EP1404792B1 - Method for cleaning a surface with an aqueous composition containing a dispersed polymer - Google Patents

Abstract

Process for enhancing the cleaning properties of an aqueous cleaning composition comprising at least one surfactant, intended for cleaning a surface which has been soiled with soiling, by adding to said cleaning composition, at least one polymer (P) comprising: hydrophobic monomer units that are uncharged or nonionizable at the working pH of the composition of the invention and optionally at least one hydrophilic monomer unit. Preferably, the polymer employed is a copolymer containing sulfur-containing functions in the ionic form (preferably containing sulfonated or sulfated functions).

Description

The present invention relates to a method for increasing the cleaning properties of an aqueous composition for cleaning a soiled surface with soiling by adding to said aqueous cleaning composition at least one polymer in insoluble particulate form. It also relates to the use, in an aqueous composition for cleaning a soiled surface with a soiling, of at least one polymer in insoluble particulate form, as an agent for improving the removal of soil from the soil. soiled surface. It also relates to a method of cleaning a soiled surface with a soil. In a very particular way the polymer used is a copolymer with sulfur functional groups in ionic form (preferably with sulphonated or sulphated functions).

Soft surfaces such as various textile, hair, human skin, and hard surfaces such as cement, ceramic, bricks, metals are soiled by various soils that are difficult to remove; indeed very often these soils are related to the support that they soil by strong chemical or electrostatic bonds that it is difficult to eliminate. It has already been proposed various methods of encapsulation of this fouling by various encapsulating products, and removal of encapsulated soiling by various means such as sweeping and aspiration. Unfortunately the known encapsulating agents participate and even accentuate the phenomenon of attraction of the soil encapsulated on the soiled support. Detergent compositions containing polymers are known from US-A-5,820,637 and US-A-5,773,856 . The present invention is specifically intended to solve the problem above; It also aims to provide an aqueous cleaning composition whose agent coating / encapsulating the dirt particle is adapted to the physico-chemical nature of the support to be cleaned.
This and other objects are achieved by the present invention.

• des unités monomères (N) hydrophobes non chargées ou non-ionisables au pH d'usage de la composition de l'invention,
• éventuellement au moins une unité monomère (F) hydrophile choisie parmi les unités monomères
  • * (F1) cationiques ou potentiellement cationiques au pH d'usage de ladite composition,
  • * (F2) amphotères au pH d'usage de ladite composition,
  • * (F3) anioniques ou potentiellement anioniques au pH d'usage de ladite composition,
  • * (F4) non chargées ou non-ionisables, à caractère hydrophile, au pH d'usage de ladite composition,
  • * ou leurs mélanges
• et éventuellement au moins une unité réticulante (R), la composition aqueuse de nettoyage étant
• une formulation détergente solide ou liquide pour le lavage du linge ou autre article en fibre textile ;
• une formulation rinçante et/ou adoucissante liquide, susceptible de former directement par dilution un bain de rinçage et/ou d'adoucissage ;
• un additif de lavage destiné à être déposé sur la surface sèche à nettoyer préalablement à une opération de lavage à l'aide d'une formulation détergente contenant ou ne contenant pas ledit polymère, ou
• une formulation détergente pour le nettoyage des surfaces dures.

A first object of the invention is a method for increasing the cleaning properties of an aqueous cleaning composition comprising at least one surfactant, for cleaning a soiled surface with a soil, by adding, to said cleaning composition, at least one polymer (P) insoluble under the conditions of use of said composition, present in the form of particles of average size ranging from 5 to 500 nm, comprising

• hydrophobic monomer units (N) that are not loaded or non-ionizable at the use pH of the composition of the invention,
• optionally at least one hydrophilic monomeric unit (F) chosen from monomeric units
  • * (F1) cationic or potentially cationic at the pH of use of said composition,
  • * (F2) amphoteric at the pH of use of said composition,
  • * (F3) anionic or potentially anionic at the pH of use of said composition,
  • * (F4) non-charged or non-ionizable hydrophilic nature, the pH of use of said composition,
  • * or their mixtures
• and optionally at least one crosslinking unit (R), the aqueous cleaning composition being
• a solid or liquid detergent formulation for washing laundry or other textile fiber article;
• a liquid rinse and / or softening formulation capable of directly forming a rinsing and / or softening bath by dilution;
• a washing additive intended to be deposited on the dry surface to be cleaned prior to a washing operation using a detergent formulation containing or not containing said polymer, or
• a detergent formulation for cleaning hard surfaces.

1. a) enduction de la surface à nettoyer par une quantité efficace de composition nettoyante aqueuse comprenant le polymère (P) non soluble dans les conditions d'usage en milieu aqueux de ladite composition,
2. b) séchage de la surface pour évaporer l'eau de la composition et générer le polymère (P) de la dispersion qui forme un produit composite polymère (P) /salissure, et
3. c) éventuellement, élimination dudit produit composite de la surface ainsi nettoyée.

The method of cleaning a soiled surface with a soil may comprise the following steps:

1. a) coating the surface to be cleaned with an effective amount of aqueous cleaning composition comprising the polymer (P) which is not soluble under the conditions of use in aqueous medium of said composition,
2. b) drying the surface to evaporate water from the composition and generate the polymer (P) of the dispersion which forms a polymeric (P) / fouling composite product, and
3. c) optionally, removing said composite product from the surface thus cleaned.

It may be a method for cleaning carpets and rugs, more particularly synthetic fiber and more particularly polyamide and / or polyester. The treatment can of course be adapted to carpets and carpets in natural and synthetic fiber, the natural fiber being for example wool, linen, hemp, or silk.

It can also be a method of cleaning the natural or synthetic fiber cloth as mentioned above, hair, skin, hard surfaces such as concrete, glass, stone, brick, ceramic, melamine, metals, wood and other synthetic surfaces such as PVC, PP, Polycarbonate, polyurethane, silicone, reinforced polyester (for example with glass fibers).

Preferably, said monomer units (N) and (F) are derived from monomers α-β monoethylenically unsaturated; preferentially, said monomer units (R) are derived from diethylenically unsaturated monomers.

The average molar mass of said polymer (measured by gel permeation chromatography (GPC) THF and expressed in polystyrene equivalents) may preferably be at least 20,000 g / mol.

• les monomères vinylaromatiques tels que styrène, vinyltoluène...
• les alkylesters d'acides α-β monoéthyléniquement insaturés tels que les acrylates et méthacrylates de méthyle, éthyle ...
• les esters de vinyle ou d'allyle d'acides carboxyliques saturés tels que les acétates, propionates, versatates de vinyle ou d'allyle
• les nitriles α-β monoethyleniquement insatures comme l'acrylonitrile.

As examples of monomers from which the hydrophobic units (N) are derived, mention may be made of:

• vinylaromatic monomers such as styrene, vinyltoluene ...
• the alkyl esters of α-β monoethylenically unsaturated acids such as methyl and ethyl acrylates and methacrylates, etc.
• vinyl or allyl esters of saturated carboxylic acids such as vinyl, allyl acetates, propionates, versatates
• α-β monoethylenically unsaturated nitriles such as acrylonitrile.

• les N,N(dialkylaminoωalkyl)amides d'acides carboxyliques α-β monoéthyléniquement insaturés comme le N,N-diméthylaminométhyl acrylamide ou méthacrylamide, le N,N-diméthylaminoéthyl acrylamide ou méthacrylamide, le N,N-diméthylamino-3-propyl acrylamide ou méthacrylamide, le N,N-diméthylaminobutyl acrylamide ou méthacrylamide
• les aminoesters α-β monoéthyléniquement insaturés comme le diméthyl aminoéthyl méthacrylate (DMAM), diméthyl aminopropyl méthacrylate, le ditertiobutylaminoéthylméthacrylate, le dipentylaminoethylméthacrylate
• des monomères précurseurs de fonctions amines tels que le N-vinyl formamide, le N-vinyl acétamide, ... qui engendrent des fonctions amines primaires par simple hydrolyse acide ou basique.

As examples of monomers from which the cationic or potentially cationic hydrophilic (F1) units are derived, mention may be made of:

• the N, N (dialkylaminoalkyl) amides of α-β monoethylenically unsaturated carboxylic acids such as N, N-dimethylaminomethyl acrylamide or methacrylamide, N, N-dimethylaminoethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, N, N-dimethylaminobutyl acrylamide or methacrylamide
• monoethylenically unsaturated α-β aminoesters such as dimethylaminoethyl methacrylate (DMAM), dimethylaminopropyl methacrylate, ditertiobutylaminoethylmethacrylate, dipentylaminoethylmethacrylate
• monomers precursors of amine functions such as N-vinyl formamide, N-vinyl acetamide, ... which generate primary amine functions by simple acid or basic hydrolysis.

• la N,N-diméthyl-N-méthacryloyloxyéthyl-N-(3-sulfopropyl) ammonium sulfobétaïne (SPE de RASCHIG), la N,N-diméthyl-N-(2-méthacrylamidoéthyl)-N-(3-sulfopropyl) ammonium bétaïne (SPP de RASCHIG), la 1-vinyl-3-(3-sulfopropyl) imidazolidium bétaïne, la 1-(3-sulfopropyl)-2-vinylpyridinium bétaïne (SPV de RASCHIG),
• les dérivés de la réaction de quatemisation des N(dialkylaminoωalkyl)amides d'acides carboxyliques α-β éthyléniquement insaturés, comme le N,N-diméthylaminométhyl acrylamide ou méthacrylamide, le N,N-diméthylamino-3-propyl acrylamide ou méthacrylamide, ou des aminoesters éthyléniquement insaturés comme le ditertiobutylaminoéthylméthacrylate, le dipentylaminoethylméthacrylate, par un chloroacétate de métal alcalin (sodium en particulier) ou de propane sultone.

By way of examples of monomers from which the hydrophilic (F 2) amphoteric units are derived, mention may be made of:

• N, N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine (RASCHIG SPE), N, N-dimethyl-N- (2-methacrylamidoethyl) -N- (3-sulfopropyl) ammonium betaine (RASCHIG SPP), 1-vinyl-3- (3-sulfopropyl) imidazolidium betaine, 1- (3-sulfopropyl) -2-vinylpyridinium betaine (RASCHIG SPV),
• derivatives of the quaternization reaction of N (dialkylaminoalkyl) amides of α-β ethylenically unsaturated carboxylic acids, such as N, N-dimethylaminomethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, or ethylenically unsaturated aminoesters such as ditertiobutylaminoethyl methacrylate, dipentylaminoethyl methacrylate, with an alkali metal chloroacetate (particularly sodium) or propane sultone.

• des monomères possédant au moins une fonction carboxylique, comme les acides ou anhydrides carboxyliques α-β éthyléniquement insaturés, les acides ou anhydrides acrylique, méthacrylique, maleique, fumarique, itaconique, N-méthacroyl alanine, N-acryloyl-hydroxy-glycine et leurs sels hydrosolubles
• des monomères possédant au moins une fonction soufrée, de préférence sulfate ou sulfonate, comme le 2-sulfooxyethyl méthacrylate, l'acide vinylbenzène sulfonique, l'acide allylsulfonique, le 2-acrylamido-2méthylpropane sulfonique, l'acrylate ou le méthacrylate de sulfoéthyle , l'acrylate ou le méthacrylate de sulfopropyle et leurs sels hydrosolubles
• des monomères possédant au moins une fonction phosphonate ou phosphate, comme l'acide vinylphosphonique, l'acide vinyldiphosphonique, les esters de phosphates éthyléniquement insaturés tels que les phosphates dérivés du méthacrylate d'hydroxyéthyle (Empicryl 6835 de RHODIA) et ceux dérivés des méthacrylates de polyoxyalkylènes et leurs sels hydrosolubles
• des monomères α-β monoéthyléniquement insaturés précurseurs de fonction(s) anionique(s), tels que ceux dont l'hydrolyse engendre des fonctions carboxylates (acrylate de tertiobutyle, acrylate de diméthyl aminoéthyle, anhydride maléique, ...)

