 32 g. Aucun liquide de rinçage n'est utilisé dans cet essai Ces lames de verre sont lavées avec le programme « normal » qui donne une température de lavage maximum de 65 °C. A la fin du lavage, le lave-vaisselle est maintenu fermée pendant 3 heures.

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

• The glass slides are placed in an automatic dishwasher and the detergent powder formula is placed in the tank provided for this purpose, with a dosage of 32 g. No rinse aid 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 hydrophilic glass slides thus treated is then characterized by the contact angle technique, described in Examples 2 to 4. Sample formulation example 13 example 14 Example 15 example 16 Sodium tripolyphosphate 0 45 0 45 Sodium carbonate 30 20 30 20 Sodium disilicate 15 10 15 10 Sodium citrate 20 0 20 0 Sodium sulphate 12 8 14 10 Sodium polyacrylate CP5 from BASF 6 0 6 0 Plurafac LF 403 2 2 2 2 Bleach system (perborate, 1 H ₂ O + TAED **) 10 10 10 10 Other additives (including benzatriaole, enzymes, perfume) 3 3 3 3 Polymer of Example 1 2 2 0 0 pH 10.5 10.4 10.5 10.4 Polymer charge Q 0.05 0.05 / / Contact angle 13 12 24 22 ** 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 permanent 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 automatic dishwashers

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 rinse liquids mentioned below. Formulation Example 17 example 18 Example 19 Nonionic surfactant C13-3OP-70E (linear fatty alcohol EO / OP) 12 12 12 Citric acid 3 3 3 Polymer of Example 1 0 polymer (1%) polymer (2%) Water qsp to 100 qsp to 100 qsp to 100 pH 5 5 5 Polymer charge Q / 0.30 0.30 Contact angle 24 16 15

Example 17 is given for comparison.

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

EXAMPLES 20 to 22: Hand washing dishwashing formulation

The contact lens hydrophilization test 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. Formulation Example 20 Example 21 Example 22 Sodium alkylsulphonate (C14) 24 24 12 Ethoxylated fatty alcohol C12 - 1,5 EO 5 5 3 Ethoxylated fatty alcohol C10 - 7OE 4 4 4 Polymer of Example 1 0 polymer (2%) polymer (2%) Water qsp to 100 qsp to 100 qsp to 100 pH 7 7 7 Polymer charge Q / 0.15 0.15 Contact angle 28 19 15

Example 20 is given for comparison.

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

EXAMPLES 23 to 25: Detergent formulations for cleaning hard surfaces (tiles, wash basins, bathtubs)

The hydrophilization test of the contact angle glass 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. Formulation example 23 example 24 example 25 Sodium alkylsulphonate (C12) 12 24 12 Ethoxylated fatty alcohol C12 - 6 EO 5 5 3 Ethanol 2 4 4 Polymer of Example 1 0 polymer (2%) polymer (2%) Water qsp to 100 qsp to 100 qsp to 100 pH 7 7 7 Polymer charge Q / 0.15 0.15 Contact angle 35 19 16

Example 23 is given for comparison.

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

Claims (26)

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 monomeric compound of general formula I:

   

   in which

   - R₁ is a hydrogen atom or a methyl group, preferably a methyl group;

   - R₂, R₃ and R₄ 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 which is compatible with the water-soluble or water-dispersible nature of the polymer;

   (b) at least one hydrophilic monomer chosen from C₃-C₈ carboxylic acids containing monoethylenic unsaturation, anhydrides thereof and water-soluble salts thereof;

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

   - the molar ratio (a)/(b) is between 25/75 and 70/30[-the copolymer is

   

   in which

   - the sum of x+y+z is equal to 100%,

   - x, y and z represent the molar percentages of units derived, respectively, from acrylamide, from acrylic acid and from MAPTAC in the copolymer

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

   the average charge Q on the polymer defined by the equation: $$\mathrm{Q}\mathrm{=}\frac{\left[\mathrm{a}\right]\mathrm{-}\left[\mathrm{b}\right]\mathrm{\Gamma }}{\left[\mathrm{a}\right]}$$

   

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

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

   - Γ represents the rate of neutralization of monomers (b) defined by: $$\mathrm{\Gamma }\mathrm{=}\frac{\left[{\mathrm{COO}}^{\mathrm{-}}\right]}{\left[\mathrm{COOH}\right]\mathrm{+}\left[{\mathrm{COO}}^{\mathrm{-}}\right]}$$

