EP1196523B1 - Cleansing composition comprising a water soluble or water dispersible polymer - Google Patents

Abstract

This invention relates to a cleaning composition comprising at least one surfacatant or at least one cosmetic vehicle and a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units: (a) at least one monomer compound of general formula I: (b) at least one hydrophilic monomer carrying a functional group with an acidic nature which is copolymerizable with (a) and which is capable of being ionized in the application medium; (c) optionally at least one hydrophilic monomer compound with ethylenic unsaturation with a neutral charge, carrying one or more hydrophilic groups, which is copolymerizable with (a) and (b).

Description

The present invention relates to a cleaning composition or rinsing agent for the treatment of industrial hard surfaces or community, including glass, glass, ceramic, tile, hard organic polymer, metal, wood ... intended to confer on them hydrophilic properties as well as protective (anticorrosion) properties of the glass, dishes and decorations by washing-up media during washings repeated in automatic dishwasher.

The invention more particularly relates to a composition cleaning agent for the treatment of a hard surface which is suitable for conferring this one of residual hydrophilic properties so as to avoid the presence subsequent traces due in particular to the drying of water drops deposited on said surface.

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

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

So far, there is no satisfactory solution to this problem.

To solve the problem of shrinkage and drying drops of water, the solution is to increase the hydrophilicity of the surface in order to achieve the lowest possible contact angle between the hard surface to treat and the drop of water.

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

JP 61 60 9884 -A- discloses a composition for treatment anti-static materials made of synthetic fibers, plastic films or paper, comprising a polymer derived from a polycationic monomer and a guanidine salt.

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

   dans laquelle

• R₁ est un atome d'hydrogène, un groupe méthyle ou éthyle ;
• R₂, R₃, R₄, R₅, R₆ identiques ou différents sont des groupes alkyle, hydroxyalkyle ou aminoalkyle, linéaire ou ramifié en C₁-C₆, de préférence en C₁-C₄.
• m est un nombre entier de 0 à 10, de préférence de 0 à 2 ;
• n est un nombre entier de 1 à 6, de préférence 2 à 4 ;
• Z représente un groupe -C(O)O-, -C(O)NH- ou un atome d'oxygène ;
• A représente un groupe (CH₂)_p, p étant un nombre entier de 1 à 6, de préférence de 2 à 4;
• B représente une chaíne polyméthylène linéaire ou ramifiée en C₂-C₁₂, avantageusement C₃-C₆, éventuellement interrompue par un ou plusieurs hétéroatomes ou hétérogroupes O ou NH, et éventuellement substituée par un ou plusieurs groupes hydroxyles ou amino, de préférence hydroxyles ;
• X identiques ou différents représentent des contre-ions ;

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

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

A first subject of the invention consists of a cleaning or rinsing composition 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

• R ₁ is a hydrogen atom, a methyl or ethyl group;
• R ₂ , R ₃ , R ₄ , R ₅ and R _{6, which may be} identical or different, are linear or branched C ₁ -C ₆ , preferably C ₁ -C ₄ , alkyl, hydroxyalkyl or aminoalkyl groups.
• m is an integer of 0 to 10, preferably 0 to 2;
• n is an integer of 1 to 6, preferably 2 to 4;
• Z represents a group -C (O) O-, -C (O) NH- or an oxygen atom;
• A represents a group (CH ₂ ) _p , p being an integer from 1 to 6, preferably from 2 to 4;
• B represents a linear or branched C ₂ -C ₁₂ polymethylene chain, advantageously C ₃ -C ₆ , optionally interrupted by one or more heteroatoms or heterogroups O or NH, and optionally substituted by one or more hydroxyl or amino groups, preferably hydroxyl groups; ;
• X identical or different represent counter ions;

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

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

The monomer (a) can be prepared for example according to the following reaction schemes:

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

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

This property of hydrophilization of the surface allows more than reduce fogging on the surface; this profit can be exploited in cleaning formulas for windows and mirrors, especially in theaters bath.

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

Unless otherwise indicated, when 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 copolymer is preferably random.

• Z représente C(O)O, C(O)NH ou O, tout préférentiellement C(O)NH;
• n est égal à 2 ou 3, tout particulièrement 3
• m va de 0 à 2, de préférence est égal à 0 ou 1, tout particuliètrement à 0 ;
• B représente
  
     avec q de 1 à 4, de préférence égal à 1 ;
• R₁ à R₆ identiques ou différents représentent un groupe méthyle ou éthyle.

Preferably, in the general formula (I) of the monomer (a),

• Z represents C (O) O, C (O) NH or O, most preferably C (O) NH;
• n is 2 or 3, especially 3
• m is 0 to 2, preferably 0 or 1, most preferably 0;
• B represents
  
  with q from 1 to 4, preferably 1;
• R ₁ to R _{6, which may be} identical or different, represent a methyl or ethyl group.

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

X ^- representing the chloride ion.

p = 2 à 4Other monomers (a) of particular interest are:

p = 2 to 4

Anions X are in particular a halogen anion, preferably chlorine, sulphonate, sulphate, hydrogen sulphate, phosphate, phosphonate, citrate, formate and acetate.

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

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

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, esters of acrylic acid or methacrylic acid and polyethylene glycol or polypropylene glycol mono C ₁ -C ₂₅ alkyl ethers, vinyl acetate, vinylpyrrolidone, methylvinylether.

The level of monomers (a) is advantageously between 3 and 80 mol%, preferably 10 to 60 mol%.

The level of monomers (b) is advantageously between 10 and 95 mol%, preferably 20 to 70 mol%.

The level of monomers (c) is advantageously between 0 and 50%, preferably 0 and 30%, most preferably 5 to 25% molar.

The molar ratio of cationic monomer to monomer anionic (a) / (b) is advantageously between 80/20 and 5/95, preferably between 60/40 and 20/80.

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

It will be possible in particular to refer to the processes described in US 4 387,017 and EP 156,646.

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

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

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

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

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

avec x ayant une valeur moyenne de 0 à 50%, de préférence de 0 à 30%, tout particulièrement de 5 à 25%,
   y ayant une valeur moyenne de 10 à 95%, de préférence de 20 à 70%,
   z ayant une valeur moyenne de 3 à 80%, de préférence de 10 à 60%,
   et le rapport y/z étant de manière préférée de l'ordre de 4/1 à 1/2,
avec x+y+z = 100%, x, y et z représentant les % molaires de motifs dérivés respectivement d'acrylamide, d'acide acrylique (sel de sodium) et de DIQUAT.A particularly preferred copolymer is the following:

with x having an average value of 0 to 50%, preferably 0 to 30%, most preferably 5 to 25%,
y having an average value of 10 to 95%, preferably 20 to 70%,
z having an average value of 3 to 80%, preferably 10 to 60%,
and the ratio y / z being preferably of the order of 4/1 to 1/2,
with x + y + z = 100%, x, y and z representing the mol% of units respectively derived from acrylamide, acrylic acid (sodium salt) and DIQUAT.

avec x ayant une valeur moyenne de 0 à 50% de préférence de 0 à 30%, tout particulièrement de 5 à 25%,
   y ayant une valeur moyenne de 10 à 95%, de préférence de 20 à 70%,
   z ayant une valeur moyenne de 3 à 80%, de préférence de 10 à 60%,
   et le rapport y/z étant de manière préférée de l'ordre de 4/1 à 1/2, avec x+y+z = 100%, x, y et z représentant les % molaires de motifs dérivés respectivement d'acrylamide, d'acide acrylique (sel de sodium) et de DIQUAT.Other preferred polymers are as follows:

with x having an average value of 0 to 50%, preferably 0 to 30%, most preferably 5 to 25%,
y having an average value of 10 to 95%, preferably 20 to 70%,
z having an average value of 3 to 80%, preferably 10 to 60%,
and the ratio y / z being preferably of the order of 4/1 to 1/2, with x + y + z = 100%, x, y and z representing the mol% of units respectively derived from acrylamide, of acrylic acid (sodium salt) and DIQUAT.