As examples of monomers from which the hydrophilic units (F3) anionic or potentially anionic are derived, mention may be made of:

• monomers having at least one carboxylic function, such as α-β ethylenically unsaturated carboxylic acids or anhydrides, acrylic, methacrylic, maleic or fumaric acids or anhydrides, itaconic, N-methacrylalanine, N-acryloyl-hydroxy-glycine and their water-soluble salts
• monomers having at least one sulfur function, preferably sulphate or sulphonate, such as 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulphonic acid, acrylate or sulphoethyl methacrylate, sulfopropyl acrylate or methacrylate and their water-soluble salts
• monomers having at least one phosphonate or phosphate function, such as vinylphosphonic acid, vinyldiphosphonic acid, esters of ethylenically unsaturated phosphates such as phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 from Rhodia) and those derived from methacrylates of polyoxyalkylenes and their water-soluble salts
• monoethylenically unsaturated α-β monomers precursors of anionic function (s), such as those whose hydrolysis gives rise to carboxylate functions (tertiary butyl acrylate, dimethylaminoethyl acrylate, maleic anhydride, etc.)

• les hydroxyalkylesters d'acides α-β éthyléniquement insaturés comme les acrylates et méthacrylates d'hydroxyéthyle, d'hydroxypropyle...
• les amides d'acides α-β éthyléniquement insaturés comme l'acrylamide, le N,N-diméthyl méthacrylamide, le N-méthylolacrylamide ...
• les monomères α-β éthyléniquement insaturés portant un segment polyoxyalkyléné hydrosoluble du type polyoxyde d'éthylène, comme les polyoxyde d'éthylène α-méthacrylates (BISOMER S20W, S10W, ... de LAPORTE) ou α,ω-diméthacrylates, le SIPOMER BEM de RHODIA (méthacrylate de polyoxyéthylène ω-béhényle), le SIPOMER SEM-25 de RHODIA (méthacrylate de polyoxyéthylène ω-tristyrylphényle) ...
• les monomères α-β éthyléniquement insaturés précurseurs d'unités ou de segments hydrophiles tels que l'acétate de vinyle qui, une fois polymérisé, peut être hydrolysé pour engendrer des unités alcool vinylique ou des segments alcool polyvinylique
• les monomères α-β éthyléniquement insaturés de type uréido et en particulier le méthacrylamido de 2-imidazolidinone éthyle (Sipomer WAM II de RHODIA).

As examples of monomers from which the hydrophilic units (F4) are unfilled or nonionizable, mention may be made of:

• hydroxyalkyl esters of α-β ethylenically unsaturated acids such as hydroxyethyl and hydroxypropyl acrylates and methacrylates, etc.
• amides of α-β ethylenically unsaturated acids such as acrylamide, N, N-dimethyl methacrylamide, N-methylolacrylamide, etc.
• α-β ethylenically unsaturated monomers bearing a water-soluble polyoxyalkylene segment of the polyethylene oxide type, such as ethylene polyoxide α-methacrylates (BISOMER S20W, S10W, ... from LAPORTE) or α, ω-dimethacrylates, SIPOMER BEM from RHODIA (polyoxyethylene ω-behenyl methacrylate), SIPOMER SEM-25 from RHODIA (oxy-tristyrylphenyl polyoxyethylene methacrylate) ...
• α-β ethylenically unsaturated monomers precursors of hydrophilic units or segments such as vinyl acetate which, once polymerized, can be hydrolysed to generate vinyl alcohol units or polyvinyl alcohol segments
• α-β-ethylenically unsaturated monomers of the ureido type and in particular 2-imidazolidinone ethyl methacrylamido (Sipomer WAM II from RHODIA).

• le divinylbenzène
• le diméthacrylate d'éthylène glycol -
• le méthacrylate d'allyle
• le méthylène bis (acrylamide)
• le glyoxal bis (acrylamide).

As examples of monomers from which the crosslinking units (R) are derived, mention may be made of:

• divinylbenzene
• ethylene glycol dimethacrylate -
• allyl methacrylate
• methylene bis (acrylamide)
• glyoxal bis (acrylamide).

Said polymers (P) are in insoluble particulate form; the diameter of said particles may range from 5 to 500 nm, preferably from 5 to 300 nm, more particularly from 5 to 100 nm, more particularly from 10 to 50 nm.
Aqueous dispersions (latex) of said polymer (P) can be obtained in a known manner by radical polymerization in aqueous medium of the ethylenically unsaturated monomers. Methods for obtaining nanoparticulate latexes of small diameter are described in Colloid Polym. Sci. 266: 462-469 (1988) ) and in Journal of Colloid and Interface Science. Flight. 89. No 1, September 1982 pages185 and following. A method for preparing latex of particles of average size less than 100 nm, in particular of average size ranging from 1 to 60 nm, more particularly from 5 to 40 nm, is described in EP-A-644,205 .

The choice and the relative amounts of the monomer or monomers from which the (N), (F) and (R) units of the polymer (P) are derived are such that said polymer (P) has a glass transition temperature Tg of order of -40 ° C to 150 ° C, preferably of the order of 0 to 110 ° C, more particularly of the order of 40 to 110 ° C and remains insoluble in the conditions of use of the composition of the 'invention. According to the invention, said polymer (P) is considered insoluble when less than 15%, preferably less than 10% of its weight is soluble in the aqueous or wet medium of use of the composition of the invention; that is to say, in particular under the conditions of temperature and pH of said medium.

• d'une formulation de nettoyage d'une moquette, le pH est généralement entre 3 et 7, préférentiellement 4 et 6 ;
• d'une formulation détergente pour le lavage du linge ou autre article en fibres textiles, le pH du bain lessiviel est généralement de l'ordre 7 à 11, préférentiellement de 8 à 10,5 ;
• d'une formulation rinçante et/ou adoucissante, le pH du bain de rinçage et/ou d'adoucissage est généralement de l'ordre 2 à 8 ;
• d'un additif de lavage ("prespotter"), le pH à considérer est celui du pH du bain lessiviel de l'opération suivante de lavage, à savoir de l'ordre 7 à 11, préférentiellement de 8 à 10,5 ;
• d'une formulation détergente pour le nettoyage des surfaces dures, le pH du bain lessiviel va de 1 à 11.

The pH of use of the composition of the invention can range from about 1 to about 12, depending on the desired use.
As it's about

• of a cleaning formulation of a carpet, the pH is generally between 3 and 7, preferably 4 and 6;
• a detergent formulation for washing laundry or other textile fiber article, the pH of the detergent bath is generally of the order of 7 to 11, preferably 8 to 10.5;
• of a rinsing and / or softening formulation, the pH of the rinsing and / or softening bath is generally of the order of 2 to 8;
• of a washing additive ("prespotter"), the pH to be considered is that of the pH of the detergent bath of the following washing operation, namely of the order 7 to 11, preferably 8 to 10.5;
• of a detergent formulation for cleaning hard surfaces, the pH of the detergent bath ranges from 1 to 11.

For a good embodiment of the invention, at least 70% of the total mass of said polymer (P) is formed of hydrophobic unit (s) (N).

When hydrophilic units (F) are present, they preferably do not represent more than 30% of the total mass of the polymer (P).

When crosslinking units (R) are present, they generally do not represent more than 20%, preferably not more than 10%, especially not more than 5% of the total weight of the polymer (P).

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• éventuellement au moins 1% de son poids d'unités monomères hydrophiles (F4) non chargées ou non-ionisables
• éventuellement pas plus de 20% de son poids d'unités réticulantes (R) non chargées ou non-ionisables.

A first embodiment of the invention consists of a method for increasing the cleaning properties of a composition by adding particles to at least one non-charged or non-ionizable polymer (P1) comprising

• at least 70% by weight of hydrophobic monomer units (N)
• optionally at least 1% of its weight of hydrophilic monomer units (F4) not loaded or nonionizable
• possibly not more than 20% of its weight of non-charged or non-ionizable crosslinking units (R).

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• de 3 à 30% de son poids d'unités monomères hydrophiles (F4) non chargées ou non-ionisables
• éventuellement pas plus de 20%, de préférence pas plus de 10% de son poids d'unités réticulantes (R) non chargées ou non-ionisables.

Preferably, according to this first embodiment, said uncharged or non-ionizable polymer (P1) comprises:

• at least 70% by weight of hydrophobic monomer units (N)
• from 3 to 30% of its weight of unfiltered or non-ionizable hydrophilic monomer units (F4)
• optionally not more than 20%, preferably not more than 10% of its weight of non-charged or non-ionizable crosslinking units (R).

Said polymer (P1) not loaded or non-ionizable can be implemented in all types of compositions for cleaning carpets and carpets mentioned above whose use pH can range from 2 to 12, namely, formulations detergents, rinsing and / or softening formulations, drying additives, foams or washing additives.

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• au moins 1% de son poids, de préférence de 3 à 30% de son poids, tout particulièrement de 1 à 20% de son poids d'unités monomères hydrophiles (F3) anioniques ou anionisables
• éventuellement pas plus de 29% de son poids d'unités monomères hydrophiles (F4) non chargées ou non-ionisables.

A second embodiment of the invention consists of a process for increasing the cleaning properties of a composition by adding particles to at least one polymer (P2) having anionic or anionizable units and free of cationic or cationizable units, comprising

• at least 70% by weight of hydrophobic monomer units (N)
• at least 1% of its weight, preferably 3 to 30% of its weight, especially 1 to 20% of its weight of hydrophilic monomer units (F3) anionic or anionizable
• optionally not more than 29% of its weight of unfiltered or non-ionizable hydrophilic monomer units (F4).

Said polymer (P2) can be used in compositions for cleaning non-cationic carpets and carpets, namely, detergent formulations, foams, drying additives, or wash additives, or in detergent formulations for cleaning hard surfaces.

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• au moins 0,1% de son poids, de préférence pas plus de 20% de son poids, tout particulièrement pas plus de 10 % de son poids d'unités monomères hydrophiles (F2) amphotères
• éventuellement des unités monomères hydrophiles (F4) non chargées ou non-ionisables
• éventuellement des unités monomères hydrophiles (F1) cationiques ou cationisables,

A third embodiment of the invention consists of a method for increasing the cleaning properties of a composition by adding particles to at least one polymer (P3) having amphoteric units, comprising

• at least 70% by weight of hydrophobic monomer units (N)
• at least 0.1% of its weight, preferably not more than 20% of its weight, especially not more than 10% of its weight of amphoteric hydrophilic (F2) monomeric units
• optionally hydrophilic monomer units (F4) that are not charged or non-ionizable
• optionally cationic or cationizable hydrophilic (F1) monomer units,

the set of hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P3), and the molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 depending on the desired use of the composition (C3) thus obtained.
Said polymer (P3) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 can be used in drying additives and aqueous ironing formulations or in detergent formulations for cleaning surfaces hard.
Said polymer (P3) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 60/40, preferably from 5/95 to 50/50, may also be used in detergent formulations and additives washing of carpets and rugs or in detergent formulations for cleaning hard surfaces.

