EP1594945B1 - Composition for cleaning or rinsing hard surfaces - Google Patents

Description

The subject of the present invention is a cleaning or rinsing composition intended for the treatment of industrial, domestic or community hard surfaces, in particular of the ceramic, tiling, glass, metal, melamine, formica or plastic type, aimed at conferring on them, in particular, anti-deposition and / or non-sticking properties of the stains; it can also provide them with antistatic properties, gloss, anti-slip properties.

• au séchage des gouttes d'eau déposées sur ladite surface (par exemple dépôt de sels minéraux).
• à l'accrochage de particules minérales ou organiques présentes dans l'air ambiant (cas du nettoyage de gratte-ciels) ou déposées par contact (cas du nettoyage des sols, des toilettes ...)
• au dépôt par éclaboussure de composés organiques gras (graisses de cuisine)
• au dépôt de savons et de leur sels métalliques
• au dépôt de composés d'origine végétales de type hydrocolloides ou polysaccharides.

The invention more particularly relates to a cleaning or rinsing composition for the treatment of a hard surface, a composition which is capable of conferring thereto anti-deposition and / or anti-adhesion residual properties, so as to avoid the subsequent presence. of traces due in particular:

• drying the drops of water deposited on said surface (for example depositing mineral salts).
• with the attachment of mineral or organic particles present in the ambient air (case of the cleaning of skyscrapers) or deposited by contact (case of the cleaning of the grounds, toilets ...)
• splashing of organic fatty compounds (cooking grease)
• to the deposit of soaps and their metal salts
• deposition of plant origin compounds of the hydrocolloid or polysaccharide type.

Commercial detergent formulations can effectively clean industrial, domestic or community hard surfaces. They generally consist of an aqueous solution of surfactants, especially nonionic and anionic surfactants, or nonionic and cationic surfactants, solvents, alcohol (s) to facilitate drying, and optionally sequestering agents and bases or acids to adjust the pH. A frequent disadvantage of these detergent formulations is that the subsequent contact of the hard surface with water leads to the formation of traces during drying. In addition, the treatment with these formulations is, for most of them, only purely curative and non-preventive. Thus, industrial or household cleaners are effective for cleaning the soiled hard surface but do not prevent or limit its future fouling, or even to promote its subsequent cleaning.

A solution to this problem has been proposed in EP-A-1196527 , EP-A-1196528 and EP-A-1196523 by depositing on the surface, by means of a cleaning or rinsing formulation, a water-soluble amphoteric organic copolymer derived from a cationic monomer and an anionic or potentially anionic monomer, in an amount sufficient to render the surface hydrophilic (or improve its hydrophilicity, in order to obtain the lowest possible contact angle between the hard surface to be treated and a drop of water) but also to ensure the retention of water near the hard surface thus treated.

It has been proposed to provide articles of textile fibers (cotton and poyester in particular) antistatic properties, anti-fouling and / or permanent antifungal, padding of said articles to 130-200 ° C, using a bath-pad solution comprising a betaine polymer or copolymer, a thermosetting aminoplast condensate and a catalyst, drying and heat treatment at 130-200 ° C ( US Patent 3,671,305 )

It has also been proposed to introduce into the detergent compositions for washing textile articles ("laundry"), zwitterionic polymers, polybetaines in particular, whose anionic groups are linked to the cationic groups by polyether chains, as an additive allowing remove particulate clay soils and as an anti-redeposition additive ( EP-B-112,592 ).

FR2813312 relates to a composition for the care of laundry comprising at least one nanolatex of a polymer insoluble in the conditions of use in aqueous or wet medium of said composition. The copolymers described in this document are obtained by radical emulsion polymerization and comprise at least 70% by weight of hydrophobic monomeric units.

The Applicant has now found that the deposition on a hard surface, by means of a cleaning or rinsing formulation, of polybetaine zwitterions having one or more permanent positive charges and one or more permanent negative charges on the same monomer unit, the number positive charges being equal to the number of negative charges on the same monomer unit, allowed to confer on the surface thus treated persistent anti-deposition and / or anti-adhesion properties of particularly effective soiling; in addition, the presence of polybetaine zwitterions makes it possible to improve the cleaning capacity of said formulation.

By "persistent antideposition properties and / or anti-adhesion" means that the treated surface retains these properties over time, including after further contact with soiling (for example rainwater, water added rinsing water distribution network or not of products of rinsing, splashing fat, soaps ...). This property of remanence can be observed beyond a dozen rinsing cycles, or even in some particular cases where the rinses are numerous (eg toilets), beyond 100 cycles of rinsing.

The above expression of "giving the surface thus treated antideposition properties" means more particularly that the treated surface, brought into contact with a soil in a predominantly aqueous medium, will not tend to "capture" said soiling, which thus significantly reduces the deposit of dirt on the surface.

The above expression of "giving the surface thus treated antiadhesive properties" means more particularly that the treated surface is likely to interact only very slightly with the soil deposited thereon, which allows a removal easy soiling of the soiled treated surface; indeed, during the drying of the dirt put in contact with the treated surface, the bonds developed between the soil and the surface are very weak; thus, breaking these links requires less energy (therefore effort) during the cleaning operation.

When it is said that the presence of polybetaine zwitterions makes it possible to "improve the cleaning capacity" of a formulation, it means that for the same amount of cleaning formulation (including a dishwashing formulation by hand), the polybetaine zwitterion-containing formulation makes it possible to clean a larger number of soiled objects than a formulation that is free of it.

In addition, the deposition on a hard surface of polybetaine zwitterions makes it possible to add antistatic properties to this surface; this property is particularly interesting in the case of synthetic surfaces.

The presence of polybetaine zwitterions in hard surface treatment formulations makes the surface hydrophilic or improves its hydrophilicity.

The hydrophilic property of the surface also makes it possible to reduce the formation of condensation on the surface; this benefit can be exploited in cleaning formulas for windows and mirrors, especially in bathrooms. In addition, the rate of drying of the surface, immediately after its treatment by the application of the polymer but also after repeated and repeated contacts with an aqueous medium is significantly improved.

A first subject of the invention consists of a composition for cleaning or rinsing in aqueous or aqueous-alcoholic medium of the hard surfaces, comprising at least one surfactant and at least one polybetaine (B), with the weight ratio polybetaine (B) / agent (s) surfactant (s) being between 1/1 and 1/1000, and said polybétaïne (B) being as defined in claim 1.

The term "hard surfaces" is to be taken broadly; these are non-textile surfaces, which can be household, community or industrial.

• céramique (surfaces telles que lavabo, baignoires, carrelages muraux ou au sol, cuvettes des toilettes...)
• verre (surfaces telles que vitres intérieures et extérieures de bâtiments ou de véhicules, miroirs,
• métal (surfaces telles que parois internes ou externes de réacteurs, lames, panneaux, tuyaux....)
• résines synthétiques (par exemple carrosseries ou surfaces intérieures de véhicules motorisés (voitures, camions, bus, trains, avions ...) surfaces en mélamine ou formica pour l'intérieur de bureaux, cuisines, ...))
• matières plastiques (par exemple polychlorure de vinyle, polyamide, pour l'intérieur des véhicules, voitures notamment)

They may be of any material, in particular of the type:

• ceramic (surfaces such as washbasin, baths, wall or floor tiles, toilet bowls ...)
• glass (such as interior and exterior windows of buildings or vehicles, mirrors,
• metal (surfaces such as inner or outer walls of reactors, blades, panels, pipes ....)
• synthetic resins (for example bodywork or interior surfaces of motorized vehicles (cars, trucks, buses, trains, airplanes ...) melamine or formica surfaces for office interiors, kitchens, ...))
• plastics (for example polyvinyl chloride, polyamide, for the interior of vehicles, cars in particular)

The "hard surfaces" according to the invention are non-porous and non-fibrillar surfaces; they are thus distinguished from textile surfaces (fabrics, carpets, clothing ... in natural, artificial or synthetic materials).

• 
  Une composition nettoyante ou rinçante à usage ménager ; elle peut être universelle ou peut être plus spécifique, comme une composition pour le nettoyage ou le rinçage
  • de salle de bain ; ladite composition empêche notamment le dépôt des sels de savon autour des baignoires et sur les lavabos, prévient la croissance et/ou le dépôt de cristaux de calcaire sur ces surfaces, et retarde l'apparition de tâches de savon ultérieures.
  • de cuisine ; ladite composition permet d'améliorer le nettoyage des plans de travail lorsque ceux-ci sont souillés par des salissures grasses insaturées susceptibles de réticuler dans le temps ; les tâches grasses partent à l'eau sans frotter.
  • des sols (en linoleum, carrelage ou ciment) ; ladite composition permet d'améliorer l'enlèvement des poussières, des salissures de types argilo-calcaires (terre, sable, boue...) ; les tâches sur le sol peuvent être nettoyées sans effort par simple balayage, sans brossage ; en outre ladite composition apporte des propriétés antidérapantes.
  • des toilettes ; ladite composition permet d'éviter l'adhésion de traces d'excréments sur la surface ; le seul flux de la chasse d'eau est suffisant pour éliminer ces traces ; l'utilisation dune brosse est inutile.
  • des vitres ou miroirs ; ladite composition permet d'éviter le dépôt de salissures particulaires minérales ou organiques sur la surface.
  • de la vaisselle, à la main ou à l'aide d'une machine automatique ; ladite composition permet, dans le cas du lavage à la main, de faciliter l'enlèvement des tâches résiduelles d'aliments sèchés, et de laver un plus grand nombre de couverts ou ustensiles avec un même volume de bain ; la surface des couverts et ustensiles encore mouillés n'est plus glissante et ainsi n'échappe pas des mains de l'utilisateur ; il a également été constaté un effet « squeaky clean », à savoir que la surface « crisse » sous l'effet d'un frottement avec le doigt. Dans le cas du lavage ou du rinçage en lave-vaisselle, ladite composition permet l'anti-redéposition des salissures alimentaires et des sels minéraux insolubles du calcium, et apporte de la brillance aux ustensiles et couverts ; la composition permet également de ne plus avoir à « prélaver » les couverts ou ustensiles avant leur introduction dans le lave-vaisselle.
• 
  Une composition nettoyante ou rinçante à usage industriel ou de collectivité ; elle peut être universelle ou plus spécifique, comme une composition pour le nettoyage
  • des réacteurs, des lames en acier, des éviers, des cuves.
  • de la vaisselle
  • des surfaces extérieures ou intérieures des bâtiments
  • des vitres des bâtiments et immeubles
  • des bouteilles