According to the invention, the copolymers can be used in particularly in cleaning compositions for hard surfaces.

In the field of cleaning, copolymers are useful for giving surfaces on which they are applied hydrophilic properties, in particular for imparting anti-stain or anti-stick trace properties.

In addition, they have the property of preventing or limiting corrosion of glass, dishes and decorations by detergent media during repeated washing in automatic dishwasher.

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

Said copolymers can be introduced into a formulation cleaning or rinsing intended to treat hard surfaces to a certain between 0.0005% and 10%, preferably between 0.001 and 5% by weight relative to the total weight of the formulation, depending on the concentration of active ingredients of the composition.

The composition according to the invention comprises less a surfactant. This is advantageously anionic and / or not ionic. It can also be cationic, amphoteric or zwitterionic.

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

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 linear C ₈ -C ₁₃ alkyl-benzenesulphonates, in which the alkyl group comprises from 10 to 16 carbon atoms, alcohol-sulphates, ethoxylated alcohol-sulphonates, hydroxyalkylsulphonates; alkyl sulphates and sulphonates, especially 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:

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

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

• les alkylphénols polyoxyalkylénés (polyéthoxyéthylénés, polyoxypropylénés, polyoxybutylénés) dont le substituant alkyle est en C₆-C₁₂ et contenant de 5 à 25 motifs oxyalkylènes ; à titre d'exemple, on peut citer les TRITON X-45, X-114, X-100 ou X-102 commercialisés par Rohm & Haas Cy. ;
• les glucosamides, glucamides, glycérolamides ;
• les alcools aliphatiques en C₈-C₂₂ polyoxyalkylénés contenant de 1 à 25 motifs oxyalkylènes (oxyéthylène, oxypropylène). A titre d'exemple, on peut citer les TERGITOL 15-S-9, TERGITOL 24-L-6 NMW commercialisés par Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 commercialisés par Shell Chemical Cy., les RHODASURF IDO60, RHODASURF LA90, RHODASURF IT070 commercialisés par la société RHODIA.
• les oxydes d'amines tels que les oxydes d'alkyl C₁₀-C₁₈ diméthylamines, les oxydes d'alkoxy C₈-C₂₂ éthyl dihydroxy éthylamines ;
• les alkylpolyglycosides décrits dans US-A-4 565 647 ;
• les amides d'acides gras en C₈-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 IDO60, RHODASURF LA90, RHODASURF IT070 marketed by Rhodia.
• amine oxides such as C ₁₀ -C ₁₈ alkyl dimethylamine oxides, C ₈ -C ₂₂ alkoxy ethyl dihydroxy ethylamine oxides;
• the alkylpolyglycosides described in US-A-4,565,647;
• C ₈ -C ₂₀ fatty acid amides;
• ethoxylated fatty acids;
• ethoxylated amines

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

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

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

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

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

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

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

The following surfactants are preferred:

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

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

The surfactants may be present, if necessary, at 0.005 to 60%, especially 0.5 to 40% by weight depending on the nature of the surfactant (s) and the purpose of the composition cleaning or rinsing.

• notamment pour le lavage en machine à laver la vaisselle
  • des "builders" (adjuvants de détergence améliorant les propriétés de surface des tensioactifs) organiques du type :
    • phosphonates organiques comme ceux de la gamme DEQUEST® de MONSANTO, (à raison de 0 à 2 % du poids total de composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
    • acides polycarboxyliques ou leurs sels hydrosolubles et les sels hydrosolubles de polymères ou de copolymères carboxyliques tels que
      • éthers polycarboxylates ou hydroxypolycarboxylates
    • acides polyacétiques ou leurs sels (acide nitriloacétique, acide N,N-dicarboxyméthyl-2-aminopentane dioïque, acide éthylènediamine tétraacétique, acide diéthylènetriamine pentaacétique, éthylènediaminetetraacétates, nitrilotriacétates comme le NERVANAID NTA Na₃ commercialisé par la société RHODIA, N-(2 hydroxyéthyl)-nitrilodiacétates ), (à raison de 0 à 10 % du poids total de composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle);
      • sels d'acides alkyl C₅-C₂₀ succiniques
      • esters polyacétals carboxyliques
      • sels d'acides polyaspartiques ou polyglutamiques
    • acide citrique, acide gluconique ou acide tartrique ou leurs sels (à raison de 0 à 10 % du poids total de composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle);
  • des "builders" (adjuvants de détergence améliorant les propriétés de surface des tensioactifs) minéraux du type :
    • polyphosphates de métaux alcalins, d'ammonium ou d'alcanolamines tels que le RHODIAPHOS HPA3,5 commercialisé par la société RHODIA, (à raison de 0 à 70 % du poids total de composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
    • pyrophosphates de métaux alcalins
    • zéolites ;
    • silicates (en quantité pouvant aller jusqu'à 50 % environ du poids total de ladite composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
    • borates, carbonates, bicarbonates, sesquicarbonates alcalins ou alcalino-terreux (en quantité pouvant aller jusqu'à 50 % environ du poids total de ladite composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
    • cogranulés de silicates hydratés de métaux alcalins et de carbonates de métaux alcalins (sodium ou de potassium) décrits dans EP-A-488 868, comme le NABION 15 commercialisé par la société RHODIA (en quantité pouvant aller jusqu'à 50 % environ du poids total de ladite composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
    (la quantité totale de "builders", organiques et/ou minéraux, pouvant représenter jusqu'à 90% du poids total de ladite composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
  • des agents de blanchiment du type perborates, percarbonates associés ou non à des activateurs de blanchiment acétylés comme la N, N, N', N'-tétraacétyl-éthylènediamine (TAED) ou des produits chlorés du type des chloroisocyanurates, ou des produits chlorés du type hypochlorites de métaux alcalins, (à raison de 0 à 30 % du poids total de ladite composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
  • des agents auxiliaires de nettoyage du type copolymères d'acide acrylique et d'anhydride maléïque ou des homopolymères d'acide acrylique (à raison de 0 à 10 %, du poids total de ladite composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
  • des charges du type sulfate de sodium, chlorure de sodium à raison de 0 à 50 % du poids total de ladite composition exprimé en matière sèche;
  • d'autres additifs divers comme des agents influant sur le pH de la composition détergente, notamment des additifs alcalinisants solubles dans le milieu lessiviel (phosphates de métaux alcalins, carbonates, perborates, hydroxydes ou des additifs acidifiants solubles dans le milieu lessiviel (acides carboxyliques ou polycarboxyliques, bicarbonates et sesquicarbonates de métaux alcalins, acides phosphoriques et polyphosphoriques, acides sulfoniques, etc) ; ou des enzymes ou des parfums, colorants, agents inhibiteurs de corrosion des métaux ;
• notamment pour le lavage à la main de la vaisselle
  • des polymères cationiques synthétiques comme le MIRAPOL A550®, le MIRAPOL A15® commercialisés par RHODIA, le MERQUAT 550® commercialisé par CALGON.
  • des polymères utilisés pour contrôler la viscosité du mélange et/ou la stabilité des mousses formées à l'utilisation, comme les dérivés de cellulose ou de guar (carboxyméthylcellulose, hydroxyéthylcellulose, hydroxypropylguar, carboxyméthylguar, carboxyméthylhydroxypropyl-guar)
  • des agents hydrotropes, comme les alcools courts en C₂-C₈, en particulier l'éthanol, les diols et glycols comme le diéthylène glycol, dipropylène-glycol,
  • des agents hydratants ou humectants pour la peau comme le glycérol, l'urée ou des agents protecteurs de la peau, comme les protéines ou hydrolysats de protéines, les polymères cationiques comme les dérivés cationiques du guar (JAGUAR C13S®, JAGUAR C162®, HICARE 1000® commercialisés par la société RHODIA,