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• des unités monomères hydrophiles (F1) cationiques ou cationisables
• des unités monomères hydrophiles (F3) anioniques ou anionisables
• éventuellement des unités monomères hydrophiles (F2) amphotères
• éventuellement des unités monomères hydrophiles (F4) non chargées ou non-ionisables,

A fourth embodiment of the invention consists of a process for increasing the cleaning properties of a composition by adding particles to at least one polymer (P4) having both units cationic or cationizable and anionic or anionizable units, comprising

• at least 70% by weight of hydrophobic monomer units (N)
• cationic or cationizable hydrophilic (F1) monomer units
• hydrophilic monomer units (F3) anionic or anionizable
• optionally hydrophilic (F 2) amphoteric monomer units
• optionally hydrophilic monomer units (F4) which are not charged or nonionizable,

all of the hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P4), and the molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 depending on the desired use of the composition (C4) thus obtained.
Said polymer (P4) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 can be used in drying additives and aqueous ironing formulations.
Said polymer (P4) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 60/40, preferably from 5/95 to 50/50, may also be used in detergent formulations and additives washing carpets and rugs.

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• au moins 1% de son poids, de préférence de 3 à 30% de son poids, tout particulièrement de 1 à 10% de son poids d'unités monomères hydrophiles (F1) cationiques ou cationisables
• éventuellement pas plus de 20% de son poids d'unités monomères hydrophiles (F4) non chargées ou non-ionisables.

A fifth embodiment of the invention consists of a process for increasing the cleaning properties of a composition by adding particles in at least one polymer (P5) having cationic or cationizable units and free of anionic or anionizable units, comprising

• at least 70% by weight of hydrophobic monomer units (N)
• at least 1% of its weight, preferably 3 to 30% of its weight, more particularly 1 to 10% of its weight of cationic or cationizable hydrophilic (F1) monomer units
• optionally not more than 20% of its weight of unfiltered or non-ionizable hydrophilic monomer units (F4).

Said polymer (P5) can be used in all types of laundry cleaning compositions mentioned above whose use pH can range from 2 to 12, namely, detergent formulations, rinse formulations and / or softening agents, drying additives, foams or washing additives.
Most preferably, when the composition (C5) sought is a detergent composition, said monomer units (F1) are cationizable units derived from at least one cationizable monomer having a pKa of less than 11, preferably less than 10, 5.

• * styrène, dont la température de transition vitreuse Tg est de 108°C ;
• * méthacrylate de méthyle / acide méthacrylique , dont la température de transition vitreuse Tg peut aller de 100°C à 130°C, selon la composition dudit copolymère ;
• * méthacrylate de méthyle / acrylate de butyle / acide méthacrylique , dont la température de transition vitreuse Tg peut aller de 60°C à 130°C, selon la composition dudit copolymère ;
• * méthacrylate de méthyle / acrylate de butyle / hydroxyéthylméthacrylate / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère ;
• * méthacrylate de méthyle/ éthylène glycol diméthacrylate / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère;
• * styrène / divinylbenzène / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 100 à 140°C, selon la composition dudit polymère ;
• * styrène / acrylate de butyle / hydroxyéthylméthacrylate / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère ;
• * Veova 10 (versatate en C₁₀ de vinyle) / méthacrylate de méthyle / acrylate de butyle/ acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère;
• * méthacrylate de méthyle/ acrylate de butyle / hydroxyéthylméthacrylate /acide méthacrylique / N,N-diméthyl-N-méthacryloyloxyéthyl-N-(3-sulfopropyl) ammonium sulfobétaïne (SPE de RASCHIG), dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère ;
• * méthacrylate de méthyle / acrylate de butyle / hydroxyéthylméthacrylate /acide méthacrylique / acide vinyl phosphonique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère ;
• * méthacrylate de méthyle / acrylate de butyle / hydroxyéthylméthacrylate /acide méthacrylique / Empicryl 6835 de RHODIA, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère ;
• * styrène/ styrènes sulfonate, dont la température de transition vitreuse Tg peut aller de 100°C à 130°C, selon la composition dudit polymère ;
• * styrène/Acrylate de Butyle/AMPS (acrylamidomethylpropanesulfonic acid), dont la température de transition vitreuse Tg peut aller de 40°C- à 130°C, selon la composition dudit polymère ;
• * styrène / acrylate de butyle / styrènes sulfonate / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 40°C à 110°C, selon la composition dudit polymère.

By way of examples of polymer (P) in particulate form, mention may be made in particular of particles or aqueous dispersions of particles (latex) of polymers or copolymers having units derived from

• styrene, whose glass transition temperature Tg is 108 ° C;
• * methyl methacrylate / methacrylic acid, whose glass transition temperature Tg can range from 100 ° C to 130 ° C, depending on the composition of said copolymer;
• * methyl methacrylate / butyl acrylate / methacrylic acid, whose glass transition temperature Tg can range from 60 ° C to 130 ° C, depending on the composition of said copolymer;
• * methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid, whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer;
• * methyl methacrylate / ethylene glycol dimethacrylate / methacrylic acid, whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer;
• * styrene / divinylbenzene / methacrylic acid, whose glass transition temperature Tg can range from 100 to 140 ° C, depending on the composition of said polymer;
• * styrene / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid, whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer;
• * Veova 10 (C ₁₀ versatate vinyl) / methyl methacrylate / butyl acrylate / methacrylic acid having a Tg glass transition temperature may range from 10 ° C to 80 ° C, depending on the composition of said polymer;
• methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid / N, N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine (RASCHIG SPE), whose glass transition temperature T g can range from 10 ° C to 80 ° C, according to the composition of said polymer;
• * methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid / vinyl phosphonic acid, whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer;
• methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid / Empicryl 6835 from RHODIA, whose glass transition temperature T g may range from 10 ° C. to 80 ° C., depending on the composition of said polymer;
• * styrene / styrenesulfonate, whose glass transition temperature Tg can range from 100 ° C to 130 ° C, depending on the composition of said polymer;
• * styrene / Butyl acrylate / AMPS (acrylamidomethylpropanesulfonic acid), whose glass transition temperature Tg can range from 40 ° C to 130 ° C, depending on the composition of said polymer;
• * styrene / butyl acrylate / styrenesulfonate / methacrylic acid, whose glass transition temperature Tg can range from 40 ° C to 110 ° C, depending on the composition of said polymer.

Said polymers (P) may be introduced in solid form or preferably in the form of aqueous dispersions (latex) having a solids content of about 10 to 50%, preferably 20 to 40% by weight, in the aqueous composition intended for cleaning to perfect.

A second object of the invention is a very preferred embodiment of the method of the invention.

• insoluble dans les conditions de mise en oeuvre dudit procédé et d'usage de ladite composition
• présent sous forme de particules de taille moyenne de 5 à 500nm, de préférence de 5 à 100nm, tout particulièrement de 5 à 50nm, en dispersion dans ladite composition aqueuse
• et comprenant
  • des unités monomères hydrophobes (N) non-chargées ou non-ionisables au pH d'usage de ladite composition et
  • et au moins une unité monomère non-carboxylée hydrophile soufrée, de préférence sulfonée ou sulfatée, (F') anionique ou amphotère,

dérivées de monomères α-β monoéthyléniquement insaturés.The second object of the invention therefore consists in a process for increasing the cleaning properties of an aqueous cleaning composition comprising at least one surfactant, intended for cleaning a soiled surface by a soiling, by adding, to said cleaning composition, of at least one polymer (P) in an amount effective to improve the removal of soiling from said surface, said polymer (P) being a copolymer (P ')

• insoluble under the conditions of implementation of said process and of use of said composition
• present in the form of particles of average size of 5 to 500 nm, preferably of 5 to 100 nm, very particularly of 5 to 50 nm, in dispersion in said aqueous composition
• and including
  • hydrophobic (N) monomer units that are not charged or non-ionizable at the pH of use of said composition and
  • and at least one hydrophilic, preferably sulphonated or sulphated, non-carboxylic monomer unit (F '), anionic or amphoteric,

derived from monomers α-β monoethylenically unsaturated.

Preferably, said copolymer (P ') does not comprise more than 10% of its weight of carboxylated monomer units COO ^- and / or not more than 10% of its weight of non-amphoteric monomer units carrying a charge cationic.
Said copolymer (P ') is very preferably free of carboxyl charges and cationic charges (non-amphoteric).

Examples of monomers from which the hydrophobic units (N) are derived have already been mentioned above.

• des monomères possédant au moins une fonction sulfate ou sulfonate, comme le 2-sulfooxyethyl méthacrylate, l'acide vinylbenzène sulfonique, l'acide allylsulfonique, le 2-acrylamido-2méthylpropane sulfonique, l'acrylate

ou le méthacrylate de sulfoéthyle, l'acrylate ou le méthacrylate de sulfopropyle et leurs sels hydrosolubles ;

• la N,N-diméthyl-N-méthacryloyloxyéthyl-N-(3-sulfopropyl) ammonium sulfobétaïne (SPE de RASCHIG), la N,N-diméthyl-N-(2-méthacrylamidoéthyl)-N-(3-sulfopropyl) ammonium bétaïne (SPP de RASCHIG), la 1-vinyl-3-(3-sulfopropyl) imidazolidium bétaïne, la 1-(3-sulfopropyl)-2-vinylpyridinium bétaïne (SPV de RASCHIG).

By way of examples of monomers from which the hydrophilic anionic or amphoteric functional groups containing sulfur functional groups (F '), preferably sulphonated or sulphated, are derived, mention may be made of:

• monomers having at least one sulphate or sulphonate function, such as 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulphonic acid, acrylate

or sulfoethyl methacrylate, sulfopropyl acrylate or methacrylate and their water-soluble salts;

• N, N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine (RASCHIG SPE), N, N-dimethyl-N- (2-methacrylamidoethyl) -N- (3-sulfopropyl) ammonium betaine (RASCHIG SPP), 1-vinyl-3- (3-sulfopropyl) imidazolidium betaine, 1- (3-sulfopropyl) -2-vinylpyridinium betaine (RASCHIG SPV).

• au moins une unité réticulante (R) non-carboxylique et non-cationique
• et/ou au moins une unité dérivée d'un monomère possédant au moins une fonction phosphonate ou phosphate
• et/ou au moins une unité hydrophile non-chargée ou non-ionisable.

Said copolymer (P ') may further comprise units derived from other non-carboxylated and non-cationic or non-potentially cationic α-β ethylenically unsaturated monomers at the use pH of the composition.
Thus, said copolymer may optionally furthermore comprise:

• at least one non-carboxylic and non-cationic crosslinking unit (R)
• and / or at least one unit derived from a monomer having at least one phosphonate or phosphate function
• and / or at least one unfilled or non-ionizable hydrophilic unit.

Examples of monomers from which the crosslinking units (R) are derived have already been mentioned above.

Examples of monomers having at least one phosphonate or phosphate function have already been mentioned above (in the list of monomers called F3).

Examples of monomers from which the unfilled or non-ionizable hydrophilic units are derived have already been mentioned above (F4).

Said copolymer (P ') may further comprise units derived from cationic or potentially cationic carboxylic and / or non-amphoteric α-β ethylenically unsaturated monomers at the use pH of the composition, and in an amount corresponding to not more than 10 % by weight of units derived from carboxylated α-β ethylenically unsaturated monomers and not more than 10% of units derived from cationic or potentially cationic non-amphoteric α-β ethylenically unsaturated α-β monomers.