The composition according to the invention, capable of providing the hard surfaces to be treated with anti-deposition and / or anti-adhesion properties, can be:

• 
  A cleaning or rinsing composition for household purposes; it can be universal or can be more specific, such as a composition for cleaning or rinsing
  • bathroom; said composition prevents in particular the deposition of soap salts around the baths and on the washbasins, prevents the growth and / or deposition of limestone crystals on these surfaces, and delays the appearance of subsequent soap stains.
  • of the kitchen ; said composition makes it possible to improve the cleaning of the worktops when they are soiled by unsaturated fatty soils that may crosslink over time; the greasy stains leave the water without rubbing.
  • floors (in linoleum, tiles or cement); said composition makes it possible to improve the removal of dust, soils of clay-limestone types (earth, sand, mud, etc.); the tasks on the floor can be cleaned effortlessly by simply sweeping, without brushing; in addition, said composition provides anti-slip properties.
  • toilets ; said composition prevents the adhesion of traces of excrement on the surface; the only flow of flush is enough to remove these traces; the use of a brush is useless.
  • windows or mirrors; said composition makes it possible to prevent the deposit of particulate mineral or organic dirt on the surface.
  • dishes, by hand or with the help of an automatic machine; said composition makes it possible, in the case of hand washing, to facilitate the removal of residual stains from dried foods, and to wash a larger number of cutlery or utensils with the same volume of bath; the surface of cutlery and utensils still wet is no longer slippery and so does not escape the hands of the user; it has also been found a "squeaky clean" effect, namely that the surface "crunch" under the effect of a rub with the finger. In the case of washing or rinsing in the dishwasher, said composition allows the anti-redeposition of food soils and insoluble mineral salts of calcium, and brings brilliance to utensils and cutlery; the composition also makes it possible to no longer have to "pre-wash" cutlery or utensils before they are introduced into the dishwasher.
• 
  A cleaning or rinsing composition for industrial or community use; it can be universal or more specific, like a composition for cleaning
  • reactors, steel blades, sinks, tanks.
  • dishes
  • exterior or interior surfaces of buildings
  • windows of buildings and buildings
  • bottles

The composition according to the invention can be in any form and can be used in many ways.

• d'un liquide gélifié ou non, à déposer tel quel, notamment par pulvérisation,
  • directement sur les surfaces à nettoyer ou rincer, ou
  • sur une éponge ou un autre support (article en cellulose par exemple, tissé ou non-tissé) avant d'être appliqué sur la surface à traiter
• d'un liquide gélifié ou non, à diluer dans de l'eau (éventuellement additionnée d'un autre solvant) avant d'être appliqué sur la surface à traiter
• d'un liquide gélifié ou non, emprisonné dans un sachet hydrosoluble
• d'une mousse
• d'un aérosol
• d'un liquide absorbé sur un support absorbant en un article tissé ou non-tissé notamment (lingette)
• d'un solide, tablette notamment, éventuellement emprisonnée dans un sachet hydrosoluble, ladite composition pouvant représenter tout ou partie de la tablette.

So, it can be in the form

• a gelled liquid or not, to be deposited as such, in particular by spraying,
  • directly on surfaces to be cleaned or rinsed, or
  • on a sponge or other support (cellulose article for example, woven or non-woven) before being applied to the surface to be treated
• of a gelled liquid or not, to be diluted in water (possibly added with another solvent) before being applied on the surface to be treated
• a gelled liquid or not, trapped in a water-soluble sachet
• a foam
• an aerosol
• a liquid absorbed on an absorbent support in a woven or non-woven article in particular (wipe)
• a solid, including tablet, possibly trapped in a water-soluble bag, said composition may represent all or part of the tablet.

For a good embodiment of the invention, said polybetaine (B) is present in the composition subject of the invention in an amount effective to provide said surfaces with anti-deposition and / or anti-adhesion properties soils may be deposited on said surfaces .

Said composition which is the subject of the invention may contain, according to its application, from 0.001 to 10% of its weight of at least one polybetaine (B).

The pH of the composition or the pH of use of the composition according to the invention may vary, depending on the applications and the surfaces to be treated, from 1 to 14, or even from 0.5 to 14.

Extreme pHs are typical in industrial or community cleaning applications. In the field of household applications, the pH range from 1 to 13 depending on the applications.

Said composition may be used for cleaning or rinsing hard surfaces, in such quantity that, after possible rinsing and drying, the amount of polybetaine (B) deposited on the surface is from 0.0001 to 10 mg / m ² preferably from 0.001 to 5 mg / m ² of treated surface.

Unless otherwise indicated, when we speak of molar mass, it will be the average molar mass, expressed in g / mol. This can be determined by aqueous gel permeation chromatography (GPC), by light scattering (DDL or MALLS), with an aqueous eluent or an organic eluent (for example dimethylacetamide, dimethylformamide, etc.) according to the polymer composition.

By definition, polybetaines are polymeric zwitterions carrying one or more positive charges and one or more negative charges on the same betaine monomer unit. On a single betaine monomer unit, the number of positive charge (s) is equal to the number of negative charge (s).

According to the invention, the polybetaine (B) has a permanent anionic charge and a permanent cationic charge at both pH strongly acidic and pH strongly basic; these fillers are permanent in a pH range of 1 to 14.

The permanent anionic charge can be provided by one or more anions sulfonate, phosphate, phosphonate, phosphinate, ethenolates ....

The cationic charge is provided by one or more onium or inium cations of the family of nitrogen (ammonium, pyrididium, imidazolinium cations), phosphorus (phosphonium, etc.) or sulfur (sulfonium, etc.).

The betaine functions of polybetaine (B) are carried by pendant groups.

For the same betaine monomer unit, the atom carrying the permanent cationic charge is preferentially connected to the anionic charge bearing anion by an optionally substituted hydrocarbon multivalent group, in particular an alkylene group, optionally substituted by one or more hydroxyl groups. .

• 
  formules (I) à (IV) dans lesquelles,
  • les symboles R¹ , R² et R⁵, semblables ou différents représentent un radical alkyle contenant de 1 à 7 atomes de carbone, de préférence de 1 à 2 atomes de carbone
  • les symboles R³ et R⁴ représentent des radicaux hydrocarbonés formant avec l'atome d'azote un hétérocycle azoté comportant éventuellement un ou plusieurs autres hétéroatomes, d'azote notamment
  • le symbole R⁶ représente un radical hydrocarboné formant avec l'atome d'azote un hétérocycle azoté, saturé ou insaturé, comportant éventuellement un ou plusieurs autres hétéroatomes, d'azote notamment
  • le symbole R représente un radical alkylène linéaire ou ramifié comprenant de 1 à 15 atomes de carbone, de préférence de 2 à 4 atome de carbone, éventuellement substitué par un ou plusieurs groupes hydroxy, ou un radical benzylène
  • le symbole A représente S(=O)(=O) , OP(=O)(=O), OP(=O)(OR'), P(=O)(OR') ou P(=O)(R'), où R' représente un radical alkyle contenant de 1 à 7 atomes de carbone ou un radical phényle
• 
  formule (V) dans laquelle
  • les symboles R¹ , R² et R ont la définition donnée ci-dessus
  • le symbole W représente une fonction éthénolate de formule
    
            O-C(O^(-) = C(C≡N)₂
    
            O-C(O)-C^(-) (C≡N)₂
    
            O-C(O)-C (-C=N) (=C=N^(-))
    
    
• 
  formule (VI) dans laquelle,
  • les symboles R¹ et R², ont la définition donnée ci-dessus
  • le symboles R⁷, semblable ou différent de R¹ ou R², représente un radical alkyle contenant de 1 à 7 atomes de carbone, de préférence de 1 à 2 atomes de carbone
  • le symbole A' représente -O-P(=O)-O-

Groups bearing equal positive and negative charges have one or more betaine functions which can be represented, in the case of the cations of the nitrogen family , by the formulas (I) to (V) having a cationic charge in the center of the function and an anionic charge at the end of the function and of formula (VI) having an anionic charge at the center of the function and a cationic charge at the end of the function, as follows:

-N ⁽⁺⁾ (R ¹ ) (R ² ) -RAO ^(-) (I)

- (R ³ ) C = N ⁽⁺⁾ (R ⁴ ) -RAO ^(-) (II)

- (R ³ ) (R) CN ⁽⁺⁾ (R ⁴ ) (R ⁵ ) -RAO ^(-) (III)

-N ⁽⁺⁾ (= R ⁶ ) -RAO ^(-) (IV)

-N ⁽⁺⁾ (R ¹ ) (R ² ) -RW ^(-) (V)

-R-A '(- O ^(-) -RN ⁽⁺⁾ (R ¹ ) (R ² ) (R ⁷ ) (VI)

• 
  formulas (I) to (IV) in which,
  • the symbols R ¹ , R ² and R ⁵ , which are identical or different, represent an alkyl radical containing from 1 to 7 carbon atoms, preferably from 1 to 2 carbon atoms
  • the symbols R ³ and R ⁴ represent hydrocarbon radicals forming, with the nitrogen atom, a nitrogenous heterocycle possibly comprising one or more other heteroatoms, in particular nitrogen
  • the symbol R ⁶ represents a hydrocarbon radical forming with the nitrogen atom a saturated or unsaturated nitrogenous heterocycle optionally comprising one or more other heteroatoms, in particular nitrogen
  • the symbol R represents a linear or branched alkylene radical comprising from 1 to 15 carbon atoms, preferably from 2 to 4 carbon atoms, optionally substituted by one or more hydroxyl groups, or a benzylene radical;
  • the symbol A represents S (= O) (= O), OP (= O) (= O), OP (= O) (OR '), P (= O) (OR') or P (= O) ( R '), where R' represents an alkyl radical containing from 1 to 7 carbon atoms or a phenyl radical
• 
  formula (V) in which
  • the symbols R ¹ , R ² and R have the definition given above
  • the symbol W represents an ethenolate function of formula
    
    OC (O ^(-) = C (C≡N) ₂
    
    OC (O) -C ^(-) (C≡N) ₂
    
    OC (O) -C (-C = N) (= C = N ^(-) )
    
    
• 
  formula (VI) in which,
  • the symbols R ¹ and R ² , have the definition given above
  • the symbol R ⁷ , which is similar to or different from R ¹ or R ² , represents an alkyl radical containing from 1 to 7 carbon atoms, preferably from 1 to 2 carbon atoms
  • the symbol A 'represents -OP (= O) -O-