   

   
   in which [COOH] and [COO^-] represent, respectively, the molar concentrations of units derived from acrylic acid in carboxylic acid and carboxylate form at the pH at which the cleaning composition is used,
   being greater than 0 and possibly going down to 0.4, advantageously down to 0.2.
2. Detergent composition according to Claim 1, characterized in that the molecular mass of the copolymer is at least 1000, advantageously at least 10,000, and not more than 20,000,000, advantageously not more than 10,000,000.
3. Cleaning composition according to either of Claims 1 and 2, characterized in that the said copolymer of formula I represents from 0.001% to 10% of the total weight of the said composition.
4. Cleaning composition according to one of Claims 1 to 3, characterized in that the copolymer/surfactant weight ratio is between 1/2 and 1/100, advantageously between 1/5 and 1/50.
5. Cleaning composition according to one of Claims 1 to 4, for cleaning glass panels, the said composition comprising:

   - from 0.001% to 10%, preferably from 0.005% to 3%, by weight of at least one water-soluble or water-dispersible copolymer as defined in either of Claims 1 and 2

   - from 0.005% to 20%, preferably from 0.5% to 10%, by weight of at least one nonionic and/or an ionic surfactant;

   - the remainder being formed of water, of solvents such as alcohols and/or of various additives, and having a pH of between 6 and 11 and a molar ratio z/y of between 40/60 and 60/40.
6. Cleaning composition according to Claim 5, for cleaning glass panels, the said composition comprising an amine oxide as nonionic surfactant.
7. Cleaning composition according to one of Claims 1 to 4, for washing up crockery in an automatic dishwasher, characterized in that the composition comprises:

   - from 0.1% to 5% and advantageously from 0.2% to 3% by weight of the water-soluble or water-dispersible copolymer defined in either of Claims 1 and 2, relative to the total weight of solids in the composition;

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

   - up to 90%, relative to the total weight of detergent composition expressed as solids, of detergent adjuvants ("builders");

   - up to 30%, relative to the total weight of the said detergent composition expressed as solids, of a bleaching agent such as perborate or percarbonate, optionally combined with a bleaching activator;

   - up to 10%, relative to the total weight of the said detergent composition expressed as solids, of auxiliary cleaning agents;

   - up to 50%, relative to the total weight of the said composition expressed as solids, of fillers such as sodium sulphate or sodium chloride;

   - up to 10%, relative to the total weight of the said composition expressed as solids, of fragrances, dyes, and metal-corrosion inhibitors of various additives, in particular of agents which have an influence on the pH of the detergent composition, and enzymes in the case of solid compositions,
   the said composition having a pH of between 8 and 12 and a molar ratio z/y of between 40/60 and 60/40.
8. Cleaning composition according to one of Claims 1 to 4, for rinsing washing-up crockery in an automatic dishwasher, characterized in that the composition comprises:

   - from 0.02% to 10% and preferably from 0.1% to 5% by weight of water-soluble or water-dispersible copolymer defined in either of Claims 1 and 2, relative to the total weight of the composition;

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

   - from 0% to 10% and preferably from 0.5% to 5% by weight, relative to the total weight of solids, of a calcium-sequestering organic acid, preferably citric acid;

   - from 0% to 15% and preferably from 0.5% to 10% by weight, relative to the total weight of the said composition expressed as solids, of an auxiliary detergent such as a copolymer of acrylic acid and of maleic anhydride or acrylic acid homopolymers,
   the said composition having a pH of between 4 and 7 and a molar ratio z/y of between 30/70 and 55/45.
9. Cleaning composition according to one of Claims 1 to 4, for doing the washing-up by hand, characterized in that the composition comprises:

   - from 0.1 to 5 parts by weight, relative to the total weight of the said composition, of water-soluble or water-dispersible copolymer defined in either of Claims 1 and 2;

   - 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,
   the said composition having a pH of between 6 and 8 and a molar ratio z/y of between 40/60 and 60/40.
10. Cleaning composition according to one of Claims 1 to 4, 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 either of Claims 1 and 2, relative to the total weight of the said composition;

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

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

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

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

    - from 0% to 50% and preferably from 0.1% to 20%, relative to the weight of the formulation, of an inorganic and/or organic detergent adjuvant ("builder");

    - optionally, a hydrotropic agent, fillers and pH regulators,
    the said composition having a pH of between 8 and 12 and a molar ratio z/y of between 40/60 and 60/40.
11. Cleaning composition according to one of Claims 1 to 4 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 the said composition, of water-soluble or water-dispersible copolymer according to either of Claims 1 and 2;

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

    - from 0.1% to 25% by weight, relative to the total weight of the composition, of at least one organic or inorganic detergent adjuvant ("builder");

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

    - optionally, pH regulators, dyes, optical brighteners, soiling-suspending agents, detergent enzymes, compatible bleaching agents, gel-formation regulators, freezing-thawing stabilizers, bactericides, preserving agents, solvents, fungicides, insect repellents, hydrotropic agents, fragrances, opacifiers and pearlescent agents,
    the said composition having a pH of between 3 and 1 and a molar ratio z/y of between 30/70 and 60/40.
12. Cleaning composition according to one of Claims 1 to 4, for cleaning toilet pans, characterized in that it comprises:

    - from 0.05% to 5% by weight of water-soluble or water-dispersible copolymer according to either of Claims 1 and 2;

    - from 0.1% to 40% and preferably between 0.5% and about 15% by weight, relative to the total weight of the composition, of an inorganic acid cleaning agent chosen from phosphoric acid, sulphamic acid, hydrochloric acid, hydrofluoric acid, sulphuric acid, nitric acid or chromic acid and mixtures thereof, or an organic acid chosen from acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid, lactic acid, malonic acid, oxalic acid, succinic acid and tartaric acid, as well as mixtures thereof; or an acid salt, in particular sodium bisulphate, and mixtures thereof;

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

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

    - various additives, in particular a preserving agent intended to prevent the growth of microorganisms, a dye, a fragrance and/or an abrasive agent,
    the said composition having a pH of between 0.5 and 4 and a molar ratio z/y of between 25/75 and 50/50.
13. Cleaning composition according to one of Claims 1 to 4 for rinsing shower walls, characterized in that it comprises:

    - from 0.02% to 5% by weight and advantageously from 0.05% to 1% by weight of water-soluble or water-dispersible copolymer according to either of Claims 1 and 2;

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

    - optionally, from 0.01% to 5% by weight of a metal-chelating agent,
    the said composition having a pH of between 7 and 11 and a molar ratio z/y of between 40/60 and 60/40.
14. Cleaning composition according to one of Claims 1 to 4 for cleaning glass-ceramic plates, characterized in that it comprises:

    - from 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;

    - from 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 butyl diglycol;

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

    - optionally, a basifying agent or a sequestering agent,
    the said composition having a pH of between 7 and 11 and a ratio z/y of between 40/60 and 60/40.
15. 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 monomeric compound of general formula I:

    

    in which

    - R₁ is a hydrogen atom or a methyl group, preferably a methyl group;

    - R₂, R₃ and R₄ 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 which is compatible with the water-soluble or water-dispersible nature of the polymer;

    (b) at least one hydrophilic monomer chosen from C₃-C₈ carboxylic acids containing monoethylenic unsaturation, anhydrides thereof and water-soluble salts thereof;

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

    - the molar ratio (a)/(b) is between 25/75 and 70/30

    - the copolymer is

    

    in which

    - the sum of x+y+z is equal to 100%,

    - x, y and z represent the molar percentages of units derived, respectively, from acrylamide, from acrylic acid and from MAPTAC in the copolymer

    - x is between 10% and 40%, preferably between 10 and 30%,
    the average charge Q on the polymer defined by the equation: $$\mathrm{Q}\mathrm{=}\frac{\left[\mathrm{a}\right]\mathrm{-}\left[\mathrm{b}\right]\mathrm{\Gamma }}{\left[\mathrm{a}\right]}$$

    

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

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

    - Γ represents the rate of neutralization of monomers (b) defined by: $$\mathrm{\Gamma }\mathrm{=}\frac{\left[{\mathrm{COO}}^{\mathrm{-}}\right]}{\left[\mathrm{COOH}\right]\mathrm{+}\left[{\mathrm{COO}}^{\mathrm{-}}\right]}$$

    

    
    in which [COOH] and [COO^-] represent, respectively, the molar concentrations of monomers (b) in carboxylic acid and carboxylate form at the pH at which the cleaning composition is used,

    being greater than 0 and possibly going down to 0.4, advantageously down to 0.2,

    in order to give hydrophilization properties to a hard surface onto which it has been applied.
16. Use, in a liquid cleaning composition for a hard surface, of at least one copolymer as defined in one of Claims 1 to 4, to improve the drying speed of a surface onto which the said composition has been applied.
17. Use according to Claim 15, characterized in that the hydrophilization properties are chosen from the long-lasting "run-resistance" and "anti-misting" properties and the long-lasting "stain-resistance" or "mark-resistance" properties.
18. Use according to one of Claims 15 to 17, characterized in that from 0.0001 to 6 g/m², preferably from 0.001 to 2 g/m², of surface area of the said water-soluble or water-dispersible copolymer is deposited onto the surface to be treated.
19. Use according to one of Claims 15 to 18, to give hydrophilizing properties to a glass or ceramic surface, or to improve the drying speed of such a surface.
20. Use according to Claims 17 to 19, for cleaning or rinsing washing-up crockery by hand or in an automatic dishwasher.
21. Use according to Claims 17 to 19, for cleaning glass panels.
22. Use according to Claims 17 to 19, for cleaning tiles, baths and sinks.
23. Use according to Claims 17 to 19, for cleaning toilet pans.
24. Use according to Claims 17 to 19, for cleaning the walls of showers.
25. Use according to Claims 17 to 19, for cleaning glass-ceramic plates.
26. Use according to one of Claims 15 to 18, for the external cleaning of motor vehicles.