• au moins 70% de la masse totale dudit copolymère (P') est formée d'unité(s) hydrophobes (N)
• de 1 à 30 % de la masse totale dudit copolymère (P') est formée d'unité(s) anioniques ou amphotères à fonctions soufrées (F'), de préférence sulfonées ou sulfatées
• lorsqu'elles sont présentes, les unités monomères à fonctions phosphonates ou phosphates ne représentent pas plus de 10% de la masse totale dudit copolymère (P').

L'ensemble des unités hydrophiles (à savoir les unités (F'), celles à fonctions phosphonates ou phosphates et les unités hydrophiles non-chargées) ne représentent, de préférence, pas plus de 30% de la masse totale du copolymère (P).
Lorsque des unités réticulantes (R) sont présentes, celles-ci ne représentent généralement pas plus de 20%, de préférence pas plus de 10%, tout particulièrement pas plus de 5% de la masse totale du copolymère (P').For a good realization of the second object of the invention:

• at least 70% of the total mass of said copolymer (P ') is formed of hydrophobic unit (s) (N)
• from 1 to 30% of the total weight of said copolymer (P ') is formed from anionic or amphoteric units with sulfur functional groups (F'), preferably sulphonated or sulphated
• when present, the monomeric units with phosphonate or phosphate functions do not represent more than 10% of the total mass of said copolymer (P ').

All of the hydrophilic units (namely the units (F '), those with phosphonate or phosphate functional groups and the unfilled hydrophilic units) preferably represent not more than 30% of the total mass of the copolymer (P). .
When crosslinking units (R) are present, they generally do not represent more than 20%, preferably not more than 10%, especially not more than 5% of the total weight of the copolymer (P ').

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• au moins 1% de son poids, de préférence de 3 à 30% de son poids d'unités monomères anioniques soufrées (F'), de préférence sulfonées ou sulfatées, et/ou
• au moins 0,1% de son poids, de préférence pas plus de 20% de son poids, tout particulièrement pas plus de 10 % de son poids d'unités monomères amphotères hydrophiles (F'), de préférence sulfonées ou sulfatées
• éventuellement pas plus de 29% de son poids d'unités hydrophiles non chargées ou non-ionisables.

A preferred embodiment of the second subject of the invention consists in using in an aqueous cleaning composition, a copolymer (P ") comprising

• at least 70% by weight of hydrophobic monomer units (N)
• at least 1% of its weight, preferably 3 to 30% of its weight of anionic sulfur (F ') monomer units, preferably sulphonated or sulphated, and / or
• at least 0.1% of its weight, preferably not more than 20% of its weight, especially not more than 10% of its weight of hydrophilic (F ') amphoteric monomer units, preferably sulphonated or sulphated
• possibly not more than 29% of its weight of unfilled or non-ionizable hydrophilic units.

Said polymer (P ") can be used in all types of compositions for cleaning non-cationic carpets and carpets whose use pH can range from 2 to 12, namely, detergent formulations, foams, cleaning additives ("prespotter") or for cleaning hard surfaces (ceramic glass, formica ...).

It is recalled that preferentially, said copolymer (P ') does not include more than 10% of its weight of carboxylated monomer units COO ^- and / or not more than 10% by weight of monomer units non- amphoteric compounds carrying a cationic or potentially cationic charge.
Said copolymer (P ") is very preferably free of carboxylated charges and cationic charges (non-amphoteric).

• * méthacrylate de méthyle / acrylate de butyle / hydroxyéthylméthacrylate / acide méthacrylique / N,N-diméthyl-N-méthacryloyloxyéthyl-N-(3-sulfopropyl) ammonium sulfobétaïne (SPE de RASCHIG), dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit copolymère ;
• * styrène/ styrènes sulfonate, dont la température de transition vitreuse Tg peut aller de 100°C à 130°C, selon la composition dudit copolymère ;
• * styrène/Acrylate de Butyle/AMPS (acrylamidomethylpropanesulfonic acid), dont la température de transition vitreuse Tg peut aller de 40°C à 130°C, selon la composition dudit copolymère ;
• * styrène / acrylate de butyle / styrène sulfonate / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 40°C à 110°C, selon la composition dudit copolymère.

By way of examples of copolymers (P), (P ') and (P "), mention may be made of the polymers or copolymers of:

• methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid / N, N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine (RASCHIG SPE), whose glass transition temperature T g can range from 10 ° C to 80 ° C, according to the composition of said copolymer;
• styrene / styrenesulfonate, whose glass transition temperature Tg can range from 100 ° C. to 130 ° C., depending on the composition of said copolymer;
• * styrene / Butyl acrylate / AMPS (acrylamidomethylpropanesulfonic acid), whose glass transition temperature Tg can range from 40 ° C to 130 ° C, depending on the composition of said copolymer;
• styrene / butyl acrylate / styrene sulfonate / methacrylic acid, whose glass transition temperature Tg can range from 40 ° C to 110 ° C, depending on the composition of said copolymer.

The amount of polymer (P) or copolymers (P ') and (P ") present in particulate form in dispersion in the cleaning composition according to the invention can range from 0.05 to 50% by dry weight of said composition , and this according to the application sought.
Thus, said polymer (P) or copolymers (P ') and (P ") can be implemented as follows: % of polymer (P)
(in dry) In a cleaning composition Used 0.01 - 5 preferably 0.05 - 3 As a detergent formulation for washing clothes 0.05 - 3 preferably 0.1 - 2 Rinse and / or softening formulation 0.05 - 50 preferably 0.1 -15 Spraying on the surface to be treated (carpet, carpet, before mechanical action i.brushing, suction ...) 0.05-10 preferably 0.1-5 prespotter wash additive) 0.01 - 5 preferably 0.01 - 0.5 For hard surfaces

The aqueous cleaning composition in which said polymer (P) or copolymer (P ') and (P ") is dispersed comprises at least one anionic, nonionic, amphoteric, zwitterionic or cationic surfactant. surfactant, expressed in dry may represent from 0.1 to 50% of the weight of the composition, and this depending on the type of composition.

Other constituents may be present, in addition to the particles of polymer (P) or copolymer (P ') and (P ") dispersed in the aqueous cleaning composition The nature of these constituents depends on the desired use of said composition.

• au moins un agent tensioactif naturel et/ou synthétique,
• au moins un adjuvant de détergence ("builder")
• éventuellement un agent ou un système oxydant,
• et une série d'additifs spécifiques.

Thus, when it comes to a detergent formulation, for washing laundry, it generally comprises:

• at least one natural and / or synthetic surfactant,
• at least one builder
• optionally an oxidizing agent or system,
• and a series of specific additives.

The detergent formulation may comprise surfactants in an amount corresponding to about 3 to 40% by weight, based on the detergent formulation, surfactants such as

Anionic surfactants

• 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, where 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;
• sulfated alkylamides of formula RCONHR'OSO ₃ M where R represents a C ₂ -C ₂₂ , preferably C ₆ -C ₂₀ , alkyl radical, R 'represents a C ₂ -C ₃ alkyl radical, M represents 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 alkylsulfonates or C ₈ -C ₂₂ secondary compounds, the alkylglycerol sulphonates, the sulphonated polycarboxylic acids described in GB-A-1,082,179 paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, sulfosuccinate monoesters or diesters, N-acyl sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates; the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine); ...);

Nonionic surfactants

• polyoxyalkylenated alkylphenols (polyoxyethylenated, 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 .;
• glucosamide, glucamide, glycerolamide;
• 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 marketed by Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy. ;
• the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with propylene glycol, such as PLURONIC marketed by BASF;
• the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with ethylenediamine, such as TETRONIC marketed by BASF;
• 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 fatty amides;
• ethoxylated amines.

Amphoteric and zwitterionic surfactants

• les alkyldiméthylbétaïnes, les alkylamidopropyldiméthylbétaïnes, les alkyltriméthylsulfobétaïnes, 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.

Agent de blanchiment afin d'améliorer l'enlèvement de salissures oxydables :

• agents oxydants de type : sources de peroxides, telle que l'eau oxygénée, les peroxides organiques, les peracides preformés et des mélanges des composés ci-dessus . Les agents de blanchiments potentiels sont décrits dans le brevet EP 0629694 B1 publié le 21 décembre 1994 . La concentration de l'agent de binchiment peut varier de 0,01% à 50%, préférentiellement de 0,1 à 20% en masse de la formulation.

• alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, condensation products of fatty acids and protein hydrolysates;
• alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms.

Bleaching agent to improve the removal of oxidizable dirt:

• oxidizing agents of the type: sources of peroxides, such as hydrogen peroxide, organic peroxides, preformed peracids and mixtures of the above compounds. The potential bleaching agents are described in the patent EP 0629694 B1 published on December 21, 1994 . The concentration of the binchiment agent may vary from 0.01% to 50%, preferably from 0.1 to 20% by weight of the formulation.

Builder builders improving the properties of surfactants can be used in amounts of about 5-50%, preferably about 5-30% by weight for liquid detergent formulations or about 10% by weight. -80%, preferably 15-50% by weight for powder detergent formulations, detergency builders such as:

Inorganic detergency builders

• polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines
• tetraborates or borate precursors;
• silicates, in particular those having a SiO ₂ / Na ₂ O ratio in the range of 1.6 / 1 to 3.2 / 1 and the layered silicates described in US-A-4,664,839 ;
• alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates);
• cogranulates of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488,868 ;
• crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X, etc .; particle size zeolite A of the order of 0.1-10 micrometers is preferred.

Organic detergency additives

• water-soluble polyphosphonates (ethane 1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts ...);
• water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as:
  • polycarboxylate ethers (oxydisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts);
  • hydroxypolycarboxylate ethers;
  • citric acid and its salts, mellitic acid, succinic acid and their salts;
  • salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2-hydroxyethyl) -nitrilodiacetates);
  • C5-C20 alkyl succinic acids and their salts (2-dodecenylsuccinates, lauryl succinates);
  • polyacetal carboxylic esters;
  • polyaspartic acid, polyglutamic acid and their salts;
  • polyimides derived from the polycondensation of aspartic acid and / or glutamic acid;
  • polycarboxymethyl derivatives of glutamic acid or other amino acids.

The detergent formulation may further comprise at least one oxygen-releasing bleaching agent comprising a percompound, preferably a persalt. Said bleaching agent may be present in an amount corresponding to about 1 to 30%, preferably 4 to 20% by weight, based on the detergent formulation.

As examples of per-compounds which may be used as bleaching agents, particular mention should be made of perborates such as sodium perborate monohydrate or tetrahydrate; peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate.

The preferred bleaching agents are sodium perborate, mono- or tetrahydrate and / or sodium carbonate peroxyhydrate.

Said agents are generally associated with a bleaching activator generating in situ in the detergent medium, a peroxy carboxylic acid, in an amount corresponding to about 0.1 to 12%, preferably 0.5 to 8% by weight relative to the detergent formulation. Among these activators, mention may be made of tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluryl, sodium p-acetoxybenzenesulphonate, pentaacetylglucose and octaacetyllactose.

Mention may also be made of non-oxygenated bleaches acting by photoactivation in the presence of oxygen, agents such as aluminum phthalocyanines and / or sulphonated zinc.

The detergent formulation may further comprise soil release, anti-redeposition, chelant, dispersant, fluorescence, suds suppressor, softener, enzyme and other miscellaneous additives.