• 
  formule (VII) dans laquelle les symboles R¹ , R² , R et A ont la définition donnée ci-dessus
• 
  formule (VIII) dans laquelle
  • les symboles R¹ , R², R⁷ et R ont la définition donnée ci-dessus
  • le symbole A' représente -O-P(=O)-O-

In the case of cations of the phosphorus family , betaine functions of formulas (VII) and (VIII) may be mentioned

-P ⁽⁺⁾ (R ¹ ) (R ² ) -RAO ^(-) (VII)

-R-A '(- O ^(-)) -RP ⁽⁺⁾ (R ¹⁾ (R ²⁾ (R ⁷⁾ (VIII)

• 
  formula (VII) in which the symbols R ¹ , R ² , R and A have the definition given above
• 
  formula (VIII) in which
  • the symbols R ¹ , R ² , R ⁷ and R have the definition given above
  • the symbol A 'represents -OP (= O) -O-

• 
  formule (IX) dans laquelle les symboles R¹ , R et A ont la définition donnée ci-dessus
• 
  formule (X) dans laquelle
  • les symboles R¹, R² et R ont la définition donnée ci-dessus
  • le symbole A' représente -O-P(=O)-O-

In the case of cations of the sulfur family , mention may be made of the betaine functions of formulas (IX) and (X)

-S ⁽⁺⁾ (R ¹ ) -RAO ^(-) (IX)

-R-A '(- O ^(-) -RS ⁽⁺⁾ (R ¹ ) (R ² ) (X)

• 
  formula (IX) in which the symbols R ¹ , R and A have the definition given above
• 
  formula (X) in which
  • the symbols R ¹ , R ² and R have the definition given above
  • the symbol A 'represents -OP (= O) -O-

The betaine functions can be connected to the carbon atoms of the hydrocarbon chain (also called the backbone) of the polybetaine (B) via, in particular, a divalent or polyvalent hydrocarbon-based unit (for example alkylene or arylene) optionally interrupted by one or several heteroatoms, oxygen in particular, an ester unit, an amide unit, or by a valence bond.

Preferably, the hydrocarbon chain (or backbone) of polybetaine (B) is a polyalkylene chain (linear or branched) optionally interrupted by one or more heteroatoms of nitrogen and / or sulfur.

The polybetaine (B) according to the invention may be a homopolymer formed of similar betaine units, or a copolymer formed of betaine units, at least two of which are different.

Said polybetaine (B) may further contain at least one nonionic or nonionic unit at the pH of the composition or at the pH of use of the composition comprising polybetaine (B), and / or at least one anionic unit or potentially anionic at the pH of the composition or at the pH of use of the composition comprising polybetaine (B). These units may be hydrophilic or hydrophobic.

Non-ionic, non-ionogenic, anionic or potentially anionic units are limited in number to keep said polybetaine (B) its main characteristic of zwitterion.

Polybetaine (B) contains less than 50% of its weight or more precisely less than 70 mol% of nonionic, nonionic, anionic or potentially anionic units; very preferably polybetaine (B) may contain less than 50 mol%, and more particularly less than 30 mol% of nonionic, nonionic, anionic or potentially anionic units.

Among the nonionic units that may be present, those derived from ethylenically unsaturated nonionic monomers such as acrylamide, vinyl acetate (capable of forming, by hydrolysis, vinyl alcohol units), the C ₁ -C ₄ alkyl esters of acrylic acid and of methacrylic acid, the hydroxyalkyl esters of C ₁ -C ₄ acrylic acid and methacrylic acid, including acrylate and methacrylate ethylene glycol and propylene glycol, polyalkoxylated esters of acrylic acid and methacrylic acid, including polyethylene glycol and polypropylene glycol esters ....

• des monomères possédant au moins une fonction carboxylique, comme les acides carboxyliques α-β éthyléniquement insaturés ou les anhydrides correspondants, tels que les acides ou anhydrides acrylique, méthacrylique, maleique, l'acide fumarique, l'acide itaconique, le N-méthacroyl alanine, le N-acryloylglycine et leurs sels hydrosolubles
• des monomères précurseurs de fonctions carboxylates, comme l'acrylate de tertiobutyle, qui engendrent, après polymérisation, des fonctions carboxyliques par hydrolyse.

Among the nonionic units with a pH of less than or equal to 3, or potentially anionic at a higher pH, those derived from ethylenically unsaturated monomers such as

• monomers having at least one carboxylic function, such as α-β ethylenically unsaturated carboxylic acids or corresponding anhydrides, such as acrylic, methacrylic, maleic, fumaric acid, itaconic acid or N-methacroyl alanine acids or anhydrides; N-acryloylglycine and their water-soluble salts
• monomers precursors of carboxylate functions, such as tert-butyl acrylate, which generate, after polymerization, carboxylic functions by hydrolysis.

• les N,N(dialkylaminowalkyl)amides d'acides carboxyliques α-β monoéthyléniquement insaturés comme le N,N-diméthylaminométhyl -acrylamide ou -méthacrylamide, le 2(N,N-diméthylamino)éthyl-acrylamide ou -méthacrylamide, le 3(N,N-diméthylamino)propyl-acrylamide ou -méthacrylamide, le 4(N,N-diméthylamino)butyl-acrylamide ou -méthacrylamide
• les aminoesters α-β monoéthyléniquement insaturés comme le 2(diméthyl amino)éthylméthacrylate (DMAM), le 3(diméthyl amino)propylméthacrylate, le 2(tertiobutylamino)éthylméthacrylate, le 2(dipentylamino)éthylméthacrylate, le 2(diéthylamino)éthylméthacrylate
• 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.

Among the nonionic units with a pH greater than or equal to 9, mention may be made of those derived from ethylenically unsaturated monomers such as

• the N, N (dialkylaminowalkyl) amides of α-β monoethylenically unsaturated carboxylic acids such as N, N-dimethylaminomethyl-acrylamide or methacrylamide, 2 (N, N-dimethylamino) ethyl-acrylamide or methacrylamide, 3 (N N, N-dimethylamino) propyl-acrylamide or methacrylamide, 4 (N, N-dimethylamino) butyl-acrylamide or -methacrylamide
• α-β monoethylenically unsaturated amino esters, such as 2 (dimethylamino) ethylmethacrylate (DMAM), 3 (dimethylamino) propylmethacrylate, 2 (tert-butylamino) ethylmethacrylate, 2 (dipentylamino) ethylmethacrylate, 2 (diethylamino) ethylmethacrylate,
• monomers precursors of amine functions such as N-vinyl formamide, N-vinyl acetamide, ... which generate primary amine functions by simple acid or basic hydrolysis.

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

Among the anionic units (whose first pKa is less than 3), 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
• monomers having at least one phosphonate or phosphate function, such as vinylphosphonic acid, esters of ethylenically unsaturated phosphates such as phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 from Rhodia) and those derived from polyoxyalkylene methacrylates and their water-soluble salts.

Preferably, the polybetaine (B) contains no monomeric units other than betaines carrying as much anionic charge (s) as permanent cationic charge (s) at a pH ranging from from 1 to 14. If other units are present, they are rather potentially anionic units, in an amount of less than 50 mol%, preferably less than 30 mol%.

• un ou plusieurs radicaux hydrocarbonés mono- ou poly-éthyléniquement insaturés (notamment vinyle, allyle, styrényle ...)
• un ou plusieurs radicaux esters mono- ou poly-éthyléniquement insaturés (notamment acrylate, méthacrylate, maléate ...)
• un ou plusieurs radicaux amides mono- ou poly-éthyléniquement insaturés (notamment acrylamido, méthacrylamido ...)

Said polybetaine (B) can in particular be obtained by radical polymerization or copolymerization in aqueous solution of ethylenically unsaturated betaine monomers, especially ethylenically unsaturated monomers bearing at least one betaine function of formula (I) to (X) above, and optionally ethylenically unsaturated monomers other.
Said monomers may have, by way of example:

• one or more mono- or poly-ethylenically unsaturated hydrocarbon radicals (in particular vinyl, allyl, styrenyl, etc.)
• one or more mono- or poly-ethylenically unsaturated ester radicals (in particular acrylate, methacrylate, maleate, etc.)
• one or more mono- or poly-ethylenically unsaturated amide radicals (in particular acrylamido, methacrylamido, etc.)

• les alkyl ou hydroxyalkyl sulfonates ou phosphonates de dialkylammonium alkyl acrylates ou méthacrylates, acrylamido ou méthacrylamido, comme :
  • 
    le sulfopropyl diméthyl ammonium éthyl méthacrylate, commercialisé par RASCHIG sous le nom SPE :
    
    • 
      le sulfoéthyl diméthyl ammonium éthyl méthacrylate et le sulfobutyl diméthyl ammonium éthyl méthacrylate :
      
      dont la synthèse est décrite dans l'article « Sulfobetaine Zwitterionomers based on n-butyl acrylate and 2-Ethoxyethyl acrylate : monomer synthesis and copolymerization behavior », Journal of Polymer Science 40, 511-523 (2002 ).
    • 
      le sulfohydroxypropyl diméthyl ammonium éthyl méthacrylate
      
    • 
      le sulfopropyl diméthylammonium propyl acrylamide :
      
      dont la synthèse est décrite dans l'article " Synthesis and solubility of the poly(sulfobetaine)s and the corresponding cationic polymers: 1. Synthesis and characterization of sulfobetaines and the corresponding cationic monomers by nuclear magnetic resonance spectra", Wen-Fu Lee and Chan-Chang Tsai, Polymer, 35 (10), 2210-2217 (1994 ).
  • 
    le sulfopropyl diméthylammonium propyl méthacrylamide, commercialisé par RASCHIG sous le nom SPP :
    
  • 
    le sulfohydroxypropyl diméthylammonium propyl méthacrylamide,
    
  • 
    le sulfopropyl diéthyl ammonium éthyl méthacrylate :
    
    dont la synthèse est décrite dans l'article « Poly(sulphopropylbetaines) : 1. Synthesis and characterization », V. M. Monroy Soto and J. C. Galin, Polymer, 1984, Vol 25, 121-128 .
• les monomères bétaïnes hétérocycliques , comme :
  • 
    les sulfobétaines dérivées de la pipérazine :
    
    
    dont la synthèse est décrite dans l'article «Hydrophobically Modified Zwitterionic Polymers : Synthesis, Bulk Properties, and Miscibility with Inorganic Salts », P. Koberle and A. Laschewsky, Macromolecules 27, 2165-2173 (1994 )
  • 
    les sulfobétaines dérivées des 2-vinylpyridine et 4-vinylpyridine, comme la 2-vinyl (3-sulfopropyl) pyridinium bétaïne (2SPV), commercialisée par RASCHIG sous le nom SPV,
    
    et la 4-vinyl (3-sulfopropyl) pyridinium bétaïne (4SPV) dont la synthèse est décrite dans l'article «Evidence of ionic aggregates in some ampholytic polymers by transmission electron microscopy», V. M. Castaño and A. E. González, J. Cardoso, O. Manero and V. M. Monroy, J. Mater. Res., 5 (3), 654-657 (1990 ) :
    