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

• especially for washing in the dishwashing machine
  • builders (detergency builders improving the surface properties of surfactants) organic of the type:
    • organic phosphonates, such as those of the DEQUEST® range of MONSANTO, (in a proportion of 0 to 2% of the total weight of detergent composition expressed as dry matter in the case of a dishwashing composition);
    • 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" (detergency builders 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 marketed by Rhodia (in an amount of up to about 50% by weight total 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 type, percarbonates associated or not with acetylated bleach activators such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED) or chloroisocyanurate-type chlorinated products, or chlorinated products of the type hypochlorites of alkali metals, (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 sodium sulfate type, sodium chloride in a proportion of 0 to 50% of the total weight of said composition expressed as dry matter;
  • other various additives such as agents affecting the pH of the detergent composition, especially alkalizing additives soluble in the washing medium (alkali metal phosphates, carbonates, perborates, hydroxides or acidifying additives soluble in the washing medium (carboxylic acids or polycarboxylic, bicarbonates and sesquicarbonates of alkali metals, phosphoric and polyphosphoric acids, sulfonic 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 foams formed in use, such as cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropyl-guar)
  • hydrotropic agents, such as short C ₂ -C ₈ alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol,
  • skin moisturizing or humectant agents such as glycerol, urea or skin-protecting agents, such as proteins or protein hydrolysates, cationic polymers such as cationic derivatives of guar (JAGUAR C13S®, JAGUAR C162®, HICARE 1000® marketed by Rhodia,

The compositions 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 from 0.001 to 0.1 g / m ² of surface to be treated.

According to a particularly advantageous mode, the composition cleaning agent according to the invention is used for surface treatment glass, including windows. This treatment can be carried out by the various known techniques. We can mention in particular the cleaning techniques windows by spraying a jet of water using Karcher® type appliances.

The quantity of polymer introduced will generally be such that when using the cleaning composition, after any 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 indicated in 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 composition of the invention is also of interest for cleaning the dishes by hand or automatic machine. In this last case, said copolymer may be present either in the detergent formula used in the wash cycle, either in the rinsing liquid.

Dishwashing detergent formulations in automatic dishwashers advantageously comprise from 0.1 to 5%, preferably from 0.2 to 3% by weight of water-soluble copolymer or hydrodispersible relative to the total weight of dry matter of the composition.

Detergent compositions for dishwashers include also at least one surfactant, preferably nonionic in 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 various additives and fillers, as already mentioned above. These formulas usually include 30 to 95% of an agent builder, chosen among silicates, phosphates, carbonates. They include also an oxidizing system, introduced at a content of between 3 and 25%.

Surprisingly, it has been discovered that the use of a copolymer according to the invention in a composition for washing in the dishwasher, protected glass and dishes against corrosion by the environment detergent during repeated washings.

Dishwashing formulations for dishwashers automatically 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 0.2 to 15%, preferably 0.5 to 5% by weight relative to the total weight of said composition of an agent surfactant, preferably nonionic or a mixture of nonionic surfactant and anionic.

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, optionally polyoxyethylenated carboxylic amides.

They furthermore comprise from 0 to 40%, preferably from 3 to 30%. % by weight relative to the total weight of the composition of an organic acid sequestering calcium, preferably citric acid.

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

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 aimed more particularly at formulations aqueous lathering liquid detergents for hand washing of the washing up.

• 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 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.
• bactericidal or disinfecting agents such as triclosan
• synthetic cationic polymers
• polymers for controlling the viscosity of the mixture and / or the stability of foams formed upon use
• hydrotropic agents
• moisturizing or humectant or skin-protecting agents
• dyes, perfumes, preservatives

as already mentioned above.

Another subject of the invention consists of a composition cleaning agent for external cleaning, in particular of the bodywork, 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, either in a rinsing product.

• des agents tensioactifs non ioniques (à raison de 0 à 30%, de préférence de 0.5 à 15 % de la formulation),
• des agents tensioactifs amphotères et/ou zwitterioniques (à raison de 0 à 30%, de préférence de 0.5 à 15 % de la formulation)
• des agents tensioactifs cationiques (à raison de 0 à 30%, de préférence de 0.5 à 15 % de la formulation);
• des agents tensioactifs anioniques (à raison de 0 à 30%, de préférence de 0.5 à 15 % de la formulation);

• des adjuvants de détergence ("builders") organiques ou minéraux
• des agents hydrotropes
• des charges, des agents régulant le pH

The cleaning composition for motor vehicles advantageously comprises from 0.05 to 5% by weight of copolymer 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 type of composition may be at least 1% of the formulation)

The composition of the invention is also particularly suitable for the cleaning of hard surfaces other than those described above, ceramics (tiling, bathtubs, washbasins, etc ...).

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

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

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

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

Anionic surfactant may optionally be present in 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 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 invention may also contain other minority ingredients which are cleaning additives.

For example, the composition may contain adjuvants of detergents ("builders") organic or mineral as mentioned previously.

In general, the detergency builder is used in a quantity between 0.1 and 25% by weight relative to the total weight of the composition.

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

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

The composition of the invention can also be used by cleaning the toilet bowls.

A composition particularly suitable for this purpose comprises from 0.05 to 5% by weight of copolymer used according to the invention.

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

The amount of acidic ingredients is preferably between 0.1 to about 40%, and preferably 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, between about 5 and about 30% by weight.

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

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

Cationic surfactants can also be added to the cleaning composition of toilet bowls according to the invention for bring germicidal properties. The skilled person will see that agents Amphoteric surfactants can also be used. Mixtures of Various surfactants can be used if desired.

The cleaning composition of toilet bowls 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: an agent preservative intended to prevent the growth of microorganisms in the product, dye, perfume, and / or abrasive.

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

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

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

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

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

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

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

The composition according to the invention can also be works for the cleaning of 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 n-butyldiéthylèneglycol ;
• 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 n-butyldiethylene glycol;
• 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.

• au moins un copolymère hydrosoluble ou hydrodispersable tel que décrit dans l'invention
• au moins un biocide cationique, amphotère ou aminé, de préférence cationique
• et éventuellement au moins un agent tensioactif non-ionique, amphotère, zwitterionique, de préférence nonionique.

Another object of the invention is an aqueous biocidal cleaning composition for the treatment of hard surfaces comprising:

• at least one water-soluble or water-dispersible copolymer as described in the invention
• at least one cationic, amphoteric or amine biocide, preferably cationic
• and optionally at least one nonionic surfactant, amphoteric, zwitterionic, preferably nonionic.

The biocide is preferably present in the composition aqueous biocidal cleaner at a concentration in the range of 0.1% to 20% weight, preferably of the order of 0.5% to 5% by weight.

The copolymer may be present in the aqueous biocidal cleaning composition at a concentration of the order of 0.01% to 20% by weight, preferably in the range of 0.05 to 5% by weight. said The copolymer, in itself, generally does not have any biocidal activity.