Anti-fouling agents

They can be used in amounts of about 0.01-10%, preferably about 0.1-5%, and more preferably of the order of 0.2-3% by weight.

• les dérivés cellulosiques tels que les hydroxyéthers de cellulose, la méthylcellulose, l'éthylcellulose, l'hydroxypropyl méthylcellulose, l'hydroxybutyl méthylcellulose ;
• les polyvinylesters greffés sur des troncs polyalkylènes tels que les polyvinylacétates greffés sur des troncs polyoxyéthylènes ( EP-A-219 048 ) ;
• les alcools polyvinyliques ;
• les copolymères polyesters à base de motifs éthylène téréphtalate et/ou propylène téréphtalate et polyoxyéthylène téréphtalate, avec un rapport molaire (nombre de motifs) éthylène téréphtalate et/ou propylène téréphtalate / (nombre de motifs) polyoxyéthylène téréphtalate de l'ordre de 1/10 à 10/1, de préférence de l'ordre de 1/1 à 9/1, les polyoxyéthylène téréphtalates présentant des unités polyoxyéthylène ayant un poids moléculaire de l'ordre de 300 à 5000, de préférence de l'ordre de 600 à 5000 ( US-A-3 959 230 , US-A-3 893 929 , US-A-4 116 896 , US-A-4 702 857 , US-A-4 770 666 ) ;
• les oligomères polyesters sulfonés obtenus par sulfonation d'un oligomère dérivé de l'alcool allylique éthoxylé, du diméthyltéréphtalate et du 1,2-propylènediol, présentant de 1 à 4 groupes sulfonés ( US-A-4 968 451 ) ;
• les copolymères polyesters à base de motifs propylène téréphtalate et polyoxyéthylène téréphtalate et terminés par des motifs éthyles, méthyles ( US-A-4 711 730 ) ou des oligomères polyesters terminés par des groupes alkylpolyéthoxy ( US-A-4 702 857 ) ou des groupes anioniques sulfopolyéthoxy ( US-A-4 721 580 ), sulfoaroyles ( US-A-4 877 896 ) ;
• les copolymères polyesters sulfonés dérivés d'acide, anhydride ou diester téréphtalique, isophtalique et sulfoisophtalique et d'un diol ( FR-A-2 720 399 ).

Mention may be made more particularly of agents such as:

• cellulosic derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose;
• polyvinyl esters grafted on polyalkylene trunks such as polyvinyl acetates grafted onto polyoxyethylene trunks ( EP-A-219 048 );
• polyvinyl alcohols;
• polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio (number of units) of ethylene terephthalate and / or propylene terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 at 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 ( US-A-3,959,230 , US-A-3 893 929 , US-A-4,116,896 , US-A-4,702,857 , US-A-4,770,666 );
• the sulphonated polyester oligomers obtained by sulphonation of an oligomer derived from ethoxylated allyl alcohol, dimethylterephthalate and 1,2-propylene diol, having from 1 to 4 sulphonated groups ( US-A-4,968,451 );
• polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl, methyl units ( US-A-4,711,730 ) or polyester oligomers terminated by alkylpolyethoxy groups ( US-A-4,702,857 ) or sulfopolyethoxy anionic groups ( US-A-4,721,580 ), sulfoaroyles ( US-A-4,877,896 );
• sulfonated polyester copolymers derived from terephthalic, isophthalic and sulfoisophthalic acid, anhydride or diester and a diol ( FR-A-2,720,399 ).

Anti-redeposition agents.

They can be used in amounts generally of about 0.01-10% by weight for a powdered detergent formulation, of about 0.01-5% by weight for a liquid detergent formulation.

• les monoamines ou polyamines éthoxylées, les polymères d'amines éthoxylées ( US-A-4 597 898 , EP-A-11 984 ) ;
• la carboxyméthylcellulose ;
• les oligomères polyesters sulfonés obtenus par condensation de l'acide isophtalique, du sulfosuccinate de diméthyle et de diéthylène glycol ( FR-A-2 236 926 ) ;
• les polyvinylpyrollidones.

Mention may be made in particular of agents such as:

• ethoxylated monoamines or polyamines, polymers of ethoxylated amines ( US-A-4,597,898 , EP-A-11 984 );
• carboxymethylcellulose;
• sulphonated polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulphosuccinate and diethylene glycol ( FR-A-2,236,926 );
• polyvinylpyrollidones.

Chelating agents

The chelating agents of iron and magnesium may be present in amounts of the order of 0.1-10%, preferably of the order of 0.1-3% by weight.

• les aminocarboxylates tels que les éthylènediaminetétraacétates, hydroxyéthyléthylènediaminetriacétates, nitrilotriacétates ;
• les aminophosphonates tels que les nitrilotris-(méthylènephosphonates) ;
• les composés aromatiques polyfonctionnels tels que les dihydroxydisulfobenzènes.

We can mention among others:

• aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethylethylenediaminetriacetates, nitrilotriacetates;
• aminophosphonates such as nitrilotris- (methylenephosphonates);
• polyfunctional aromatic compounds such as dihydroxydisulfobenzenes.

Polymeric dispersing agents,

• les sels hydrosolubles d'acides polycarboxyliques de masse moléculaire de l'ordre de 2000 à 100 000, obtenus par polymérisation ou copolymérisation d'acides carboxyliques éthyléniquement insaturés tels que acide acrylique, acide ou anhydride maléique, acide fumarique, acide itaconique, acide aconitique, acide mésaconique, acide citraconique, acide méthylènemalonique, et tout particulièrement les polyacrylates de masse moléculaire de l'ordre de 2 000 à 10 000 ( US A-3 308 067 ), les copolymères d'acide arylique et d'anhydride maléique de masse moléculaire de l'ordre de 5 000 à 75 000 ( EP-A-66 915 )
• les polyéthylèneglycols de masse moléculaire de l'ordre de 1000 à 50 000.

They may be present in an amount of about 0.1-7% by weight, to control the hardness of calcium and magnesium, agents such as

• water-soluble salts of polycarboxylic acids with a molecular mass of the order of 2,000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and most particularly polyacrylates of molecular weight in the range of 2,000 to 10,000 ( US A-3,308,067 ), copolymers of arylic acid and of maleic anhydride with a molecular mass of the order of 5,000 to 75,000 ( EP-A-66 915 )
• polyethylene glycols of molecular weight of the order of 1000 to 50 000.

Fluorescence agents (brighteners),

They may be present in an amount of about 0.05-1.2% by weight, agents such as: stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanines, thiophenes ... (" The production and application of fluorescent brightening agents "- Mr. Zahradnik, published by John Wiley & Sons, New York-1982 ).

Foam suppressing agents.

• les acides gras monocarboxyliques en C₁₀-C₂₄ ou leurs sels alcalins, d'ammonium ou alcanolamines, les triglycérides d'acides gras ;
• les hydrocarbures saturés ou insaturés aliphatiques, alicycliques, aromatiques ou hétérocycliques, tels que les paraffines, les cires ;
• les N-alkylaminotriazines ;
• les monostéarylphosphates, les monostéarylalcoolphosphates ;
• les huiles ou résines polyorganosiloxanes éventuellement combinées avec des particules de silice.

They can be present in amounts of up to 5% by weight, agents such as:

• C ₁₀ -C ₂₄ monocarboxylic fatty acids or their alkali metal, ammonium or alkanolamine salts, triglycerides of fatty acids;
• saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic hydrocarbons, such as paraffins, waxes;
• N-alkylaminotriazines;
• monostearyl phosphates, monostearyl alcohol phosphates;
• polyorganosiloxane oils or resins optionally combined with silica particles.

Softening agents

They may be present in amounts of about 0.5-10% by weight, agents such as clays.

enzymes

• les protéases, amylases, lipases, cellulases, peroxydases ( US-A-3 553 139 , US-A-4 101 457 , US-A-4 507 219 , US-A-4 261 868 ).

They may be present in an amount of up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent formulation, enzymes such as:

• proteases, amylases, lipases, cellulases, peroxidases ( US-A-3,553,139 , US-A-4,101,457 , US-A-4,507,219 , US-A-4,261,868 ).

Other additives

• des agents tampons,
• des parfums,
• des pigments.

We can mention among others:

• buffering agents,
• perfumes,
• pigments.

The detergent composition may be used by any means, in particular by spraying, leaching, coating, impregnating, soaking, padding, in a proportion of from 0.1 g / l to 400 g / l, preferably from 1 g / l to 50 g / l. l for carrying out spraying operations at a temperature of the order of 25 to 90 ° C.

• associations d'agents tensioactifs cationiques (diester de triéthanolamine quatemisé par du diméthylsulfate, N-méthylimidazoline tallow ester méthyl sulfate, chlorure de dialkyldiméthylammonium, chlorure d'alkylbenzyldiméthylammonium, sulfate de méthyle et d'alkylimidazolinium, sulfate de méthyle et de méthyl-bis(alkylamidoéthyl)-2 hydroxyéthylammonium...) en quantité pouvant aller de 3 à 50%, de préférence de 4 à 30% de ladite formulation éventuellement associés à des tensioactifs non ioniques (alcools gras éthoxylés, alkylphénols éthoxylés ...) en quantité pouvant aller jusqu'à 3% ;
• agents oxydants de type : sources de peroxides, telle que l'eau oxygénée, les peroxides organiques, les peracides preformés et des mélanges des composés ci-dessus . Les agents de blanchiments potentiels sont décrits dans le brevet EP 0629694 B1 publié le 21 décembre 1994 . La concentration de l'agent de blanchiment peut varier de 0,01% à 50%, préférentiellement de 0,1 à 20% en masse de la formulation.- azurants optiques (0,1 à 0,2%);
• éventuellement agents anti-transfert de couleur (polyvinylpyrrolidone, polyvinyloxazolidone, polyméthacrylamide... 0,03 à 25%, de préférence 0,1 à 15%)
• colorants,
• parfums,
• solvants, notamment des alcools (méthanol, éthanol, propanol, isopropanol, éthylèneglycol, glycérine)
• limiteurs de mousse.

The cleaning composition may be a liquid aqueous rinse formulation, which may facilitate the subsequent cleaning.
This can be carried out in a proportion of from 0.2 to 10 g / l, preferably from 2 to 10 g / l.
In addition to the polymer (P) or the copolymer (P ') and (P "), other constituents of the type may be present.

• combinations of cationic surfactants (quaternized triethanolamine diester with dimethylsulfate, N-methylimidazoline tallow ester methyl sulfate, dialkyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, methylimidazolinium methyl sulfate, methyl-bis (alkylamidoethyl) sulfate) ) -2 hydroxyethylammonium ...) in an amount ranging from 3 to 50%, preferably from 4 to 30% of said formulation optionally combined with nonionic surfactants (ethoxylated fatty alcohols, ethoxylated alkylphenols, etc.) in an amount that can go up to 3%;
• oxidizing agents of the type: sources of peroxides, such as hydrogen peroxide, organic peroxides, preformed peracids and mixtures of the above compounds. The potential bleaching agents are described in the patent EP 0629694 B1 published on December 21, 1994 . The concentration of the bleaching agent may vary from 0.01% to 50%, preferably from 0.1 to 20% by weight of the optical brightener formulation (0.1 to 0.2%);
• optionally anti-color transfer agents (polyvinylpyrrolidone, polyvinyloxazolidone, polymethacrylamide ... 0.03 to 25%, preferably 0.1 to 15%)
• colorants,
• perfumes,
• solvents, in particular alcohols (methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin)
• foam limiters.