  • 
    la 1-vinyl-3-(3-sulfopropyl) imidazolium bétaïne :
    
    dont la synthèse est décrite dans l'article " Aqueous solution properties of a poly(vinyl imidazolium sulphobetaine)", J. C. Salamone, W. Volkson, A.P. Oison, S.C. Israel, Polymer, 19, 1157-1162 (1978 )
• les alkyl ou hydroxyalkyl sulfonates ou phosphonates de dialkylammonium alkyl allyliques, comme la sulfopropyl méthyl diallyl ammonium bétaine :
  
  dont la synthèse est décrite dans l'article «New poly(carbobetaine)s made from zwitterionic diallylammonium monomers », Favresse, Philippe ; Laschewsky, Andre , Macromolecular Chemistry and Physics , 200(4), 887-895 (1999 ).
• les alkyl ou hydroxyalkyl sulfonates ou phosphonates de dialkylammonium alkyl styréniques, comme :
  
  dont la synthèse est décrite dans l'article «Hydrophobically Modified Zwitterionic Polymers : Synthesis, Bulk Properties, and Miscibility with Inorganic Salts », P. Koberle and A. Laschewsky, Macromolecules 27, 2165-2173 (1994 ).
• les bétaïnes issues de diènes et d'anhydrides éthyléniquement insaturés comme :
  
  dont la synthèse est décrite dans l'article «Hydrophobically Modified Zwitterionic Polymers : Synthesis, Bulk Properties, and Miscibility with Inorganic Salts », P. Koberle and A. Laschewsky, Macromolecules 27, 2165-2173 (1994 )
• les phosphobétaines, comme :
  
  ou encore :
  
  La synthèse du MPC et du VPC est décrite dans EP 810 239 B1 (Biocompatibles, Alister et al.)
• les bétaines issues d'acétals cycliques, comme le ((dicyanoéthanolate)éthoxy)diméthylammoniumpropylméthacrylamide :
  
  dont la synthèse décrite par M-L. Pujol-Fortin et al dans l'article «Poly(ammonium alkoxydicyanatoethenolates) as new hydrophobic and highly dipolar poly(zwitterions). 1. Synthesis», Macromolecules 24, 4523-4530 (1991 ).

By way of example, mention may be made of polybetaines derived from the following betaine monomers:

• alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl acrylates or methacrylates, acrylamido or methacrylamido, such as:
  • 
    sulfopropyl dimethyl ammonium ethyl methacrylate, marketed by RASCHIG under the name SPE:
    
    • 
      sulfoethyl dimethyl ammonium ethyl methacrylate and sulfobutyl dimethyl ammonium ethyl methacrylate:
      
      whose synthesis is described in the article "Sulfobetaine Zwitterionomers based on n-butyl acrylate and 2-Ethoxyethyl acrylate: monomer synthesis and copolymerization behavior", Journal of Polymer Science 40, 511-523 (2002) ).
    • 
      sulfohydroxypropyl dimethyl ammonium ethyl methacrylate
      
    • 
      sulfopropyl dimethylammonium propyl acrylamide:
      
      whose synthesis is described in the article " Synthesis and solubility of the poly (sulfobetaine) s and the corresponding cationic polymers: 1. Synthesis and characterization of sulfobetaines and the corresponding cationic monomers by nuclear magnetic resonance spectra ", Wen-Fu Lee and Chan-Chang Tsai, Polymer, (10) ), 2210-2217 (1994) ).
  • 
    sulfopropyl dimethylammonium propyl methacrylamide, marketed by RASCHIG under the name SPP:
    
  • 
    sulfohydroxypropyl dimethylammonium propyl methacrylamide,
    
  • 
    sulfopropyl diethyl ammonium ethyl methacrylate:
    
    whose synthesis is described in the article Poly (sulphopropylbetaines): 1. Synthesis and Characterization, VM Monroy Soto and JC Galin, Polymer, 1984, Vol 25, 121-128 .
• heterocyclic betaine monomers, such as:
  • 
    sulphobetaines derived from piperazine:
    
    
    whose synthesis is described in the article "Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts", P. Koberle and A. Laschewsky, Macromolecules 27, 2165-2173 (1994). )
  • 
    sulphobetaines derived from 2-vinylpyridine and 4-vinylpyridine, such as 2-vinyl (3-sulphopropyl) pyridinium betaine (2SPV), marketed by RASCHIG under the name SPV,
    
    and 4-vinyl (3-sulfopropyl) pyridinium betaine (4SPV), the synthesis of which is described in the article Evidence of ionic aggregates in some ampholytic polymers by electron microscopy transmission, VM Castaño and AE Gonzalez, J. Cardoso, O. Manero and VM Monroy, J. Mater. Res., 5 (3), 654-657 (1990) ):
    
  • 
    1-vinyl-3- (3-sulfopropyl) imidazolium betaine:
    
    whose synthesis is described in the article " Aqueous solution properties of a polyvinyl imidazolium sulphobetaine, JC Salamone, W. Volkson, PA Oison, SC Israel, Polymer, 19, 1157-1162 (1978) )
• allylic alkyl dialkylammonium alkyl or hydroxyalkyl sulphonates or phosphonates, such as sulphopropyl methyl diallyl ammonium betaine:
  
  whose synthesis is described in the article "New poly (carbobetaine) made from zwitterionic diallylammonium monomers", Favresse, Philippe; Laschewsky, Andre, Macromolecular Chemistry and Physics, 200 (4), 887-895 (1999). ).
• styrenic alkyl dialkylammonium alkyl or hydroxyalkyl sulfonates or phosphonates, such as:
  
  whose synthesis is described in the article "Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts", P. Koberle and A. Laschewsky, Macromolecules 27, 2165-2173 (1994). ).
• betaines derived from dienes and ethylenically unsaturated anhydrides such as:
  
  whose synthesis is described in the article "Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts", P. Koberle and A. Laschewsky, Macromolecules 27, 2165-2173 (1994). )
• Phosphobetaines, such as:
  
  or :
  
  The synthesis of MPC and VPC is described in EP 810 239 B1 (Biocompatible, Alister et al.)
• betaines derived from cyclic acetals, such as ((dicyanoethanolate) ethoxy) dimethylammoniumpropylmethacrylamide:
  
  whose synthesis described by ML. Pujol-Fortin et al in the article "Poly (ammonium alkoxydicyanatoethenolates) as new hydrophobic and highly dipolar poly (zwitterions). 1. Synthesis, Macromolecules 24, 4523-4530 (1991) ).

Said polybetaine (B) according to the invention can also be obtained in known manner by chemical modification of a so-called precursor polymer polymer. Thus a polysulfobetaine can be obtained by chemical modification, using a sultone (propanesultone, butanesultone), a halogenoalkylsulfonate or any other sulfonated electrophilic compound, a polymer with pendant amine functions.

Some examples of synthesis are given below:

• • " Synthesis and aqueous solution behaviour of copolymers containing sulfobetaine moieties in side chains", I.V. Berlinova, I.V. Dimitrov, R.G. Kalinova, N.G. Vladimirov, Polymer 41, 831-837 (2000 )
• • " Poly(sulfobetaine)s and corresponding cationic polymers: 3. Synthesis and dilute aqueous solution properties of poly(sulfobetaine)s derived from styrene-maleic anhydride)", Wen-Fu Lee and Chun-Hsiung Lee, Polymer 38 (4), 971-979 (1997 )
• • " Poly(sulfobetaine)s and corresponding cationic polymers. VIII. Synthesis and aqueous solution properties of a cationic poly(methyl iodide quaternized styrene-N,N-dimethylaminopropyl maleamidic acid) copolymer", Lee, Wen-Fu; Chen, Yan-Ming, Journal of Applied Polymer Science 80, 1619-1626 (2001 )
• • " Synthesis of polybetaines with narrow molecular mass distribution and controlled architecture", Andrew B. Lowe, Norman C. Billingham and Steven P. Armes, Chern. Commun., 1555-1556 (1996 )
• • " Synthesis and Properties of Low- Polydispersity Poly(sulfopropylbetaine)s and Their Block Copolymers", Andrew B. Lowe, Norman C. Billingham, and Steven P. Armes, Macromolecules 32, 2141-2146 (1999 )
• • demande de brevet japonais publiée le 21 décembre 1999, sous le numéro 11-349826 .

The principal routes of access to polysulfobetaines by chemical modification of the precursor polymer by sultones and halogenoalkylsufonates are described in particular in the following documents:

• • " Synthesis and aqueous solution behavior of copolymers containing sulfobetaine moieties in side chains ", IV Berlinova, IV Dimitrov, RG Kalinova, NG Vladimirov, Polymer 41, 831-837 (2000) )
• • " Poly (sulfobetaine) s and corresponding cationic polymers: 3. Synthes and dilute aqueous solution properties of poly (sulfobetaines) derived from styrene-maleic anhydride), Wen-Fu Lee and Chun-Hsiung Lee, Polymer 38 (4), 971 -979 (1997) )
• • " Poly (sulfobetaine) s and corresponding cationic polymers. VIII. Synthesis and aqueous solution properties of a cationic poly (methyl iodide quaternized styrene-N, N-dimethylaminopropyl maleamidic acid) copolymer, Lee, Wen-Fu, Chen, Yan-Ming, Journal of Applied Polymer Science 80, 1619-1626 (2001) )
• • " Andrew B. Lowe, Norman C. Billingham, Steven P. Armes, Chern., Commun. )
• • " Synthesis and Properties of Low-Polydispersity Poly (Sulfopropylbetaine) and Their Block Copolymers, Andrew B. Lowe, Norman C. Billingham, and Steven P. Weapons, Macromolecules 32, 2141-2146 (1999) )
• • Japanese patent application published on December 21, 1999, under the number 11-349826 .

The preparation of polyphosphonato- and phosphinatobetaines by chemical modification is reported in "New polymeric phosphonato, phosphinato and carboxybetaines", T. Hamaide, Makromolecular Chemistry 187, 1097-1107 (1986). ).