• les sels de monoammonium quaternaire de formules R¹ R² R³ R⁴ N⁺ X^- où
  R' représente un groupe benzyle éventuellement substitué par un atome de chlore ou un groupe C₁-C₄ alkylbenzyle
  R² représente un groupe alkyle en C₈-C₂₄
  R³ et R⁴ , semblables ou différents , représentent un groupe alkyle ou hydroxyalkyle en C₁-C₄
  X^- est un anion solubilisant tel qu'halogénure (par exemple chlorure, bromure, iodure), sulfate ou méthylsulfate, R^1' R^2' R^3' R^4' N⁺ X^- où
  R^1' et R^2' , semblables ou différents, représentent un groupe alkyle en C₈-C₂₄
  R^3' et R^4' , semblables ou différents , représentent un groupe alkyle en C₁-C₄
  X^- est un anion solubilisant tel qu'halogénure (par exemple chlorure, bromure, iodure), sulfate ou méthylsulfate, R^1" R^2" R^3" R^4" N⁺ X^- où
  R^1" représente un groupe alkyle en C₈-C₂₄
  R^2", R^3" et R^4" , semblables ou différents , représentent un groupe alkyle en C₁-C₄
  X^- est un anion solubilisant tel qu'halogénure (par exemple chlorure, bromure, iodure), sulfate ou méthylsulfate
  notamment :
  • les chlorures de coco-alkyl benzyl diméthylammonium, de C₁₂-C₁₄ alkyl benzyl diméthylammonium, de coco-alkyl dichlorobenzyl diméthylammonium, de tetradecyl benzyl diméthylammonium, de didécyl diméthylammonium, de dioctyl diméthylammonium
  • les bromures de myristyl triméthylammonium, de cétyl triméthylammonium
• les sels d'amines hétérocycliques monoquatemaires tels que . les chlorures de laurylpyridinium, de cétylpyridinium, de C₁₂-C₁₄ alkyl benzyl imidazolium
• les sels d'alkyl gras triphényl phosphonium comme le bromure de myristyl triphényl phosphonium
• les biocides amphotères comme les dérivés de N-(N'-C₈-C₁₈alkyl-3-aminopropyl)-glycine, de N-(N'-(N"-C₈-C₁₈alkyl-2-aminoéthyl)-2-aminoéthyl)-glycine, de N,N-bis(N'-C₈-C₁₈alkyl-2-aminoéthyl)-glycine, tels que le (dodécyl) (aminopropyl) glycine, le (dodécyl) (diéthylènediamine) glycine
• les amines comme la N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine

Among the biocidal agents that may be present, mention may be made of:

• the quaternary monoammonium salts of formulas R ¹ R ² R ³ R ⁴ N ⁺ X ^- or
  R 'represents a benzyl group optionally substituted with a chlorine atom or a C ₁ -C ₄ alkylbenzyl group
  R ² represents an alkyl group of C ₈ -C ₂₄
  R ³ and R ⁴ , which are the same or different, represent a C ₁ -C ₄ alkyl or hydroxyalkyl group;
  X ^- is a solubilizing anion such as halide (for example chloride, bromide, iodide), sulfate or methylsulfate, R ^{1 '} R ^2' R ^{3 '} R ^4' N ⁺ X ^- or
  R ^{1 '} and R ^2' , which are the same or different, represent a C ₈ -C ₂₄ alkyl group
  R ^{3 '} and R ^4' , which are the same or different, represent a C ₁ -C ₄ alkyl group
  X ^- is a solubilizing anion such as halide (for example chloride, bromide, iodide), sulfate or methylsulfate, R ^{1 "} R ^2" R ^{3 "} R ^4" N ⁺ X ^- or
  R ^{1 "} represents a C ₈ -C ₂₄ alkyl group
  R ^{2 "} , R ^3" and R ^{4 "} , which are the same or different, represent a C ₁ -C ₄ alkyl group
  X ^- is a solubilizing anion such as halide (e.g. chloride, bromide, iodide), sulfate or methyl sulfate
  especially :
  • chloro-alkyl benzyl dimethyl ammonium chloride, C ₁₂ -C ₁₄ alkyl benzyl dimethyl ammonium chloride, coco-alkyl dichlorobenzyl dimethyl ammonium chloride, tetradecyl benzyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride
  • myristyl trimethylammonium bromides, cetyl trimethylammonium
• monoquatemarian heterocyclic amine salts such as. chlorides of laurylpyridinium, cetylpyridinium, C ₁₂ -C ₁₄ alkyl benzyl imidazolium
• triphenyl phosphonium alkyl fatty salts such as myristyl triphenyl phosphonium bromide
• amphoteric biocides, such as N- (N'-C ₈ -C ₁₈ alkyl-3-aminopropyl) -glycine derivatives of N- (N '- (N "-C ₈ -C ₁₈ alkyl-2-aminoethyl) - 2-aminoethyl) -glycine, N, N-bis (N'-C ₈ -C ₁₈ alkyl-2-aminoethyl) -glycine, such as (dodecyl) (aminopropyl) glycine, (dodecyl) (diethylenediamine) glycine
• amines such as N- (3-aminopropyl) -N-dodecyl-1,3-propanediamine

• des agents tensioactifs non-ioniques comme, les polymères blocs oxyde d'éthylène - oxyde de propylène, les esters de sorbitan polyéthoxylés, les esters gras de sorbitan, les esters gras éthoxylés (contenant de 1 à 25 unités d'oxyde d'éthylène), les alcools en C₈-C₂₂ polyéthoxylés (contenant de 1 à 25 unités d'oxyde d'éthylène), les alkylphénols en C₆-C₂₂ polyéthoxylés (contenant de 5 à 25 unités d'oxyde d'éthylène), les alkylpolyglycosides, les oxydes d'amines (tels que les oxydes de C₁₀-C₁₈ alkyldiméthylamines, les oxydes de C₈-C₂₂ alkoxyethyl dihydroxyéthylamine)
• des agents tensioactifs amphotères ou zwitterioniques comme les C₆-C₂₀ alkylamphoacétates ou amphodiacétates (tels que les cocoamphoacétates), C₁₀-C₁₈ alkyldiméthylbétaines, C₁₀-C₁₈ alkylamidopropyldiméthylbétaines, C₁₀-C₁₈ alkyldiméthyl sulphobétaines, C₁₀-C₁₈ alkylamidopropyldiméthyl sulfobétaines.

Among the possible surfactants, mention may in particular be made of:

• nonionic surfactants such as ethylene oxide propylene oxide block polymers, polyethoxylated sorbitan esters, sorbitan fatty esters, ethoxylated fatty esters (containing from 1 to 25 ethylene oxide units) , polyethoxylated C ₈ -C ₂₂ alcohols (containing from 1 to 25 ethylene oxide units), polyethoxylated C ₆ -C ₂₂ alkylphenols (containing from 5 to 25 ethylene oxide units), alkylpolyglycosides, amine oxides (such as C ₁₀ -C ₁₈ alkyldimethylamine oxides, C ₈ -C ₂₂ alkoxyethyl dihydroxyethylamine oxides)
• amphoteric or zwitterionic surfactants such as C ₆ -C ₂₀ alkylamphoacetates or amphodiacetates (such as cocoamphoacetates), C ₁₀ -C ₁₈ alkyldimethylbetaines, C ₁₀ -C ₁₈ alkylamidopropyldimethylbetaines, C ₁₀ -C ₁₈ alkyldimethylsulphobetaines, C ₁₀ -C ₁₈ alkylamidopropyldimethyl sulfobetaines.

These can be present at the rate of 1 to 25%, preferably in the range of 2 to 10% by weight of the aqueous biocidal cleaning composition.

According to the invention, besides the biocide and the copolymer according to the invention, main constituents of the aqueous biocide system of the invention, may be present, and this advantageously, other constituents, as, chelating agents (such as aminocarboxylates (ethylenediaminetetraacetates, nitrilotriacetates, N, N-bis (carboxymethyl) glutamates, citrates), alcohols (ethanol, isopropanol, glycols), adjuvants detergents (phosphates, silicates), dyes, perfumes

Said biocidal cleaning composition can be implemented for disinfection of floors, walls, work surfaces, equipment, furniture, instruments, in industry, the agri-food sector, domestic areas (kitchens, bathrooms) and in the community.