• tensioactifs anioniques tels que ceux déjà mentionnés ci-dessus, en quantité d'au moins 5% du poids de la composition ;
• tensioactifs non-ioniques tels que ceux déjà mentionnés ci-dessus, en quantité pouvant aller de 15% à 40% du poids de la composition ;
• des hydrocarbures aliphatiques, en quantité pouvant aller de 5% à 20% du poids de la composition ;
• agents oxydants de type : sources de peroxides, telle que l'eau oxygénée, les peroxides organiques, les peracides preformés et des mélanges des composés ci-dessus . Les agents de blanchiments potentiels sont décrits dans le brevet EP 0629694 B1 publié le 21 décembre 1994 . La concentration de l'agent de blanchiment peut varier de 0,01% à 50%, préférentiellement de 0,1 à 20% en masse de la formulation.

When the aqueous cleaning composition is a "prespotter", it may be in the form of an aqueous dispersion, a solid (stick), or a foam.
In addition to the polymer (P) or the copolymer (P ') and (P "), other constituents of the type may be present:

• anionic surfactants such as those already mentioned above, in an amount of at least 5% of the weight of the composition;
• nonionic surfactants such as those already mentioned above, in an amount ranging from 15% to 40% of the weight of the composition;
• aliphatic hydrocarbons, in an amount ranging from 5% to 20% of the weight of the composition;
• oxidizing agents of the type: sources of peroxides, such as hydrogen peroxide, organic peroxides, preformed peracids and mixtures of the above compounds. The potential bleaching agents are described in the patent EP 0629694 B1 published on December 21, 1994 . The concentration of the bleaching agent may vary from 0.01% to 50%, preferably from 0.1% to 20% by weight of the formulation.

When the aqueous cleaning composition is a hard surface cleaning composition, it may comprise, beside said polymer (P) or copolymer (P ') and (P "), customary additives that are soluble or dispersible, which can promote its stability, its wettability, to bring a biocidal character or to bring other additional properties.

• des agents tensioactifs (de 0,1 à 50 % en sec du poids de la composition aqueuse), notamment les
  • agents tensioactifs non-ioniques du type alkylphénols en C₆-C₁₂ polyoxyéthylénés, alcools aliphatiques en C₈-C₂₂ polyoxyéthylénés et/ou polyoxypropylénés, les copolymères bloc oxyde d'éthylène - oxyde de propylène, les amides carboxyliques éventuellement polyoxyéthylénés,
  • agents tensioactifs anioniques ou amphotères comme ceux du type savons de métaux alcalins (sels alcalins d'acides gras en C₈-C₂₄), sulfonates alcalins (alkylbenzène sulfonates en C₈-C₁₃, alkylsulfonates en C₁₂-C₁₆), alcools gras en C₆-C₁₆ oxyéthylénés et sulfatés, alkylphénols en C₈-C₁₃ oxyéthylénés et sulfatés, les sulfosuccinates alcalins (alkylsulfosuccinates en C₁₂-C₁₆), bétaïnes ...
  • agents tensioactifs cationiques d'acides gras en C8-C24, benzylés ou non
• des biocides ou bactériostatiques susceptibles d'apporter un caractère biocide aux dispersions, comme les agents tensioactifs cationiques (halogénures d'alkyldiméthylammonium ...), les biocides halogénures d'ammonium quaternaire ou de phosphonium, les biocides amphotères dérivés des glycines, les biocides phénoliques, les biocides dérivés de la chlorhexidine, les hypochlorites, les biocides ou polymères filmogènes polyammonium quaternaire ....
• des agents chélatants comme les aminocarboxylates
• des agents antisalissure filmogènes comme les polyesters téréphtaliques éventuellement sulfonés ...
• des alcools (éthanol, isopropanol, glycols)
• des adjuvants de détergence (phosphates, silicates)
• des parfums, des colorants ...

Examples of additives include:

• surfactants (from 0.1 to 50% by weight of the weight of the aqueous composition), especially the
  • nonionic surfactants of the polyoxyethylenated C ₆ -C ₁₂ alkylphenol type, polyoxyethylenated and / or polyoxypropylenated C ₈ -C ₂₂ aliphatic alcohols, ethylene oxide-propylene oxide block copolymers, optionally polyoxyethylenated carboxylic amides,
  • anionic or amphoteric surfactants such as those of the alkali metal soap type (alkaline salts of C ₈ -C ₂₄ fatty acids), alkali metal sulfonates (C ₈ -C ₁₃ alkylbenzene sulfonates, C ₁₂ -C ₁₆ alkylsulfonates), alcohols C ₆ -C ₁₆ fatty acids oxyethylenated and sulfated, C ₈ -C ₁₃ alkylphenols oxyethylenated and sulfated, alkali sulfosuccinates (C ₁₂ -C ₁₆ alkylsulfosuccinates), betaines ...
  • cationic surfactants of C8-C24 fatty acids, whether or not benzylated
• biocides or bacteriostats capable of providing a biocidal character to the dispersions, such as cationic surfactants (alkyldimethylammonium halides, etc.), quaternary ammonium or phosphonium halide biocides, glycine-derived amphoteric biocides, and phenolic biocides , biocides derived from chlorhexidine, hypochlorites, biocides or film-forming polymers polyammonium quaternary ....
• chelating agents such as aminocarboxylates
• film-forming antifouling agents such as optionally sulfonated terephthalic polyesters ...
• alcohols (ethanol, isopropanol, glycols)
• detergency builders (phosphates, silicates)
• perfumes, dyes ...

These various additives other than the polymer (P) or copolymer (P ') and (P ") and the surfactant (s) may be present in a proportion of 0 to 15% by weight of said aqueous cleaning composition.

The cleaning operation involves applying said cleaning composition, optionally diluted 1 to 1000 times, preferably 1 to 100 times, on the hard surface to be cleaned.

Application of the dispersion to the soiled surface may be carried out, for example, by dipping, fine spraying, application by sponge, mop or pre-impregnated cellulose material.

The amount of cleaning composition that can be favorably used is that corresponding to a deposit of 0.0001 to 1 g, preferably from 0.0005 to 0.1 g of copolymer (P) per m ² of hard surface to be treated.

The particles are formed of polymer chains. The most hydrophilic chains are located preferentially on the surface of the particle, thus forming the bark. The most hydrophobic chains are located inside the particle thus forming the core of the particle.

• après application ou copolymère (P') et (P") en dispersion, sur la surface à nettoyer, la phase continue liquide typiquement de l'eau s'évapore naturellement ou par chauffage ou par pénétration dans le support et forme un empilement/agregat de particules ou un film continu ou les deux simultanément au contact de la salissure à éliminer. Le composite « salissure-polymère » ainsi formé est ensuite éliminé par tout moyen connu de l'homme de l'art (balayage, aspiration, brossage, peignage, rinçage, délamination....) ;
• l'écorce de la particule de polymère (P) ou copolymère (P') et (P") est choisie selon la nature physico-chimique du support à traiter afin de minimiser l'interaction entre l'agrégat/film de polymère et la surface à traiter après élimination de la phase continue. Le problème résolu par l'invention est précisément d'éviter l'adhésion de la particule de salissure encapsulée par le polymère (P) ou copolymère (P') et (P") à la surface du support par un choix judicieux de la nature et de la teneur des monomères constitutifs du latex.

Le procédé selon l'invention est particulièrement intéressant pour améliorer les propriétés nettoyantes des compositions pour le nettoyage des moquettes en polyamide ; on utilise préférentiellement des polymères (P) dont les particules présentent en surface des motifs sulfonates et ou sulfates (copolymères P' et P") et dont la composition globale est telle que la Tg au pH d'application de la composition nettoyante soit comprise entre 60 et 110°C. De préférence, la taille des particules est alors comprise entre 5 et 50 nm.The advantages of the process using the polymers (P) or copolymer (P ') and (P ") include the following:

• after application or copolymer (P ') and (P ") in dispersion, on the surface to be cleaned, the liquid continuous phase typically of water evaporates naturally or by heating or penetration into the support and forms a stack / agregate of particles or a continuous film or both simultaneously in contact with the soil to be removed The "soil-polymer" composite thus formed is then removed by any means known to those skilled in the art (sweeping, suctioning, brushing, combing rinsing, delamination ...);
• the bark of the polymer particle (P) or copolymer (P ') and (P ") is chosen according to the physico-chemical nature of the support to be treated in order to minimize the interaction between the aggregate / polymer film and the surface to be treated after removal of the continuous phase The problem solved by the invention is precisely to prevent the adhesion of the soil particle encapsulated by the polymer (P) or copolymer (P ') and (P ") to the surface of the support by a judicious choice of the nature and content of the constituent monomers of the latex.

The process according to the invention is particularly advantageous for improving the cleaning properties of the compositions for cleaning polyamide carpets; polymers (P) are preferably used, the particles of which have, on the surface, sulphonate and / or sulphate units (P 'and P "copolymers) and whose overall composition is such that the Tg at the application pH of the cleaning composition is between 60 and 110 ° C. Preferably, the size of the particles is then between 5 and 50 nm.

The diameters of the polymer particles (P) can be determined in a well-known manner by light scattering or by transmission electron microscopy.

A third object of the invention is the use, in an aqueous cleaning composition comprising at least one surfactant for cleaning a soiled surface with a soiling, of a polymer (P) or a copolymer (P ') or (P ") as described above, as an agent for improving the removal of dirt from said surface.

The soils that can thus be eliminated are in particular greasy soils (oils for example), inorganic soils (carbon black, insoluble metal salts), proteinaceous stains (coffee stains, milk stains, fruit juice stains) that can be oxidized in most cases or decomposable by the presence of enzymes, natural soils of cellulosic type.

The following examples are given by way of non-limiting illustration.

Example 1

The detergent formulation used is adjusted to pH 4.