Preferably, the polybetaine B is chosen from alkylsulfonates or hydroxyalkylsulfonates of dialkylammonium alkyl methacrylates or methacrylamides and sulphobetaines derived from a vinylpyridine. Even more preferably, it is alkylsulfonates or hydroxyalkylsulfonates of dialkylammonium methacrylamides.

• les homopolymères formés d'unités bétaïnes choisies parmi celles de formules (-SPE-), (-SPP-), (-SHPE-) et (-SHPP-) suivantes
  
  
  
  
• les homopolymères de sulfobétaïne dérivée de 2-vinylpyridine de formule
  
• les copolymères formés d'unités bétaïnes dont deux au moins sont différentes et choisies parmi celles de formules (-SPE-), (-SPP-), (SHPE-) et (SHPP) ci-dessus
• les copolymères formés d'unités bétaïnes semblables ou différentes choisies parmi celles de formules (-SPE-), (-SPP-), (-SHPE-) et (-SHPP-) ci-dessus et d'unités acide méthacrylique, la quantité d'unités acide méthacrylique représentant moins de 50% molaire, de préférence moins de 30% molaire desdits copolymères.

Thus, in a preferred manner, polybetaine B is chosen from:

• homopolymers formed from betaine units chosen from those of formulas (-SPE-), (-SPP-), (-SHPE-) and (-SHPP-) following
  
  
  
  
• sulfobetaine homopolymers derived from 2-vinylpyridine of formula
  
• copolymers formed from betaine units of which at least two are different and chosen from those of formulas (-SPE-), (-SPP-), (SHPE-) and (SHPP) above
• copolymers formed from similar or different betaine units chosen from those of formulas (-SPE-), (-SPP-), (-SHPE-) and (-SHPP-) above and from methacrylic acid units, the amount of methacrylic acid units representing less than 50 mol%, preferably less than 30 mol% of said copolymers.

Most preferably, the homopolymers or copolymers comprising betaine units chosen from those of formulas (-SPE-), (-SPP-), (-SHPE-) and (-SHPP-) have an average molar mass in absolute mass (M _w ) ranging from 10,000 to 150,000 g / mol.

The cleaning or rinsing composition according to the invention also comprises at least one surfactant. This may be nonionic, anionic, amphoteric, zwitterionic or cationic.

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

Among the anionic surfactants , there may be mentioned by way of example:

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

A description of nonionic surfactants is given in US Patent 4,287,080 and US Patent 4,470,923 . Alkylene oxide condensates, in particular ethylene oxide and optionally propylene condensates with alcohols, polyols, alkylphenols and acid esters, may be mentioned in particular. fatty acids, fatty acid amides and fatty amines; amine oxides, sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, especially sucrose monopalmitate; long-chain tertiary phosphine oxides (8 to 28 carbon atoms); dialkyl sulfoxides; block copolymers of polyoxyethylene and polyoxypropylene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly (ethylene oxide) and fatty acid amides modified to give them a hydrophobic character (for example, mono- and diethanolamides of fatty acids containing from 10 to 18 carbon atoms ).

• les acides carboxyliques aliphatiques en C₈-C₁₈ polyoxyalkylénés contenant de 2 à 50 motifs oxyalkylènes (oxyéthylène et/ou oxypropylène), en particulier ceux en C₁₂ (moyenne) ou en C₁₈ (moyenne)
• les alcools aliphatiques en C₆-C₂₄ polyoxyalkylénés contenant de 2 à 50 motifs oxyalkylènes (oxyéthylène et/ou oxypropylène), en particulier ceux en C₁₂ (moyenne) ou en C₁₈ (moyenne) ; on peut mentionner les Antarox B12DF , Antarox FM33 , Antarox FM63 , Antarox V74 de Rhodia, Plurafac LF 400 , Plurafac LF 220 de BASF, Rhodasurf ID 060 , Rhodasurf ID 070, Rhodasurf LA 42 de Rhodia, Synperonic A5, A7, A9 de ICI
• les amine oxydes comme le dodécyl di(2-hydroxyéthyl)amine oxyde
• les phosphine oxydes, comme le tetradécyl diméthyl phosphine oxyde

We can mention everything especially

• polyoxyalkylenated C ₈ -C ₁₈ aliphatic carboxylic acids containing from 2 to 50 oxyalkylene units (oxyethylene and / or oxypropylene), in particular those containing C ₁₂ (average) or C ₁₈ (average)
• polyoxyalkylenated C ₆ -C ₂₄ aliphatic alcohols containing from 2 to 50 oxyalkylene units (oxyethylene and / or oxypropylene), in particular those containing C ₁₂ (average) or C ₁₈ (average); we can mention Antarox B12DF, Antarox FM33, Antarox FM63, Rhodia Antarox V74, Plurafac LF 400, Plurafac LF 220 from BASF, Rhodasurf ID 060, Rhodasurf ID 070, Rhodasurf LA 42 from Rhodia, Synperonic A5, A7, A9 from ICI
• amine oxides such as dodecyl di (2-hydroxyethyl) amine oxide
• phosphine oxides, such as tetradecyl dimethyl phosphine oxide

• les alkyl iminopropionates ou iminodipropionates de sodium, comme les Mirataine H2C HA et Mirataine JC HA de Rhodia.
• les alkylamphoacétates ou alkylamphodiacétates dont le groupe alkyle contient de 6 à 20 atomes de carbone, comme le Miranol C2M Conc NP commercialisé par RHODIA
• les dérivés amphotères des alkylpolyamines comme l'AMPHIONIC XL^® commercialisé par RHODIA, AMPHOLAC 7T/X^® et AMPHOLAC 7C/X^® commercialisés par BEROL NOBEL.

Among the amphoteric surfactants , mention may be made of

• sodium alkyl iminopropionates or iminodipropionates, such as Mirataine H2C HA and Mirataine JC HA from Rhodia.
• alkylamphoacetates or alkylamphodiacetates whose alkyl group contains from 6 to 20 carbon atoms, such as Miranol C2M Conc NP marketed by RHODIA
• amphoteric derivatives of alkylpolyamines such as Amphionic XL ^® marketed by Rhodia, Ampholac 7T / X ^® and Ampholac 7C / X ^® sold by Berol Nobel.

Among the zwitterionic surfactants, mention may be made of those described in US 5,108,660 ,
The preferred zwitterionic surfactants are alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyldimethylsulphobetaines or alkylamidopropyldimethylsulfobetaines, such as Mirataine JCHA or H2CHA, and Mirataine CBS sold by Rhodia, or those of the same type marketed by Sherex Company under the name "Varion CADG Betaine". "and "Varion CAS Sulfobetaine", the condensation products of fatty acids and protein hydrolysates.

Other zwitterionic surfactants are also described in US Patent 4,287,080 , and in US-A-4,557,853 .

• R¹, R² et R³, semblables ou différents, représentent H ou un groupe alkyle contenant moins de 4 atomes de carbone, de préférence 1 ou 2 atome(s) de carbone, éventuellement substitué par une plusieurs fonction(s) hydroxyle(s), ou peuvent former ensemble avec l'atome d'azote N⁺ au moins un cycle aromatique ou hétérocyclique
• R⁴ représente un groupe alkyle ou alkényle en C₈-C₂₂, de préférence en C₁₂-C₂₂, un groupe aryle ou benzyle, et
• X^- est un anion solubilisant tel que halogénure (par exemple chlorure, bromure, iodure), sulfate ou alkylsulfate (méthylsulfate), carboxylate (acétate, propionate, benzoate), alkyl ou arylsulfonate.

Among the cationic surfactants , mention may in particular be made of quaternary ammonium salts of formula

R ¹ R ² R ³ R ⁴ N ⁺ X ^-

or

• R ¹ , R ² and R ³ , which are identical or different, represent H or an alkyl group containing less than 4 carbon atoms, preferably 1 or 2 carbon atoms, optionally substituted by one or more hydroxyl functional groups ( s), or together with the nitrogen atom N ⁺ may form at least one aromatic or heterocyclic ring
• R ⁴ represents a C ₈ -C ₂₂ alkyl or alkenyl group, preferably C ₁₂ -C ₂₂ , an aryl or benzyl group, and
• X ^- is a solubilizing anion such as halide (for example chloride, bromide, iodide), sulphate or alkyl sulphate (methyl sulphate), carboxylate (acetate, propionate, benzoate), alkyl or aryl sulphonate.

There may be mentioned in particular bromides of dodecyltrimethylammonium, tetradecyltrimethylammonium, cetyltrimethylammonium, stearyl pyridinium chloride, RHODAQUAT ® TFR and RHODAMINE ® C15 marketed by RHODIA, cetyltrimethylammonium chloride (Dehyquart ACA and / or AOR from Cognis), cocobis (2-hydroxyethyl) ethylammonium chloride (Ethoquad C12 from Akso Nobel).

• les sels d'ammonium quaternaires de formule
  
          R^1' R^2' R^3' R^4' N⁺ X^-
  
  où
  • R^1' et R^2', semblables ou différents, représentent H ou un groupe alkyle contenant moins de 4 atomes de carbone, de préférence 1 ou 2 atome(s) de carbone, éventuellement substitué par une plusieurs fonction(s) hydroxyle(s), ou peuvent former ensemble avec l'atome d'azote N⁺ un cycle hétérocyclique
  • R^3' et R^4' représentent un groupe alkyle ou alkényle en C₈-C₂₂, de préférence en C₁₀-C₂₂, un groupe aryle ou benzyle, et
  • X^- est un anion tel que halogénure (par exemple chlorure, bromure, iodure), sulfate ou alkylsulfate (méthylsulfate), carboxylate (acétate, propionate, benzoate), alkyl ou arylsulfonate.

Other cationic surfactants, such as:

• quaternary ammonium salts of formula
  
  R ^{1 '} R ^2' R ^{3 '} R ^4' N ⁺ X ^-
  
  or
  • R ^{1 '} and R ^2' , which are similar or different, represent H or an alkyl group containing less than 4 carbon atoms, preferably 1 or 2 carbon atoms, optionally substituted with one or more hydroxyl functional groups (s) ), or can form together with the nitrogen atom N ⁺ a heterocyclic ring
  • R ^{3 '} and R ^4' represent a C ₈ -C ₂₂ , preferably C ₁₀ -C ₂₂ , alkyl or alkenyl group, an aryl or benzyl group, and
  • X ^- is an anion such as halide (for example chloride, bromide, iodide), sulphate or alkyl sulphate (methyl sulphate), carboxylate (acetate, propionate, benzoate), alkyl or aryl sulphonate.