Among the surfaces that can be treated are those in ceramic, glass, polyvinyl chloride, formica or other organic polymer hard, stainless steel, aluminum, wood

The cleaning and disinfection operation consists of applying said biocidal cleaning composition, optionally diluted 1 to 1000 times, preferably from 1 to 100 times, on the hard surface to be treated.

The amount of biocidal system that can be favorably used is that corresponding to a deposit of 0.01 to 10 g, preferably from 0.1 to 1 g of biocide per m ² of surface and to a deposit of 0.001 to 2 g, preferably from 0.01 to 0.5 g of copolymer of the invention per m ² of surface.

• les bactéries Gram négatives comme : Pseudomonas aeruginosa ; Escherichia coli ; Proteus mirabilis
• les bactéries Gram positives comme : Staphylococcus aureus ; Streptococcus faecium
• d'autres bactéries dangereuses dans l'alimentation comme : Salmonella typhimurium ; Listeria monocytogenes ; Campylobacter jejuni ; Yersinia enterocolitica
• les levures comme : Saccharomyces cerevisiae ; Candida albicans
• les champignons comme : Aspergillus niger ; Fusarium solani ; Pencillium chrysogenum
• les algues comme : Chlorella saccharophilia ; Chlorella emersonii ; Chlorella vulgaris ; Chlamydomonas eugametos

Among the microorganisms whose proliferation can be controlled by using the biocidal cleaning composition of the invention, mention may be made of

• Gram-negative bacteria such as: Pseudomonas aeruginosa ; Escherichia coli ; Proteus mirabilis
• Gram-positive bacteria such as: Staphylococcus aureus ; Streptococcus faecium
• other dangerous bacteria in the diet such as: Salmonella typhimurium ; Listeria monocytogenes ; Campylobacter jejuni ; Yersinia enterocolitica
• yeasts such as: Saccharomyces cerevisiae ; Candida albicans
• mushrooms such as: Aspergillus niger ; Fusarium solani ; Pencillium chrysogenum
• algae such as: Chlorella saccharophilia ; Chlorella emersonii ; Chlorella vulgaris ; Chlamydomonas eugametos

The biocidal system of the invention is particularly effective on gram-negative microorganisms Pseudomonas aeroginosa, Gram-positive Staphylococcus aureus , the fungus Aspergillus niger.

The invention also relates to the use of a water-soluble or water-dispersible copolymer as defined above for cleaning or rinsing a hard surface, in particular to give a hard surface, hydrophilization properties.

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

It likewise relates to a process for improving hydrophilicity of a hard surface, by treating said surface with a composition cleaning agent comprising at least one copolymer according to the invention.

It also relates to the use of a copolymer such that previously defined to improve the drying speed of a hard surface on which the copolymer is applied.

Another object of the invention is the use, in a detergent composition for dishwashing in the dishwasher automatically, a copolymer according to the invention as an agent for eliminating or to reduce the corrosion of the glass and the decorations present on the glass or dishes during repeated washings.

Finally, the subject of the invention is a method for the protection of glass, crockery and decorations, by washing glass and dishes in an automatic dishwasher, using a cleaning composition comprising at least one copolymer according to the invention.

The examples below are intended to illustrate the invention.

EXAMPLES 1 to 5: Preparation of the copolymers according to the invention of formula:

Référence x (mol%) y (mol%) z (mol%) viscosité de la solution en cps extrait sec % pH Polymère 1 20 40 40 29 500 mPa.s 20,5% 2,2 à 10% d'extrait sec Polymère 2 0 50 50 840 mPa.s 20,5% 1,7 à 20,5% d'extrait sec Polymère 3 0 200/3 100/3 8 700 mPa.s 20,0% 1,6 à 20,0% d'extrait sec Polymère 4 0 80 20 37 250 mPa.s 17% 1,5 à 17% d'extrait sec Polymère 5 25 50 25

Reference x (mol%) y (mol%) z (mol%) viscosity of the solution in cps dry extract% pH Polymer 1 20 40 40 29,500 mPa.s 20.5% 2.2 to 10% of dry extract Polymer 2 0 50 50 840 mPa.s 20.5% 1.7 to 20.5% dry extract Polymer 3 0 200/3 100/3 8,700 mPa.s 20.0% 1.6 to 20.0% dry extract Polymer 4 0 80 20 37 250 mPa.s 17% 1.5 to 17% dry extract Polymer 5 25 50 25

In a 1-liter reactor, the following ingredients are added: Polymer 1 Polymer 2 Polymer 3 Polymer 4 Polymer 5 Demineralized Water 633 707 632.5 737 633 Acrylamide 52% 29.3 0 0 0 29.3 Acrylic acid 30.9 33.5 55.5 89.1 30,9 Diquat Monomer 65% 236.7 256.2 212.3 170.6 118.35 Versene 100
(EDTA from Dow Chemical) 0.2 0.2 0.2 0.2 0.2

The resulting mixture is gently heated to a pH of about 2.6 under a gentle nitrogen purge at 75 ° C. After 30 minutes, when the When the temperature reaches 75 ° C., a solution of initiator based on sodium persulfate (0.1 g in 1.0 g deionized water) at one time in the reactor. Cooling is necessary to maintain the temperature at 75 ° C, and the mixture becomes viscous after about 45 minutes. Two additional portions of persulfate-based initiation solution are added after one and two hours of reaction respectively. Then, the The reaction mixture is heated to a temperature of 85 ° C and maintained at this temperature for two more hours before being cooled down to 25 ° C. The viscosity of the resulting polymer solution 1 is about 29,500 mPa.s. with a total solids content of about 20.5%. The pH of the solution to 10% is about 2.2. The residual acrylamide is less than 0.1% by weight.

EXAMPLE 6 Preparation of the polymer of formula:

   avec x = 20, y = 40, z = 40 (polymère 6)

with x = 20 , y = 40 , z = 40 (polymer 6)

The process is the same as that of Examples 1 to 5, except that the acrylic acid is replaced by N- (1-sulfo-2-isobutyl) acrylamide.

EXAMPLES 7 to 9: Cleaning formulations for window cleaning

The table below reports the composition of three cleaning formulations used for window cleaning: components Formulations (by weight) Example 7 Example 8 Example 9 Isopropylic alcohol 7 7 15 Fatty alcohol (C12) ethoxylated (7OE) 0 0 3 Sodium dodecylbenzene sulphonate 0.5 0.5 0 Ammonium hydroxide 0.3 0.3 0.3 Dipropylene glycol monomethyl ether 0.25 0.25 0.5 Copolymer No. 1 described in the invention 0.05 0.5 1 Water qs 100 qs 100 qs 100

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

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

The table below gives cleaning formulations for cleaning hard surfaces. components Formulations (by weight) Example 10 Example 11 Fatty alcohol (C12) ethoxylated (7OE) 6 8 Alkane (C12) sodium sulfonate 3 2 Welded such that pH = 10.4 such that pH = 10.4 Copolymer No. 2 described in the invention 1 0.5 Water qs 100 qs 100

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

EXAMPLES 12 to 14: Detergent formulas for automatic dishwashers

A basic detergent formula is prepared from the compounds given in the table below: compounds % weight Granulated sodium tripolyphosphate 45 Sodium carbonate 4 Granular sodium disilicate 26 Sodium perborate monohydrate 7 DAT 2 Sodium sulphate 16

To these compositions, three copolymers according to the invention (copolymer No. 2, 3 and 4 above) or two other polymers (copolymers No. 7 and No. 8 below) are added for comparison.

CORROSION TESTING OF GLASS

This simplified glass corrosion test reproduces some washing conditions of the dishwasher machines, in particular cycles of washing, rinsing and drying.