• Latex L 1a : Styrène, 100%, Tg de 108°C à pH4, taille de particule de 40 nm.
• Latex L 1b: Styrène/Styrène Sulfonate, 95/5, Tg de 104°C à pH4, taille de particule de 21 nm
• Latex L 1c: Styrène/AMPS, 95/5, Tg de 108°C à pH 4, taille de particule de 43 nm
• Latex L 1d : styrène/ABu/AMPS 72/23/5, Tg de 65°C à pH 4, taille de particule de 48 nm
• Latex L 1e : styrène/MMA/styrène sulfonate 71/24/5 Tg de 110°C, taille de particule de 13nm
• Latex L 2a : MMM/MAA 95/5 Tg de 115°C à pH 4, taille de particule de 88nm)
• Latex L 2b : MMA/ABu/MAA 95/0/5 Tg de 129°C à pH 4, taille de particule de 32 nm
• Latex L 2c : MMA/ABu/MAA 83/12/5 Tg de 83°C, taille de particule de 26 nm
• Latex L 2d : MMA/ABu/MAA 70/25/5 Tg de 54°C, taille de particule de 26 nm

The polymers and copolymers tested were used in the form of an aqueous dispersion (latex); they have been obtained by emulsion polymerization and have the following characteristics:

• Latex L 1a: Styrene, 100%, Tg of 108 ° C to pH4, particle size of 40 nm.
• Latex L 1b: Styrene / Styrene Sulfonate, 95/5, Tg 104 ° C to pH4, particle size 21 nm
• Latex L 1c: Styrene / AMPS, 95/5, Tg of 108 ° C to pH 4, particle size of 43 nm
• Latex L 1d: styrene / ABu / AMPS 72/23/5, Tg 65 ° C to pH 4, particle size 48 nm
• Latex L 1e: styrene / MMA / styrene sulfonate 71/24/5 Tg 110 ° C, particle size 13nm
• Latex L 2a: MMM / MAA 95/5 Tg of 115 ° C to pH 4, particle size of 88nm)
• Latex L 2b: MMA / ABu / MAA 95/0/5 Tg 129 ° C to pH 4, particle size 32 nm
• Latex L 2c: MMA / ABu / MAA 83/12/5 Tg of 83 ° C, particle size of 26 nm
• Latex L 2d: MMA / ABu / MAA 70/25/5 Tg of 54 ° C, particle size of 26 nm

The above abbreviations have the following meaning: MMA methyl methacrylate MAA methacrylic acid

The size of the latex particles was determined by light scattering using a Malvem Instruments Zetasizer. Formulation I II 1a 1b 1 C 1d first 2a 2b 2c 2d constituents
% in weight Latex tested L 1a L 1b L 1c L 1d L 1e L 2a L 2b L 2c L 2d 0 0 4 4 4 4 4 4 4 4 4 H202 0 2 2 2 2 2 2 2 2 2 2 Alkyl sulfate anionic surfactant
(SDS) 0 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 H20 0 97.6 93.6 93.6 93.6 93.6 93.6 93.6 93.6 93.6 93.6 Perfume 0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

In order to compare the performance of the cleaning formulas, the following comparative test is carried out.
A cleaning operation of a polyamide carpet is carried out by means of a sprayer by spraying the carpet with the aqueous base composition shown in the table above. Typically, 15 to 25 ml of formulation / m ² of surface to be treated are used. In this specific example, the carpet is presalia according to the protocol of the standard ISO / DIS 11378 well known to those skilled in the art with a soiling model such as soil B5 described in Annex B of the ISO 11118 (reference "AATCC soil") which is evenly distributed on the carpet. 15 ml of formulation (A) / m ^{2 are} then sprayed. The carpet is then allowed to dry for at least half an hour at room temperature. Finally, the treated carpet is sucked with a Hoover type conventional household vacuum cleaner. Optionally, the carpet can be brushed beforehand. In this particular example, the carpet is sucked without brushing but the vacuum cleaner has an integrated brush system.
After each application then suction, the overall appearance of the carpet is visually noted, and a touch experience is achieved. Any potential remarks are shown in the table below. The color change of the carpet is measured by image analysis (ΔL is the change in whiteness = L _after - L _before ). The lower ΔL is positive, the lower the color difference before and after washing. Plus ΔL is positive plus carpet whiteness and more ΔL is negative, the more the carpet blackens. The powder which has been aspirated by electron microscopy is analyzed. We also measure the removal of soil by a surface analysis technique, we note in the table that the difference with the vacuum (simple suction).
The results are recorded in the table below after 10 cycles (ie 10 sprays, 10 dryings and 10 aspirations). Formulation I II 1a 1b 1 C 1d first 2a 2b 2c 2d .DELTA.L 0 -5 5 2 1 0 0 2 4 3 0 To touch* + + --- - + + + - - - --- Powder removed ** 0 0 Very little + + + + + Little + 0 Dirt / + Vacuum *** - + + + ++ +++ ++ - + -

• Toucher *
  • + bon
  • — très rèche
  • - peu rèche
  • — rèche
  • — très plastique
• Poudre enlevée **
  • 0 aucune
  • + particules agregées
• Salissure/aspirateur ***
  • + référence ou égal à la référence
  • - moins bon que la référence
  • — encore pire
  • ++ meilleur que la référence
  • +++ encore meilleur

The symbols above mean:

• Touch *
  • + good
  • - very narrow
  • - little bit
  • - rick
  • - very plastic
• Powder removed **
  • 0 none
  • + Aggregated particles
• Dirt / vacuum ***
  • + reference or equal to the reference
  • - less good than the reference
  • - even worse
  • ++ better than the reference
  • +++ even better

• Une formulation à base aqueuse (II) noircit la moquette et n'aide pas à l'enlèvement des salissures.

Si la moquette devient rêche, c'est qu'une grande partie du latex n'a pas été éliminée. Cette mesure est en général bien corrélée au blanchissement de la moquette (ΔL >2). Les latex à basse Tg (2d) donnent de moins bons résultats car ils plastifient la moquette et n'éliminent pas correctement les salissures.
Les latex carboxylés (qui comportent des acrylates en surface) enlèvent bien la salissure mais sont difficiles à éliminer de la moquette, sauf si leur taille est optimisée (2a versus 2b, 2c ). Les latex à base de polystyrène donnent des résultats intéressants mais en ajoutant des motifs sulfonates en surface, on augmente considèrablement leur performance (comparaison 1a et 1b/1c/1d/1e).
Les latex sulfonates de type 1b,1c,1d et 1e sont d'excellents candidats car ils ne s'accumulent pas (ou peu) sur la moquette et ne modifient pas l'aspect de surface ni le toucher. En optimisant leur température de transition vitreuse (Tg) on obtient une bonne efficacité (comparaison de 1b, 1c et 1d). Les nanolatex 1c et 1d donnent donc de bons résultats. Le résultat est optimal avec le latex le plus dur et le plus petit, c'est-à-dire avec le latex 1e.The conclusions of these experiments are as follows:

• A water-based formulation (II) blackens the carpet and does not help with the removal of dirt.

If the carpet becomes rough, it is because a large part of the latex has not been eliminated. This measure is generally well correlated with the whitening of carpet (ΔL> 2). Low Tg latexes (2d) give less good results because they plasticize the carpet and do not remove the stains properly.
The carboxylated latices (which have acrylates on the surface) remove the soiling well but are difficult to remove from the carpet, unless their size is optimized (2a versus 2b, 2c). Polystyrene-based latexes give interesting results, but by adding sulphonate units on the surface, their performance is considerably increased (comparison 1a and 1b / 1c / 1d / 1e).
Latex sulfonate type 1b, 1c, 1d and 1e are excellent candidates because they do not accumulate (or little) on the carpet and do not change the surface appearance or feel. By optimizing their glass transition temperature (Tg), good efficiency is obtained (comparison of 1b, 1c and 1d). Nanolatex 1c and 1d therefore give good results. The result is optimal with the hardest and the smallest latex, that is to say with the latex 1e.

Example 2 Formulation of the washing additive type ("prespoter")

The purpose of this experiment is to show that the amount of polymer particles deposited on the surface to be cleaned manages the size of the final chips and thus the ability to coat or trap a stain. For this, one uses the nanolatex out of synthesis (dry extract of 30% on average), those ci are lying on surfaces of polyamide previously soiled with coffee; the coating is made to the threaded rod at different thicknesses.

After drying by evoparation in an air-conditioned room (20 ° C. and 50% RH), the size of the obtained chips is measured (by acquisition, processing and image analysis, 1 mm = 17 pixels). The edges of the samples dry faster than the center by peak effect. Typically, relatively heterogeneous chips are obtained.

Carboxed latex

An increasing lying-down series is performed on the nanolatex 2c. The figure 1 / 2 repeat the results. It can be seen that the size of the chips is globally increasing with the layer thickness. From this it can be deduced that the larger the quantity sprayed (or the larger droplet size), the larger are the latex aggregates. After aspiration, the intensity of the stain Residual coffee is measured in the eye and it is very clear that the task is all the more easily eliminated as the formed chips are large.

Different latexes are used: the latexes 2b, 2c and 2d have almost the same size and a variable Tg. According to figure 2/2 it is clear that the lower the Tg, the larger the chips; at the extreme no more chips are formed with the latex 2d which forms an adhesive film. The effect on the coffee stain is as follows: in the case of latex 2d, the task has not been elimed, it is brighter. In the case of the latex 2c, the elimination is satisfactory, it is not in the case of the latex 2b, the removal is substantially improved by the latex 2a. It is concluded that there is a maximum glass transition temperature Tg below which the latex has no effect on the task. This temperature is, according to the above experiment, reasonably located between 54 and 82 ° C.

Thus with acrylate type latices, the best cleaning agents have a Tg around 60 ° C and a size close to 100 nm.

Sulfur latex

Different latexes are used: the latexes L 1b, L 1d and L 1e have almost the same size and a variable Tg. According to figure 2/2 it is clear that the lower the Tg, the smaller the chips; interestingly, even low Tg form larger chips than their carboxyl counterparts. The effect on the coffee stain is as follows: in all cases, the coffee stain is clearly removed. However, increasing the Tg of the latex (from 1d, then 1b and then 1e leads to an improvement in the removal, it is concluded that the higher the Tg of the sulfur latex, the better its anti-stain activity. Preferably, the latex has a Tg greater than 100 ° C.

Claims (34)

1. A process to increase the cleaning properties of an aqueous cleaning composition comprising at least one surface active agent, intended for cleaning a surface soiled by a stain, by adding to said cleaning composition, at least one polymer (P) that is insoluble under the conditions of use of said composition, present in the form of particles having mean size ranging from 5 to 500 nm, comprising

   - hydrophobic monomer units (N) that are uncharged or non-ionizable at the pH of use of the composition of the invention,

   - optionally at least one hydrophilic monomer unit (F) selected from among the monomer units

   * (F1) cationic or potentially cationic at the pH of use of said composition,

   * (F2) amphoteric at the pH of use of said composition,

   * (F3) anionic or potentially anionic at the pH of use of said composition,

   * (F4) uncharged or non-ionizable and hydrophilic at the pH of use of said composition,

   * or mixtures thereof

   - and optionally at least one cross-linking unit (R),

   the aqueous cleaning composition being

   - a solid or liquid detergent formulation for washing clothes or other fibrous textile articles;

   - a rinsing and/or liquid softener formulation, that can directly form by dilution a rinsing and/or softening bath;

   - a washing additive intended to be deposited on the dry surface to be cleaned prior to a washing operation using a detergent formulation containing or not containing said polymer, or

   - a detergent formulation for the cleaning of hard surfaces.
2. A process according to claim 1) characterized in that the mean size of polymer particles (P) ranges from 5 to 300 nm, more specifically from 5 to 100 nm, even more preferably from 10 to 50 nm.
3. A process according to claim 1) or 2), characterized in that said polymer (P) has a glass transition temperature Tg of from -40°C to 150°C, preferably from 0 to 110°C, more specifically from 40 to 110°C.
4. A process according to any one of claims 1) to 3) characterized in that said polymer (P) is used in the form of an aqueous dispersion having a solids content of from 10 to 50% by weight, preferably from 20 to 40% by weight.
5. A process according to any one of claims 1) to 4), characterized in that said polymer is used at 0.05 to 50% dry weight of the weight of said cleaning composition.
6. A process according to any one of claims 1) to 5), characterized in that the aqueous cleaning composition is

   - a solid or liquid detergent formulation for washing clothes or other fibrous textile articles comprising from 0.01 to 5%, preferably from 0.05 to 3%, of said polymer (P), expressed as dry weight, that can directly form a washing bath by dilution;

   - a rinsing and/or liquid softener formulation, comprising from 0.05 to 3%, preferably from 0.1 to 2%, of said polymer (P), expressed as dry weight, that can directly form a rinsing and/or softening bath by dilution;

   - a washing additive comprising from 0.05 to 10%, preferably from 0.1 to 5%, of said polymer (P), expressed as dry weight, intended to be deposited on the dry surface to be cleaned prior to a washing operation using a detergent formulation containing or not containing said polymer.