• les sels de C₁₀-C₂₅alkylimidazolium comme les méthylsulfates de C₁₀-C₂₅alkylimidazolinium
• les sels de polyamines substituées comme le N-tallow-N,N',N',tri-éthanol-1,3-propylènediamine dichlorure ou diméthylsulfate, N-tallow-N,N,N',N',N'-pentaméthyl-1,3-propylène diamine dichlorure.

In particular, mention may be made of: dialkyldimethylammonium chlorides, such as ditallow dimethylammonium chloride or methylsulphate, etc., alkylbenzyldimethylammonium chlorides.

• salts of C ₁₀ -C ₂₅ alkylimidazolium as the C ₁₀ -C ₂₅ alkyl imidazolinium methyl sulfates
• substituted polyamine salts such as N-tallow-N, N ', N', tri-ethanol-1,3-propylenediamine dichloride or dimethylsulfate, N-tallow-N, N, N ', N', N'-pentamethyl -1,3-propylene diamine dichloride.

Additional examples of suitable surfactants are compounds generally used as surfactants referred to in well-known textbooks. Surface Active Agents ", Volume 1 by Schwartz and Perry and Surface Active Agents and Detergents ", Volume II by Schwartz, Perry and Berch .

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

Advantageously, the weight ratio polybetaine (B) / agent (s) surfactant (s), is between 1/1 and .1 / 1000, preferably 1/2 and 1/200.

The cleaning or rinsing composition according to the invention may further comprise at least one other additive, especially chosen from the usual additives present in the cleaning or rinsing compositions for hard surfaces.

• ◆ des agents chélatants, notamment du type phosphonates organiques et aminophosphonates hydrosolubles tels que les
  • éthane 1-hydroxy-1, 1-diphosphonates,
  • aminotri(méthylène diphosphonate)
  • vinyldiphosphonates
  • sels des oligomères ou polymères de l'acide vinylphosphonique ou vinyldiphosphonique
  • sels de co-oligomères ou copolymères statistiques de l'acide vinylphosphonique ou vinyldiphosphonique et de l'acide acrylique et/ou de l'anhydride maleïque et/ou de l'acide vinylsulfonique et/ou de l'acrylamidométhylpropane sulfonique
  • sels d'acides polycarboxyliques phosphonés
  • polyacrylates à terminaison(s) phosphonate(s)
  • sels de cotélomères de l'acide vinylphosphonique ou vinyldiphosphonique et d'acide acrylique
  comme ceux de la gamme BRIQUESET^® ou MIRAPOL A300 ou 400 de RHODIA (à raison de 0 à 10 %, de préférence de 0 à 5% du poids total de composition nettoyante);
• ◆ des agents séquestrants ou antitartre comme
  • les acides polycarboxyliques ou leurs sels hydrosolubles et les sels hydrosolubles de polymères ou de copolymères carboxyliques tels que les
    • éthers polycarboxylates ou hydroxypolycarboxylates
    • acides polyacétiques ou leurs sels (acide nitriloacétique, acide N,N-dicarboxyméthyl-2-aminopentane dioïque, acide éthylènediamine tétraacétique, acide diéthylènetriamine pentaacétique, éthylènediaminetetraacétates, nitrilotriacétates, N-(2 hydroxyéthyl)-nitrilodiacétates),
    • sels d'acides alkyl C₅-C₂₀ succiniques
    • esters polyacétals carboxyliques
    • sels d'acides polyaspartiques ou polyglutamiques
    • acide citrique, acide adipique, acide gluconique ou acide tartrique ou leurs sels
  • des copolymères d'acide acrylique et d'anhydride maléïque ou des homopolymères d'acide acrylique, tels que le Rhodoline DP 226 35 de Rhodia et le Sokalan CP5 de BASF (à raison de 0 à 10 %, du poids total de ladite composition nettoyante) ;
  • des polyvinylstyrènes sulfonés ou leurs copolymères avec l'acide acrylique, méthacrylique ...
  (à raison de 0 à 10 %, du poids total de composition nettoyante);
• ◆ des "builders" (adjuvants de détergence améliorant les propriétés de surface des tensioactifs) minéraux du type :
  • polyphosphates de métaux alcalins, d'ammonium ou d'alcanolamines tels que le RHODIAPHOS HD7 commercialisé par la société RHODIA, (à raison de 0 à 70 % du poids total de composition nettoyante) ;
  • pyrophosphates de métaux alcalins
  • silicates de métaux alcalins, de rapport SiO₂/M₂O pouvant aller de 1 à 4, de préférence de 1,5 à 3,5, tout particulièrement de 1,7 à 2,8 ; il peut s'agir de silicates amorphes ou de silicates lamellaires comme les phases α-, β-, γ- et δ- de Na₂Si₂O₅, commercialisées sous les références NaSKS-5, NaSKS-7, NaSKS-11 et NaSKS-6 par CLARIANT ;
  • borates, carbonates, bicarbonates, sesquicarbonates alcalins ou alcalino-terreux (en quantité pouvant aller jusqu'à 50 % environ du poids total de ladite composition nettoyante);
  • cogranulés de silicates hydratés de métaux alcalins de rapport SiO₂/M₂O pouvant aller de 1,5 à 3,5, et de carbonates de métaux alcalins (sodium ou de potassium) ; on peut citer en particulier les cogranulés dans lesquels la teneur pondérale en eau associée au silicate par rapport au silicate sec est d'au moins 33/100, le rapport pondéral du silicate au carbonate pouvant aller de 5/95 à 45/55, de préférence de 15/85 à 35/65, tels que décrits dans EP-A-488 868 et EP-A-561 656 , comme le NABION 15 commercialisé par la société RHODIA ;
  (la quantité totale de "builders" pouvant représenter jusqu'à 90% du poids total de ladite composition nettoyante ou rinçante) ;
• ◆ des agents de blanchiment du type perborates, percarbonates associés ou non à des activateurs de blanchiment acétylés comme la N, N, N', N'-tétraacétyl-éthylènediamine (TAED) ou des produits chlorés du type chloroisocyanurates, ou des produits chlorés du type hypochlorites de métaux alcalins, ou de l'eau oxygénée (à raison de 0 à 30 % du poids total de ladite composition nettoyante)
• ◆ des charges du type sulfate de sodium, chlorure de sodium, carbonate de sodium ou de calcium, kaolin, silice, à raison de 0 à 50 % du poids total de ladite composition;
• ◆ des catalyseurs de blanchiment contenant un métal de transition, les complexes de fer, manganèse et cobalt notamment, comme ceux du type [Mn^IV ₂(µ-O)₃(Me₃TACN)₂](PF₆)₂, [Fe^II(MeN₄py)(MeCN)](ClO₄)₂, [(Co^III)(NH₃)₅(OAc)](OAc)₂, décrits dans US-A-4,728,455 , 5,114,606 , 5,280,117 , EP-A-909 809 , US-A-5,559,261 , WO 96/23859 , 96/23860 et 96/23861 (à raison de 0 à 5 % du poids total de ladite composition nettoyante)
• ◆ des agents influant sur le pH de la composition, solubles dans le milieu nettoyant ou rinçant, notamment
  • des additifs alcalinisants phosphates de métaux alcalins, carbonates, perborates, hydroxydes de métaux alcalins) ou
  • des additifs acidifiants éventuellement nettoyants comme les acides minéraux (acide phosphoriques, polyphosphoriques, sulfamique, chlorhydrique, fluorhydrique, sulfurique, nitrique, chromique), les acides carboxyliques ou polycarboxyliques (acide acétique, hydroxyacétique, adipique, citrique, formique, fumarique, gluconique, glutarique, glycolique, malique, maléique, lactique, malonique, oxalique, succinique et tartrique) ou des sels d'acides comme le bisulfate de sodium, bicarbonates et sesquicarbonates de métaux alcalins.