Nature of the glass

The glass used consists of microscope slides of dimension 2.5 x 7.5 cm, previously cleaned with ethanol, blades whose composition given below is close to that of table glasses: Yes 33.4% by weight It 3.4% by weight mg 1.7% by weight N / A 14.0% by weight al 0.6% by weight

Operating mode

200 ml of an aqueous solution of washing containing 6g / l of product to be tested. The container is introduced and maintained in an oven at 65 ° C for 1 hour.

In this container, a glass slide is totally immersed in inclined position. The container is then closed and placed in an oven at 65 ° C. The blade is removed from the container after 72 hours, rinsed twice on each face to the permuted water with a squeegee, brushed with the finger to remove the film possibly formed, dried in ambient air for 2 hours.

At the end of the test, the blade is weighed after cooling to room temperature and the relative mass variation (in% x 1000) is calculated. The test is repeated again for confirmation of results.

Corrosion visible to the eye is evaluated with respect to a reference not subject to the test.

The corrosion assessment is done visually with a scale from 1 to 5 points, taking as reference the glasses in new condition, by 9 people trained.

• 1 point correspond à un état parfait.
• 2 points correspondent à un endommagement à peine visible (traces blanches ou colorées sur les verres sans décors ; matification du décor du verre).
• 3 points correspondent à un endommagement très net, spontanément visible (verres sans décors globalement colorés ou blanchis, avec éventuellement la présence de défauts locaux ; les décors de verre sont mats, avec ternissement des couleurs).
• 4 points correspondent à un endommagement très important (les verres sans décors présentent aussi de larges taches blanches ; les décors de verre ont partiellement disparu).
• 5 points correspondent à des surfaces totalement dégradées (la surface est entièrement endommagée ; les décors ont disparu).

The points are distributed as follows:

• 1 point corresponds to a perfect state.
• 2 points correspond to a barely visible damage (white or colored marks on glasses without decorations, matification of glass decor).
• 3 points correspond to a very clear damage, spontaneously visible (glasses without scenery generally colored or bleached, possibly with the presence of local defects, the glass decorations are matt, with fading colors).
• 4 points correspond to a very important damage (the glasses without decorations also have large white spots, the glass decors have partially disappeared).
• 5 points correspond to completely degraded surfaces (the surface is completely damaged, the decorations have disappeared).

Finally, the pH of the solutions is measured at room temperature before immersion of the blade and at the end of the experiment.

This simplified test makes it possible to quickly reproduce different types of glass corrosion obtained by repeated washing in the dishwasher, the succession of washing-rinsing-drying cycles, and this, in conditions of concentration and temperature close to those used in dishwashers.

The results of the test are given in the table below: Example Comparative Example 12 Comparative Example 13 Comparative Example 14 Example 15 Example 16 Example 17 Composition Basic formula: 98% Sodium sulphate: 2% Basic formula: 98% Polymer 7: 2% Basic formula: 98% Polymer 7: 2% Basic formula: 98% Polymer 2: 2% Basic formula: 98% Polymer 3: 2% Basic formula: 98% Polymer 4: 2% final pH 10.33 10.35 10.35 10.32 10.33 10.35 Mass loss 10 ^-3 % 213 235 210 57 60 90 Visual appreciation 4.5 4.5 4.5 1 1 1.5

Examples 12, 13 and 14 are given for comparison.

Examples 15, 16 and 17 show that the polymers of the invention provide effective glass protection against corrosion, which is not obtained with Examples 12, 13 and 14.

EXAMPLES 15 to 17: Formulations for rinsing dishes in the dishwasher automatic

Formulation Example 15 Example 16 Example 17 Nonionic surfactant C13-3OP-7OE
(linear fatty alcohol EO / OP) 12 12 12 Citric acid 3 3 3 Polymer Polymer 1
(2%) polymer 3
(2%) polymer 5
(2%) Water qsp to 100 qsp to 100 qsp to 100

EXAMPLES 18 and 19: Hand washing dishwashing formulation

Formulation example 18 example 19 Sodium alkylsulphonate (C14) 24 12 Ethoxylated fatty alcohol C12 - 1,5 EO 5 3 Ethoxylated fatty alcohol C10 - 7OE 4 4 Polymer polymer 4
(2%) polymer 6
(2%) Water qsp to 100 qsp to 100

EXAMPLES 20 and 21: Detergent formulations for cleaning surfaces hard (tiles, washbasins, bathtubs)

Formulation example 20 example 21 Sodium alkylsulphonate (C12) 24 12 Ethoxylated fatty alcohol C12 - 6 EO 5 3 Ethanol 4 4 Polymer polymer 3
(2%) polymer 5
(2%) Water qsp to 100 qsp to 100

EXAMPLES 22 to 25: Detergent formulas for automatic dishwashers

Sample formulation Example 22 Example 23 Example 24 Example 25 Sodium tripolyphosphate 0 0 60 35 Sodium carbonate 35 30 0 20 Sodium disilicate 20 15 23 10 Sodium citrate 20 15 0 0 Sodium sulphate 0 20 0 19 Sodium polyacrylate CP5 from BASF 6 5 0 0 Plurafac LF 403 2 1 2 2 Bleach system (perborate, 1 H ₂ O + TAED **) 12 10 10 10 Other additives (including benzatriazole, enzymes, perfume) 3 3 3 3 Polymer 3 2 1 2 1

EXAMPLES 26 to 28: Biocidal formulations

Example 26 Example 27 Example 28 Nonionic surfactant
(C10 alcohol, 6 ethylene oxide units) 5% 5% 5% Rhodaquat biocide RP50% of active ingredient 1,5% 1,5% 1,5% Polymer% of active ingredient Polymer 1
0.15 or 0.2% Polymer 3
0,5% Polymer 4
0.2% Water

Rhodaquat RP50 biocide is a 50% aqueous solution of active ingredient of C12-C14 alkyl benzyl dimethyl ammonium chloride marketed by Rhodia.

The formulation of Example 26 is tested on white ceramic according to the following protocol:

1. Add 3g of dilute biocide aqueous solution to the surface of the ceramic tile (5cmx5cm) previously sterilized by cleaning at isopropyl alcohol. Dry at 45 ° C in an oven.

2. Place the tile surface vertically and sprinkle it with a gram of water using a hand-held sprayer. This corresponds to a washing without mechanical action. Between 0 and 15 washes are thus carried out before drying at 45 ° C.

3. Add 0.25ml of an aqueous medium containing approximately 108 CFU / ml of Gram-negative bacteria, Pseudomonas aeruginosa, spread on the hard surface previously treated.

4. Leave at room temperature for 3 hours, for allow the biocide to migrate out of the surface of the polymer and kill the bacteria on the surface.

5. Dry at 37 ° C for at least 30 minutes.

6. Recover surviving microorganisms using a sterile wadding wipe previously moistened with a neutralizing solution. Thoroughly clean the entire surface by wiping 4 times in all directions.

7. Introduce the buffer into 9 ml of neutralizing medium; adjust to 10ml with water. Transfer the bacterial suspension to Nutrient Agar in Petri dishes by successive 10-fold dilutions.

8. Incubate the dishes at 37 ° C for 48 hours and count the surviving microorganisms.

• The neutralizing medium contains 3% polysorbate Tween 80 and 2% soy lecithin.
• A control test is carried out by performing steps 1 to 7 on the surface of a white ceramic tile (5 cm × 5 cm) previously sterilized but not treated with the biocidal system.
• The log ₁₀ for reducing the number of bacteria is calculated as follows: log 10 discount = log 10 N / n N being the number of bacteria (in CFU / ml) surviving in the control test
  where n is the number of bacteria (in CFU / ml) surviving in the test using the biocidal system.

results

• Les résultats montrent :
  • qu'une solution aqueuse d'agent biocide seul ne résiste pas aux 15 rinçages.
  • que l'interaction entre le biocide et le polymère apporte une protection à long terme de la surface contre les bactéries, sans dégradation des performances bactéricides à court terme
  • que le polymère en lui-même n'a pas d'action biocide.