   - a detergent formulation for cleaning hard surfaces comprising from 0.01 to 5%, preferably from 0.01 to 0.5%, by weight of said polymer (P), expressed as dry weight.
7. A process according to any one of claims 1) to 6), characterized in that said monomer units (N) and (F) are derived from α-β monoethylenically unsaturated monomers, and optional monomer units (R) are derived from diethylenically unsaturated monomers.
8. A process according to any one of claims 1) to 7), characterized in that the hydrophobic units (N) are derived from vinyl aromatic monomers, from alkylesters of α-β monoethylenically unsaturated acids, from vinyl or allyl esters of saturated carboxylic acids, from α-β monoethylenically unsaturated nitriles.
9. A process according to any one of claims 1) to 8), characterized in that the cationic or cationizable hydrophilic units (F1) are derived from N,N(dialkylaminoωalkyl)amides of α-β monoethylenically unsaturated carboxylic acids, from α-β monoethylenically unsaturated aminoesters, from precursor monomers of primary amine functions by hydrolysis.
10. A process according to any one of claims 1) to 9), characterized in that hydrophilic amphoteric units (F2) are derived from N,N-dimethyl-N-methacryloyloxyethyl-N-(3-sulfopropyl) ammonium sulfobetaine, N,N-dimethyl-N-(2-methacrylamidoethyl)-N-(3-sulfopropyl) ammonium betaine, 1-vinyl-3-(3-sulfopropyl) imidazolidium betaine, 1-(3-sulfopropyl)-2-vinylpyridinium betaine, derivatives of the quaternization reaction of N(dialkylaminoωalkyl)amides of α-β ethylenically unsaturated carboxylic acids or α-β monoethylenically unsaturated aminoesters with an alkali metal chloroacetate or propane sultone.
11. A process according to any one of claims 1) to 10), characterized in that the anionic or anionizable hydrophilic units (F3) are derived from α-β monoethylenically unsaturated monomers having at least one carboxyl function, α-β monoethylenically unsaturated monomers having at least one sulfur-containing function, preferably a sulfate- or sulfonate-containing function, α-β monoethylenically unsaturated monomers having at least one phosphonate or phosphate function, and water soluble salts thereof, α-β monoethylenically unsaturated monomer precursors of a carboxylate function or functions via hydrolysis.
12. A process according to any one of claims 1] to 11), characterized in that the uncharged or non-ionizable hydrophilic units (F4) are derived from hydroxyalkylesters of α-β monoethylenically unsaturated acids, amides of α-β monoethylenically unsaturated acids, α-β ethylenically unsaturated monomers carrying a polyalkylene oxide-substituted water soluble segment, α-β monoethylenically unsaturated monomer precursors of vinyl alcohol units or of polyvinyl alcohol segments by polymerization then hydrolysis, or of ethyl-2-imidazolidinone methacrylamide.
13. A process according to any one of claims 1) to 12), characterized in that the cross-linking units (R) are derived from divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, methylene bis (acrylamide), glyoxal bis (acrylamide).
14. A process according to any one of claims 1) to 13), characterized in that at least 70% of the total mass of said polymer (P) is formed by a hydrophobic unit or units (N) and in that, when they are present, hydrophilic units (F) do not represent more than 30% of the total mass of the polymer (P) and cross-linking units (R) do not represent more than 20%, preferably not more than 10%, more specifically not more than 5% of the total mass of the polymer (P).
15. A process according to claim 14), characterized in that the polymer (P) is an uncharged or non-ionizable copolymer (P1) comprising

    • at least 70% of its weight hydrophobic monomer units (N)

    • optionally at least 1%, preferably from 3 to 30% of its weight uncharged or non-ionizable hydrophilic monomer units (F4)

    • optionally not more than 20%, preferably not more than 10% of its weight uncharged or non-ionizable cross-linking units (R)
16. A process according to claim 14), characterized in that the polymer (P) is a copolymer (P2) having anionic or anionizable units, and not having cationic or cationizable units, comprising

    • at least 70% of its weight hydrophobic monomer units (N)

    • at least 1% of its weight, preferably from 3 to 30% of its weight, more specifically from 1 to 20% of its weight anionic or anionizable hydrophilic monomer units (F3)

    • optionally not more than 29% of its weight uncharged or non-ionizable hydrophilic monomer units (F4).
17. A process according to claim 14), characterized in that the polymer (P) is a copolymer (P3) having amphoteric units, comprising

    • at least 70% of its weight hydrophobic monomer units (N)

    • at least 0.1% of its weight, preferably not more than 20% of its weight, more specifically not more than 10% of its weight amphoteric hydrophilic monomer units (F2)

    • optionally uncharged or non-ionizable hydrophilic monomer units (F4)

    • optionally cationic or cationizable hydrophilic monomer units (F1) all of the hydrophilic monomer units (F) representing preferably at least 1% of the weight of the polymer (P3), and the molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 according to the desired use of said composition. ,
18. A process according to claim 17), characterized in that the cleaning composition is a drying additive or an aqueous ironing formulation, or a formulation for cleaning hard surfaces when the molar ratio of cationic charges to anionic charges ranges from 1/99 to 80/20.
19. A process according to claim 17), characterized in that the cleaning composition is a detergent formulation, a washing additive, or a formulation for cleaning hard surfaces when the molar ratio of cationic charges to anionic charges ranges from 1/99 to 60/40, preferably from 5/95 to 50/50.
20. A process according to claim 14), characterized in that the polymer (P) is a copolymer (P4) having both cationic or cationizable units and anionic or anionizable units, comprising

    • at least 70% of its weight hydrophobic monomer units (N)

    • cationic or cationizable hydrophilic monomer units (F1)

    • anionic or anionizable hydrophilic monomer units (F3)

    • optionally amphoteric hydrophilic monomer units (F2)

    • optionally uncharged or non-ionizable hydrophilic monomer units (F4)

    all of the hydrophilic monomer units (F) representing preferably at least 1% of the weight of the polymer (P4), and the molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 according to the desired use of the cleaning composition.
21. A process according to claim 20), characterized in that the cleaning composition is a detergent formulation, a washing additive, when the molar ratio of cationic charges to anionic charges ranges from 1/99 to 60/40, preferably from 5/95 to 50/50.
22. A process according to claim 14), characterized in that the polymer (P) is a copolymer (P5) having cationic or cationizable units and not having anionic or anionizable units, comprising

    • at least 70% of its weight hydrophobic monomer units (N)

    • at least 1% of its weight, preferably from 3 to 30% of its weight, more specifically from 1 to 10% of its weight cationic or cationizable hydrophilic monomer units (F1)

    • optionally not more than 20% of its weight uncharged or non-ionizable hydrophilic monomer units (F4)
23. A process according to any one of claims 1) to 14), characterized in that said polymer is a copolymer (P')

    - insoluble in conditions of use of said process and use of the aqueous cleaning composition

    - present in the form of particles of mean size from 5 to 500 nm, preferably from 5 to 100 nm, more specifically from 5 to 50 nm, in dispersion in said aqueous composition

    - and comprising

    • hydrophobic monomer units (N) that are uncharged or non-ionizable at the pH of use of said composition and,

    • and at least one anionic or amphoteric non-carboxylate hydrophilic sulfur-containing, preferably sulfonate- or sulfate-containing, monomer unit (F'),

    derived from α-β monoethylenically unsaturated monomers.
24. A process according to claim 23) characterized in that the anionic or amphoteric non-carboxylate hydrophilic sulfur-containing, preferably sulfonate- or sulfate-containing, monomer unit (F'), is derived from at least one monomer selected from among

    • 2-sulfooxyethyl methacrylate, vinylbenzene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic, sulfoethyl acrylate or methacrylate, sulfopropyle acrylate or methacrylate and water soluble salts thereof

    • N,N-dimethyl-N-methacryloyloxyethyl-N-(3-sulfopropyl) ammonium sulfobetaine, N,N-dimethyl-N-(2-methacrylamidoethyl)-N-(3-sulfopropyl) ammonium betaine, 1-vinyl-3-(3-sulfopropyl) imidazolidium betaine, 1-(3-sulfopropyl)-2-vinylpyridinium betaine.
25. A process according to claim 23) or 24), characterized in that said copolymer (P') does not comprise more than 10% of its weight of carboxylate COO^-monomer units and/or not more than 10% of its weight of non-amphoteric monomer units carrying a cationic charge.
26. A process according to claim 25), characterized in that said copolymer (P') has no carboxylate COO^- monomer units and/or non-amphoteric monomer units carrying a cationic charge.
27. A process according to one of claims 23) to 26), characterized in that said copolymer (P') further comprises:

    • at least one non-carboxylic and non-cationic cross-linking unit (R)

    • and/or at least one unit derived from a monomer having at least one phosphonate or phosphate function

    • and/or at least one uncharged or non-ionizable hydrophilic unit.
28. A process according to claim 27), characterized in that said copolymer (P') comprises at least one unit derived from at least one monomer having at least one phosphonate or phosphate function selected from among vinyl phosphonic acid, vinyl diphosphonic acid, esters of ethylenically unsaturated phosphates, in particular phosphates derived from hydroxyethyl methacrylate and those derived from polyalkylene oxide-substituted methacrylates and water soluble salts thereof.
29. A process according to one of claims 23) to 28), characterized in that said copolymer (P') comprises

    • at least 70% of its total weight hydrophobic units (N)

    • from 1 to 30% of its total mass of anionic or amphoteric sulfur-containing, preferably sulfonate or sulfate, function (F') unit or units,

    when they are present, not more than 10% of its total mass of monomer units having phosphonate or phosphate functions.
30. A process according to claim 29), characterized in that said copolymer (P') comprises

    • at least 70% of its weight hydrophobic monomer units (N)

    • at least 1% of its weight, preferably from 3 to 30% of its weight anionic sulfur-containing, preferably sulfonate or sulfate, monomer units (F') and/or

    • at least 0.1% of its weight, preferably not more than 20% of its weight, more specifically not more than 10% of its weight amphoteric hydrophilic, preferably sulfonate or sulfate, monomer units (F')

    • optionally not more than 29% of its weight uncharged or non-ionizable hydrophilic units.
31. A process according to any one of claims 1) to 30), characterized in that the surface to be cleaned is a textile made of synthetic and/or natural fiber, human hair, human skin, concrete-, glass-, stone-, brick-, ceramic-, melamine-, metal-, wood-type hard surfaces and other synthetic surfaces.
32. A process according to any one of claims 23) to 30), characterized in that the surface to be cleaned is a polyamide textile and in that said copolymer (P') has a glass transition temperature Tg ranging from 60 to 110°C.
33. A use, in an aqueous cleaning composition comprising at least one surface active agent intended for cleaning a surface soiled by a stain, of a polymer (P) or a copolymer (P') described in any of claims 1) to 4), 7) to 15), 16) 17), 20), 22), 23) to 29), as an agent improving removal of a stain from said surface.
34. A process for cleaning a surface soiled by a stain containing the following steps:

    a) coating the surface to be cleaned by an effective amount of aqueous cleaning composition comprising the polymer (P) or copolymer (P') described in any one of claims 1) to 4), 7) to 15), 16), 17), 20), 22), 23) to 30), insoluble under the conditions of use in aqueous medium of said composition,

    b) drying the surface to evaporate the water from the composition and generate the polymer (P) or copolymer (P') from the dispersion which forms a (co)polymer (P) or (P')/stain composite, and

    c) optionally, removal of said composite product from the surface cleaned in this way.

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