• ◆ des polymères utilisés pour contrôler la viscosité du mélange et/ou la stabilité des mousses formées à l'utilisation, comme les dérivés de cellulose ou de guar (carboxyméthylcellulose, hydroxyéthylcellulose, hydroxypropylguar, carboxy-méthylguar, carboxyméthylhydroxypropyl-guar...), la gomme xanthane, le succinoglycane (RHEOZAN^® commercialisé par RHODIA), la gomme caroube, les carragénanes (à raison de 0 à 2 % du poids total de ladite composition nettoyante)
• ◆ des agents hydrotropes, comme les alcools courts en C₂-C₈, en particulier l'éthanol, les diols et glycols comme le diéthylène glycol, dipropylène-glycol, le xylène sulfonate de sodium, le naptalène sulfonate de sodium (à raison de 0 à 10g pour 100g de ladite composition nettoyante)
• ◆ des agents hydratants ou humectants pour la peau comme le glycérol, l'urée ou des agents protecteurs de la peau, comme les protéines ou hydrolysats de protéines, les huiles végétales comme l'huile de soja, les polymères cationiques comme les dérivés cationiques du guar (JAGUAR C13S^®, JAGUAR C162^®, HICARE 1000^® commercialisés par la société RHODIA, (à raison de 0 à 40% du poids total de ladite composition nettoyante)
• ◆ des biocides ou désinfectants comme
  • les biocides cationiques, par exemple
    • * les sels de monoammonium quaternaire tels que
      • les chlorures de coco-alkyl benzyl diméthylammonium, de C₁₂-C₁₄ alkyl benzyl diméthylammonium, de coco-alkyl dichlorobenzyl diméthylammonium, de tetradecyl benzyl diméthylammonium, de didécyl diméthylammonium, de dioctyl diméthylammonium
      • les bromures de myristyl triméthylammonium, de cétyl triméthylammonium
    • * les sels d'amines hétérocycliques monoquaternaires tels que les chlorures de laurylpyridinium, de cétylpyridinium, de C₁₂-C₁₄ alkyl benzyl imidazolium
    • * les sels d'alkyl gras triphényl phosphonium comme le bromure de myristyl triphényl phosphonium
    • * les biocides polymères, comme ceux dérivés de la réaction
      • de l'épichlorhydrine et de la diméthylamine ou de la diéthylamine
      • de l'épichlorhydrine et de l'imidazole
      • du 1,3-dichoro-2-propanol et de la diméthylamine
      • du 1,3-dichoro-2-propanol et du 1,3-bis-diméthylamino-2-propanol
      • du dichlorure d'éthylène et du 1,3-bis-diméthylamino-2-propanol
      • du bis (2-chloroéthyl)ether et de la N,N'-bis(diméthylaminopropyl) urée ou thiourée
      • les chlorhydrates de polymère de biguanidine, comme le VANTOCIL IB
  • les biocides amphotères comme les dérivés de N-(N'-C₈-C₁₈alkyl-3-aminopropyl)-glycine, de N-(N'-(N"-C₈-C₁₈alkyl-2-aminoéthyl)-2-aminoéthyl)-glycine, de N,N-bis(N'-C₈-C₁₈alkyl-2-aminoéthyl)-glycine, tels que le (dodécyl) (aminopropyl) glycine, le (dodécyl) (diéthylènediamine) glycine
  • les amines comme la N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine
  • les biocides halogénés comme les iodophores et sels d'hypochlorites, tels que le dichloroisocyanurate de sodium
  • les biocides phénoliques comme le phénol, le résorcinol, les crésols, l'acide salicylique
  • les biocides hydrophobes comme
    • le parachlorométaxylenol, le dichlorométaxylenol
    • le 4-chloro-m-crésol
    • le résorcinol monoacétate
    • les mono- ou poly-alkyl ou aryl phénols, crésols ou résorcinols, comme l'o-phenyl-phénol, le p-tert-butyl-phénol, le 6-n-amyl-m-crésol,
    • les alkyl et/ou aryl chloro ou bromophénols, comme l'o-benzyl-p-chlorophénol
    • les diphényléthers halogénés, comme le 2',4,4'-trichloro-2-hydroxy-diphényl éther (triclosan), le 2,2'-dihydroxy-5,5'-dibromo-diphényl éther.
    • le chlorophénésine (éther p-chloro-phénylglycérique).
  à raison de 0 à 5% du poids total de ladite composition nettoyante.
• ◆ des solvants ayant une bonne activité nettoyante ou dégraissante, comme
  • les alkylbenzenes de type octyl benzene,
  • les oléfines ayant un point d'ébullition d'au moins 100°C, comme les alpha-olefines, preferentiellement le 1-decene or 1-dodecene
  • les éthers de glycol de formule générale, R1 O(R2O)mH où R1 est un groupe alkyle présentant de 3 à 8 carbones et chaque R2 est soit un ethylene ou propylene et m est un nombre qui varie de 1 à 3 ; on peut citer les monopropyleneglycol monopropyl ether, dipropyleneglycol monobutyl ether, monopropyleneglycol monobutyl ether, diethyleneglycol monohexyl ether, monoethyleneglycol monohexyl ether, monoethyleneglycol monobutyl ether et leurs mélanges.
  • les diols présentant de 6 à 16 atomes de carbone dans leur structure moléculaire ; les diols sont particulièrement intéressants car en plus de leur propriétés dégraissantes, ils peuvent aider à éliminer les sels de calcium (savons) ; les diols contenant de 8 à 12 atomes de carbone sont préférés, tout préférentiellement le 2,2,4-trimethyl-1,3-pentanediol.
  • d'autres solvants tels que l'huile de pin, les terpenes d'orange, l'alcool benzylique, le n-hexanol, les esters phatliques alcools possédant 1 à 4 atomes de carbone, le butoxy propanol, le Butyl Carbitol et le 1(2-n-butoxy-1-methylethoxy)propane-2-ol aussi appelé butoxy propoxy propanol ou dipropylene glycol monobutyl ether, le diglycol hexyl (Hexyl Carbitol), butyl triglycol, les diols comme le 2,2,4-trimethyl-1,3-pentanediol, et leurs mélanges.
  (à raison de 0 à 30% du poids total de ladite composition nettoyante)
• ◆ des nettoyants industriels comme les solutions de sels alcalins du type phosphates, carbonates, silicates ... de sodium, potassium, (à raison de 0 à 50% du poids total de ladite composition nettoyante)
• ◆ les solvants organiques hydrosolubles peu nettoyants comme le methanol, l'ethanol, l'isopropanol, l'ethylene glycol, le propylene glycol, et leur mélanges, (à raison de 0 à 40% du poids total de ladite composition nettoyante)
• ◆ des cosolvants comme la monoéthanolamide et/ou les béta-aminoalcanols, particulièrement intéressants dans les compositions de pH supérieur à 11, tout particulièrement supérieur à 11,7 , car ils aident à réduire la formation de films et de traces sur les surfaces dures (ils peuvent être mis en oeuvre à raison de 0,05 à 5% du poids de la composition nettoyante) ; des systèmes solvants comprenant de la monoéthanolamide et/ou des béta-aminoalcanols sont décrits dans US 5,108,660 .
• ◆ des agents antimousses comme les savons notamment. Les savons sont des sels alcalins d'acides gras, notamment les sels de sodium, potassium, ammonium et d'alcanol ammonium d'acides gras supérieurs contenant environ de 8 à 24 atomes de carbone, et de préférence d'environ 10 à environ 20 atomes de carbone ; on peut notamment citer les sels de mono-, di- et triéthanolamine de sodium et de potassium ou de mélanges d'acides gras dérivés de l'huile de coprah et d'huile de noix broyée. La quantité de savon peut être d'au moins 0,005 % en poids, de préférence de 0,5 % à 2 % en poids par rapport au poids total de la composition. Des exemples supplémentaires de matériaux de régulation de la mousse sont les solvants organiques, la silice hydrophobe, l'huile de silicone et les hydrocarbures.
• ◆ des abrasifs, comme la silice, le carbonate de calcium
• ◆ des additifs divers tels que des enzymes, des parfums, des colorants, des agents inhibiteurs de corrosion des métaux, des conservateurs, des brillanteurs optiques, des agents opacifiants ou perlescents ...