The results of the above test are shown in the following table. Example Polymer Log10 reduction after 0 wash Log10 reduction after 15 washes 26 Polymer 1: 0.15% 6 6 without polymer 6 0 without biocide and 0.15% of Polymer 1 0 0

• The results show :
  • that an aqueous solution of biocidal agent alone is not resistant to rinsing.
  • the interaction between the biocide and the polymer provides long-term protection of the surface against bacteria, without degradation of short-term bactericidal performance
  • that the polymer itself has no biocidal action.

Claims (41)

1. Cleaning or rinsing composition 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

   R₁ is a hydrogen atom or a methyl or ethyl group;

   R₂, R₃, R₄, R₅ and R₆, which are identical or different, are linear or branched C₁-C₆, preferably C₁-C₄, alkyl, hydroxyalkyl or aminoalkyl groups;

   m is an integer from 0 to 10, preferably from 0 to 2;

   n is an integer from 1 to 6, preferably 2 to 4;

   Z represents a -C(O)O- or -C(O)NH- group or an oxygen atom;

   A represents a (CH₂)_p group, p being an integer from 1 to 6, preferably from 2 to 4;

   B represents a linear or branched C₂-C₁₂, advantageously C₃-C₆, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups O or NH, and optionally substituted by one or more hydroxyl or amino groups, preferably hydroxyl groups;

   X, which are identical or different, represent counterions;

   (b) at least one hydrophilic monomer carrying a functional group with an acidic nature which is copolymerizable with (a) and which is capable of being ionized in the application medium; and

   (c) optionally at least one monomer compound with ethylenic unsaturation with a neutral charge which is copolymerizable with (a) and (b), preferably a hydrophilic monomer compound with ethylenic unsaturation with a neutral charge, carrying one or more hydrophilic groups, which is copolymerizable with (a) and (b).
2. Cleaning or rinsing composition according to claim 1, characterized in that, in the general formula I:

   Z represents C(O)O, C(O)NH or O, very preferably C(O)NH;

   n is equal to 2 or 3, very particularly 3;

   m ranges from 0 to 2 and is preferably equal to 0 or 1, very particularly to 0;

   B represents

   

      with q from 1 to 4, preferably equal to 1;

   R₁ to R₆, which are identical or different, represent a methyl or ethyl group.
3. Cleaning or rinsing composition according to claim 1, in which the monomer (a) is represented by the following formula:

   

   p = 2 to 4.
4. Cleaning or rinsing composition according to one of claims 1 to 3, in which the monomer (a) is:

   

      X^- representing the chloride ion.
5. Cleaning or rinsing composition according to any one of the preceding claims, in which the monomer (b) is chosen from C₃-C₈ carboxylic, sulphonic, sulphuric, phosphonic and phosphoric acids with monoethylenic unsaturation.
6. Cleaning or rinsing composition according to any one of the preceding claims, in which the monomer (b) is chosen from acrylic acid, methacrylic acid, α-ethacrylic acid, β,β-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylideneacetic acid, propylideneacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-(methacroyl)alanine, N-(acryloyl)hydroxyglycine, sulphopropyl acrylate, sulphoethyl acrylate, sulphoethyl methacrylate, styrenesulphonic acid, vinylsulphonic acid, vinylphosphonic acid, phosphoethyl acrylate, phosphonoethyl acrylate, phosphopropyl acrylate, phosphonopropyl acrylate, phosphoethyl methacrylate, phosphonoethyl methacrylate, phosphopropyl methacrylate, phosphonopropyl methacrylate and the alkali metal and ammonium salts thereof.
7. Cleaning or rinsing 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, C₁-C₄ hydroxyalkyl esters of acrylic acid and of methacrylic acid, in particular ethylene glycol and propylene glycol acrylate and methacrylate, polyalkoxylated esters of acrylic acid and of methacrylic acid, in particular the polyethylene glycol and polypropylene glycol esters, esters of acrylic acid or of methacrylic acid and of polyethylene glycol or polypropylene glycol C₁-C₂₅ monoalkyl ethers, vinyl acetate, vinylpyrrolidone or methyl vinyl ether.
8. Cleaning or rinsing composition according to any one of the preceding claims, in which X is chosen from halogen, in particular chlorine, sulphonate, sulphate, hydrogensulphate, phosphate, phosphonate, citrate, formate and acetate anions.
9. Cleaning or rinsing composition according to any one of the preceding claims, characterized in that the water-soluble or water-dispersible copolymer is obtained by copolymerization

   of 3 to 80 mol%, preferably 10 to 60 mol%, of the monomer (a);

   of 10 to 95 mol%, preferably 20 to 70 mol%, of the monomer (b);

   of 0 to 50 mol%, preferably 0 to 30 mol%, very particularly of 5 to 25 mol%, of the monomer (c).
10. Cleaning or rinsing composition according to any one of the preceding claims, characterized in that the molar ratio by weight of the total of the monomers (a) to the total of the monomers (b) is between 80/20 and 5/95, preferably 60/40 and 20/80.
11. Cleaning or rinsing composition according to any one of the preceding claims, characterized in that the molecular mass of the copolymer is at least 1000, advantageously at least 10,000, and at most 20,000,000, advantageously at most 10,000,000.
12. Cleaning or rinsing composition according to any one of the preceding claims, characterized in that the copolymer is chosen from the following compounds:

    

    

    

    

    

    

    

    with x having a mean value of 0 to 50%, preferably of 0 to 30%, very particularly of 5 to 25%,
       y having a mean value of 10 to 95%, preferably of 20 to 70%,
       z having a mean value of 3 to 80%, preferably of 10 to 60%,
       and the y/z ratio preferably being of the order of 4/1 to 1/2,
    with x+y+z = 100%, x, y and z representing the mol% of units derived from acrylamide, from acrylic acid (sodium salt) and from Diquat respectively.
13. Cleaning composition according to one of the preceding claims, characterized in that the said copolymer of formula I represents from 0.0005 to 10%, preferably from 0.001 to 5%, by weight with respect to the total weight of the said composition.
14. Cleaning or rinsing composition according to any one of the preceding claims, characterized in that the copolymer/surfactant ratio by weight is between 1/2 and 1/100, advantageously between 1/5 and 1/50.
15. Cleaning composition according to one of claims 1 to 12 for cleaning windows, the 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 12;

    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, of solvents, such as. alcohols, and/or of various additives.
16. Cleaning composition according to claim 15 for cleaning windows, the said composition comprising an amine oxide as nonionic surfactant.
17. Cleaning composition according to one of claims 1 to 14 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 12, with respect to the total weight of dry matter of the composition;

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

    from 30 to 95% by weight with respect to the total weight of detergent composition, expressed as dry matter, of detergency adjuvants (builders);

    from 3 to 25% by weight with respect to the total weight of the composition of an oxidizing system.
18. Rinsing composition according to one of claims 1 to 14 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 12 with respect to the total weight of the composition;

    from 0.2 to 15%, preferably 0.5 to 5%, by weight with respect to the total weight of the said composition of a nonionic surfactant or a mixture of nonionic and anionic surfactants;

    from 0 to 40%, preferably from 3 to 30%, by weight with respect to the total weight of dry matter of a calcium-sequestering organic acid, preferably citric acid;

    from 0 to 15%, preferably 0 to 10%, by weight with respect to the total weight of the said composition, expressed as dry matter, of an auxiliary agent, preferably a copolymer of acrylic acid and of maleic anhydride or acrylic acid homopolymers.
19. Cleaning composition according to one of claims 1 to 14 for washing dishes by hand, characterized in that the composition comprises:

    from 0.1 to 5 parts by weight with respect to the total weight of the said composition of water-soluble or water-dispersible copolymer defined in one of claims 1 to 12;

    from 5 to 50, preferably from 10 to 40, parts by weight of at least one surfactant, preferably an anionic surfactant;

    at least one noncationic bactericide or disinfectant;

    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 hydrating or moisturizing agent or an agent for protecting the skin;

    a dye or fragrance, and a preservative.
20. Cleaning composition according to one of claims 1 to 14 for the external cleaning of motor vehicles, 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 12 with respect to the total weight of the said composition;

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

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

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

    from 0 to 30%, preferably from 0.5 to 15%, by weight of a cationic surfactant;

    the minimum amount of surfactant being at least 1%;

    an inorganic and/or organic detergency adjuvant (builder);

    optionally a hydrotropic agent, fillers or pH modifiers.
21. Cleaning composition according to one of claims 1 to 14 for cleaning ceramics, in particular tilings, baths and washbasins, characterized in that it comprises:

    from 0.02 to 5% by weight with respect to the total weight of the said composition of water-soluble or water-dispersible copolymer according to one of claims 1 to 12;

    from 0 to 30%, preferably from 0 to 20%, by weight of at least one nonionic surfactant;

    from 0 to 30%, preferably from 0 to 20%, by weight of at least one anionic surfactant, the total amount of surfactants representing from 1.5 to 50%, preferably from 5 to 30%, by weight, more particularly from 10 to 20% by weight, with respect to the total weight of the composition;

    from 0.1 to 25% by weight with respect to the total weight of the composition of at least one organic or inorganic detergency adjuvant (builder);

    optionally a foam modifier, preferably an alkali metal soap;

    optionally pH modifiers, dyes, optical brighteners, agents for suspending material from dirty marks, detergent enzymes, compatible bleaching agents, agents for controlling gel formation, freezing-thawing stabilizers, bactericides, preservatives, solvents, fungicides, insect repellents, hydrotropic agents, fragrances, opacifiers or pearlescent agents,

    the said composition exhibiting a pH of between 3 and 1 and an a/b molar ratio of between 30/70 and 60/40.
22. Cleaning composition according to one of claims 1 to 14 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 12;

    from 0.1 to 40% and preferably between 0.5 and approximately 15% by weight with respect 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 cleaning agent chosen from acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, malic acid, maleic acid, lactic acid, malonic acid, oxalic acid, succinic acid and tartaric acid and mixtures thereof, or an acid salt, preferably 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 of a gum, more particularly of a xanthan gum;

    various additives preferably chosen from preservatives intended to prevent the growth of microorganisms, dyes, fragrances and/or abrasives,

    the said composition exhibiting a pH of between 0.5 and 4, preferably between 1 and 3.
23. Cleaning composition according to one of claims 1 to 14 for rinsing shower walls, 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 according to one of claims 1 to 12;

    from 0.5 to 5% by weight of a nonionic surfactant, preferably an ethoxylated fatty acid ester or an alkylpolyglucoside;

    optionally from 0.01 to 5% by weight of a metal-chelating agent.
24. Cleaning composition according to one of claims 1 to 14 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 one of claims 1 to 12;

    from 0.1 to 1% by weight of a thickener, preferably a xanthan gum;

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

    from 0 to 7% by weight of a glycol, preferably n-butyl diethylene glycol;

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

    optionally a basifying agent or a sequestering agent.
25. Aqueous biocidal cleaning composition for the treatment of hard surfaces comprising:

    at least one water-soluble or water-dispersible copolymer according to one of claims 1 to 12;

    at least one cationic, amphoteric or aminated, preferably cationic, biocide;

    and optionally at least one nonionic, amphoteric or zwitterionic surfactant.
26. Aqueous biocidal cleaning composition according to claim 25 comprising from:

    0.01 to 20%, preferably 0.05 to 5%, by weight of a copolymer according to any one of claims 1 to 12;

    from 0.1 to 20%, preferably from 0.5 to 5%, by weight of a biocide.
27. Aqueous biocidal cleaning composition according to claim 25 or claim 26, in which the biocide is chosen from:

    quaternary monoammonium salts of formulae R¹R²R³R⁴N⁺X^- where
    R¹ represents a benzyl group optionally substituted by a chlorine atom or a C₁-C₄ alkylbenzyl group,
    R² represents a C₈-C₂₄ alkyl group,
    R³ and R⁴, which are alike or different, represent a C₁-C₄ alkyl or hydroxyalkyl group,
    X^- is a halide, sulphate or methyl sulphate solubilizing anion; R^1'R^2'R^3'R^4'N⁺X^- where
    R^1' and R^2', which are alike or different, represent a C₈-C₂₄ alkyl group,
    R^3' and R^4', which are alike or different, represent a C₁-C₄ alkyl group,
    X^- is a halide, sulphate or methyl sulphate solubilizing anion; R^1"R^2"R^3"R^4"N⁺X^- where
    R^1" represents a C₈-C₂₄ alkyl group,
    R^2", R^3" and R^4", which are alike or different, represent a C₁-C₄ alkyl group,
    X^- is a halide, sulphate or methyl sulphate solubilizing anion;

    monoquaternary heterocyclic amine salts, preferably laurylpyridinium, cetylpyridinium or (C₁₂-C₁₄ alkyl)benzylimidazolium chlorides;

    (fatty alkyl)triphenylphosphonium salts, preferably myristyltriphenylphosphonium bromide;

    amphoteric biocides, preferably N-[N'-(C₈-C₁₈ alkyl)-3-aminopropyl]glycine, N- [N'-(N"-(C₈-C₁₈ alkyl)-2-aminoethyl)-2-aminoethyl]glycine or N,N-bis[N'-(C₈-C₁₈ alkyl)-2-aminoethyl]glycine derivatives, such as (dodecyl)(aminopropyl)glycine or (dodecyl)-(diethylenediamine)glycine.
28. Use, in a cleaning composition for a hard surface, of at least one water-soluble or water-dispersible copolymer as defined in claims 1 to 12 in order to confer hydrophilization properties on a hard surface to which it has been applied.
29. Use, in a liquid cleaning composition for a hard surface, of at least one copolymer as defined in one of claims 1 to 12 in order to improve the rate of drying of a surface to which the said composition has been applied.
30. Use according to claim 28, characterized in that the hydrophilization properties are chosen from properties of "resistance to running" or "resistance to condensation" and persistent properties of "resistance to stains" or "resistance to marks".
31. Use according to one of claims 28 to 30, characterized in that from 0.0001 to 6 g/m² of surface, preferably from 0.001 to 2 g/m² of surface, of the said water-soluble or water-dispersible copolymer are deposited on the surface to be treated.
32. Use according to one of claims 28 to 31 for conferring hydrophilizing properties on a glass or ceramic surface or for improving the rate of drying of such a surface.
33. Use according to one of claims 28 to 31 for cleaning or rinsing dishes by hand or in an automatic dishwasher.
34. Use according to one of claims 28 to 31 for cleaning windows.
35. Use according to one of claims 28 to 31 for cleaning tilings, baths and washbasins.
36. Use according to one of claims 28 to 31 for cleaning toilet bowls.
37. Use according to one of claims 28 to 31 for cleaning shower walls.
38. Use according to one of claims 28 to 31 for cleaning glass-ceramic plates.
39. Use according to one of claims 28 to 31 for the external cleaning of motor vehicles.
40. Use of a copolymer according to any one of claims 1 to 12 for washing dishes in an automatic dishwasher, as agent for eliminating or decreasing the corrosion of the glass and of the designs present on the glass or the dishes during repeated washing operations.
41. Process for improving the hydrophilicity of a hard surface, which consists in treating the latter with a cleaning composition according to one of claims 1 to 12.