These include:

• ◆ chelating agents , especially of the organic phosphonate type and water-soluble aminophosphonates such as the
  • ethane 1-hydroxy-1,1-diphosphonates,
  • aminotri (methylene diphosphonate)
  • vinyldiphosphonates
  • salts of oligomers or polymers of vinylphosphonic acid or vinyldiphosphonic acid
  • random co-oligomer or copolymer salts of vinylphosphonic acid or vinyldiphosphonic acid and acrylic acid and / or maleic anhydride and / or vinylsulfonic acid and / or acrylamidomethylpropane sulfonic acid
  • salts of phosphonated polycarboxylic acids
  • Phosphonate-terminated polyacrylates
  • salts of cotellomers of vinylphosphonic acid or vinyldiphosphonic acid and acrylic acid
  as those of the range BRIQUESET ^® or MIRAPOL A300 or 400 of RHODIA (at a rate of 0 to 10%, preferably 0 to 5% of the total weight of cleaning composition);
• ◆ sequestering or anti-scaling agents
  • polycarboxylic acids or their water-soluble salts and the water-soluble salts of carboxylic polymers or copolymers such as
    • polycarboxylate ethers or hydroxypolycarboxylates
    • polyacetic acids or their salts (nitriloacetic acid, N, N-dicarboxymethyl-2-aminopentane dioic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetates, nitrilotriacetates, N- (2-hydroxyethyl) -nitrilodiacetates),
    • C ₅ -C ₂₀ alkyl succinic acid salts
    • polyacetal carboxylic esters
    • salts of polyaspartic or polyglutamic acids
    • citric acid, adipic acid, gluconic acid or tartaric acid or their salts
  • copolymers of acrylic acid and maleic anhydride or homopolymers of acrylic acid, such as Rhodoline DP 226 from Rhodia and Sokalan CP5 from BASF (from 0 to 10%, of the total weight of said cleaning composition );
  • sulfonated polyvinylstirenes or copolymers thereof with acrylic acid, methacrylic acid, etc.
  (at a rate of 0 to 10%, of the total weight of cleaning composition);
• ◆ "builders" (detergency adjuvants improving the surface properties of surfactants), of the type:
  • polyphosphates of alkali metals, of ammonium or of alkanolamines, such as RHODIAPHOS HD7 sold by RHODIA, (at a rate of 0 to 70% of the total weight of cleaning composition);
  • pyrophosphates of alkali metals
  • alkali metal silicates with an SiO ₂ / M ₂ O ratio of from 1 to 4, preferably from 1.5 to 3.5, most preferably from 1.7 to 2.8; they may be amorphous silicates or lamellar silicates, such as the α-, β-, γ- and δ- phases of Na ₂ Si ₂ O ₅ , sold under the references NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6 by CLARIANT;
  • alkali or alkaline earth borates, carbonates, bicarbonates, sesquicarbonates (in an amount of up to about 50% of the total weight of said cleaning composition);
  • cogranulates of alkali metal hydrated silicates of SiO ₂ / M ₂ O ratio ranging from 1.5 to 3.5, and of alkali metal carbonates (sodium or potassium); mention may in particular be made of cogranules in which the weight content of water associated with silicate relative to the dry silicate is at least 33/100, the weight ratio of silicate to carbonate ranging from 5/95 to 45/55, preferably from 15/85 to 35/65, as described in EP-A-488,868 and EP-A-561 656 like the NABION 15 marketed by RHODIA;
  (the total amount of "builders" may represent up to 90% of the total weight of said cleaning or rinsing composition);
• Perborate bleaching agents , percarbonates associated or not acetylated bleaching activators such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED) or chloroisocyanurate-type chlorinated products, or chlorinated products of the type hypochlorites of alkali metals, or hydrogen peroxide (at a rate of 0 to 30% of the total weight of said cleaning composition)
• ◆ fillers of the sodium sulphate, sodium chloride, sodium carbonate or calcium carbonate, kaolin, silica type, at from 0 to 50% of the total weight of said composition;
• Transition metal-containing bleach catalysts , especially iron, manganese and cobalt complexes, such as those of the type [Mn ^IV ₂ (μ-O) ₃ (Me ₃ TACN) ₂ ] (PF ₆ ) ₂ , [Fe ^II (MeN ₄ py) (MeCN)] (ClO ₄ ) ₂ , [(Co ^III ) (NH ₃ ) ₅ (OAc)] (OAc) ₂ , described in US Patent 4,728,455 , 5114606 , 5280117 , EP-A-909 809 , US Patent 5,559,261 , WO 96/23859 , 96/23860 and 96/23861 (at the rate of 0 to 5% of the total weight of said cleaning composition)
• Agents affecting the pH of the composition, which are soluble in the cleaning or rinsing medium, in particular
  • alkalizing additives phosphates of alkali metals, carbonates, perborates, alkali metal hydroxides) or
  • acidifying additives which may be cleansers such as mineral acids (phosphoric acid, polyphosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, chromic acid), carboxylic or polycarboxylic acids (acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid) glycolic, malic, maleic, lactic, malonic, oxalic, succinic and tartaric) or salts of acids such as sodium bisulfate, alkali metal bicarbonates and sesquicarbonates.
• Polymers used to control the viscosity of the mixture and / or the stability of foams formed during use, such as cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar, etc.), xanthan gum, succinoglycan (RHEOZAN ^® sold by Rhodia), locust bean gum, carrageenans (in a proportion of 0 to 2% of the total weight of said cleaning composition)
• Hydrotropic agents , such as short C ₂ -C ₈ alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol, sodium xylene sulphonate, sodium naptalene sulphonate (at the rate of 0 to 10 g per 100 g of said cleaning composition)
• Moisturizing or skin- moisturizing agents such as glycerol, urea or skin-protecting agents, such as proteins or protein hydrolysates, vegetable oils such as soybean oil, cationic polymers such as cationic derivatives of the skin, guar (JAGUAR C13S ^®, JAGUAR C162 ^®, Hicare 1000 ^® sold by the company Rhodia (in a proportion of 0 to 40% of the total weight of said cleaning composition)
• ◆ biocides or disinfectants as
  • cationic biocides , for example
    • * quaternary monoammonium salts such as
      • chloro-alkyl benzyl dimethyl ammonium chloride, C ₁₂ -C ₁₄ alkyl benzyl dimethyl ammonium chloride, coco-alkyl dichlorobenzyl dimethyl ammonium chloride, tetradecyl benzyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride
      • myristyl trimethylammonium bromides, cetyl trimethylammonium
    • * monoquaternary heterocyclic amine salts such as laurylpyridinium, cetylpyridinium, C ₁₂ -C ₁₄ alkyl benzylimidazolium chlorides
    • * triphenyl phosphonium alkyl fatty salts such as myristyl triphenyl phosphonium bromide
    • * Polymeric biocides, such as those derived from the reaction
      • epichlorohydrin and dimethylamine or diethylamine
      • epichlorohydrin and imidazole
      • 1,3-dichloro-2-propanol and dimethylamine
      • 1,3-dichloro-2-propanol and 1,3-bis-dimethylamino-2-propanol
      • ethylene dichloride and 1,3-bis-dimethylamino-2-propanol
      • bis (2-chloroethyl) ether and N, N'-bis (dimethylaminopropyl) urea or thiourea
      • the biguanidine polymer hydrochloride, such as VANTOCIL IB
  • amphoteric biocides, such as N- (N'-C ₈ -C ₁₈ alkyl-3-aminopropyl) -glycine derivatives of N- (N '- (N "-C ₈ -C ₁₈ alkyl-2-aminoethyl) - 2-aminoethyl) -glycine, N, N-bis (N'-C ₈ -C ₁₈ alkyl-2-aminoethyl) -glycine, such as (dodecyl) (aminopropyl) glycine, (dodecyl) (diethylenediamine) glycine
  • amines such as N- (3-aminopropyl) -N-dodecyl-1,3-propanediamine
  • halogenated biocides such as iodophors and hypochlorite salts, such as sodium dichloroisocyanurate
  • phenolic biocides such as phenol, resorcinol, cresols, salicylic acid
  • hydrophobic biocides as
    • parachlorometaxylenol, dichlorometaxylenol
    • 4-chloro-m-cresol
    • resorcinol monoacetate
    • mono- or poly-alkyl or aryl phenols, cresols or resorcinols, such as o-phenyl-phenol, p-tert-butyl-phenol, 6-n-amyl-m-cresol,
    • alkyl and / or aryl chloro or bromophenols, such as o-benzyl-p-chlorophenol
    • halogenated diphenyl ethers, such as 2 ', 4,4'-trichloro-2-hydroxy-diphenyl ether (triclosan), 2,2'-dihydroxy-5,5'-dibromo-diphenyl ether.
    • chlorophenesine (p-chlorophenylglyceric ether).
  at 0 to 5% of the total weight of said cleaning composition.
• Solvents with good cleaning or degreasing activity , such as
  • octyl benzene alkylbenzenes,
  • olefins having a boiling point of at least 100 ° C, such as alpha-olefins, preferably 1-decene or 1-dodecene
  • glycol ethers of the general formula, R 1 O (R 2 O) m H wherein R 1 is an alkyl group having 3 to 8 carbons and each R 2 is either ethylene or propylene and m is a number ranging from 1 to 3; mention may be made of monopropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, monopropylene glycol monobutyl ether, diethylene glycol monohexyl ether, monoethylene glycol monohexyl ether, monoethylene glycol monobutyl ether and mixtures thereof.
  • diols having from 6 to 16 carbon atoms in their molecular structure; diols are particularly interesting because in addition to their degreasing properties, they can help eliminate calcium salts (soaps); the diols containing from 8 to 12 carbon atoms are preferred, most preferably 2,2,4-trimethyl-1,3-pentanediol.
  • other solvents such as pine oil, orange terpenes, benzyl alcohol, n-hexanol, phatlic esters of alcohols having 1 to 4 carbon atoms, butoxy propanol, butyl carbitol and the like. (2-n-butoxy-1-methylethoxy) propan-2-ol also called butoxy propoxy propanol or dipropylene glycol monobutyl ether, diglycol hexyl (Hexyl Carbitol), butyl triglycol, diols such as 2,2,4-trimethyl- 1,3-pentanediol, and mixtures thereof.
  (at the rate of 0 to 30% of the total weight of said cleaning composition)
• Industrial cleaners such as alkaline salt solutions of the phosphates, carbonates, silicates, sodium, potassium type (at a level of from 0 to 50% of the total weight of said cleaning composition)
• Water- insoluble organic solvents such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and mixtures thereof (at a level of from 0 to 40% of the total weight of said cleaning composition)
• Cosolvents such as monoethanolamide and / or beta-aminoalkanols, which are particularly useful in compositions with a pH greater than 11, especially greater than 11.7, since they help reduce the formation of films and traces on hard surfaces ( they can be used at a rate of 0.05 to 5% of the weight of the cleaning composition); solvent systems comprising monoethanolamide and / or beta-aminoalkanols are described in US 5,108,660 .
• ◆ defoamers, such as soaps. Soaps are alkaline salts of fatty acids, including sodium, potassium, ammonium and higher alkanol ammonium salts of fatty acids containing from about 8 to 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms. carbon atoms; mention may especially be made of sodium and potassium mono-, di- and triethanolamine salts or mixtures of fatty acids derived from coconut oil and ground walnut oil. The amount of soap may be at least 0.005% by weight, preferably from 0.5% to 2% by weight relative to the total weight of the composition. Additional examples of foam control materials are organic solvents, hydrophobic silica, silicone oil and hydrocarbons.
• ◆ abrasives , such as silica, calcium carbonate
• ◆ various additives such as enzymes, perfumes, dyes, metal corrosion inhibitors, preservatives, optical brighteners, opacifying agents or pearls ...

The pH of the composition which is the subject of the invention or the pH of use of said composition can range from 0.5 to 14, preferably from 1 to 14.

The alkaline type compositions with a pH greater than or equal to 7.5, preferably greater than 8.5 for household applications (especially pH 8.5 to 12, in particular 8.5 to 11.5) are particularly useful for the removal of greasy soils and are particularly suitable for kitchen cleaning .

They can comprise from 0.001 to 5%, preferably from 0.005 to 2% of their weight of polybetaine (B).

• un agent séquestrant ou antitartre (en quantité allant de 0 à 40%, de préférence de 1 à 40%, plus préférentiellement de 2 à 30% et tout particulièrement de 5 à 20% du poids de la composition)
• un biocide ou désinfectant cationique, notamment de type ammonium quaternaire, comme les chlorures de N-alkyl benzyl dimethyl ammonium, chlorure de N-alkyl dimethyl ethylbenzyl ammonium, halogénure de N-didecydimethylammonium, et chlorure de di- N-alkyl dimethyl ammonium (en quantité pouvant aller de 0 à 60%, de préférence de 0 à 40%, plus préférentiellement de 0 à 15% et tout particulièrement de 0 à 5% du poids de la composition)
• au moins un agent tensioactif non-ionique, amphotère, zwitterionique, ou anionique ou leur mélange ; lorsqu'un agent tensioactif cationique est présent, ladite composition comprend en outre préférentiellement un agent tensioactif amphotère et/ou non-ionique (la quantité totale d'agents tensioactifs peut aller de 0 à 80%, de préférence de 0 à 50% , tout particulièrement de 0 à 35% du poids de la composition)
• si nécessaire, un agent de régulation de pH, en une quantité permettant d'atteindre, éventuellement après dilution ou mise en solution de la composition, un pH d'utilisation allant de 7,5 à 13 ; l'agent de régulation de pH peut notamment être un système tampon comprenant de la monoethanolamine et/ou un beta-aminoalkanol et potentiellement mais préférentiellement des matériaux alcalins « co-tampon » du groupe de l'ammoniaque, des C2-C4 alkanolamines, des hydroxydes d'alcalins, silicates, borates, carbonates, bicarbonates et leur mélanges. Les cotampons préférés sont les hydroxydes alcalins.
• de 0,5 à 98%, de préférence de 25 à 95%, tout particulièrement de 45 à 90% en poids d'eau
• un solvant organique nettoyant ou dégraissant, en quantité pouvant représenter de 0 à 60%, de préférence de 1 à 45%, tout particulièrement de 2 à 15% du poids de ladite composition
• un co-solvant comme la monoethanolamine et/ou les beta-aminoalkanols, en quantité pouvant représenter de 0 à 10%, de préférence de 0,05 à 10%, tout particulièrement de 0,05 à 5% du poids de ladite composition
• un solvant organique hydrosoluble peu nettoyant, en quantité pouvant représenter de 0 à 25%, de préférence de 1 à 20 %, tout particulièrement de 2 à 15% du poids de ladite composition
• éventuellement un agent de blanchiment, un parfum ou d'autres additifs usuels.

The alkaline compositions generally comprise, in addition to the polybetaine (B), at least one additive chosen from

• a sequestering or antiscaling agent (in an amount ranging from 0 to 40%, preferably from 1 to 40%, more preferably from 2 to 30% and most preferably from 5 to 20% by weight of the composition)
• a cationic biocide or disinfectant , especially of the quaternary ammonium type, such as N-alkylbenzyl dimethyl ammonium chloride, N-alkyl dimethyl ethylbenzyl ammonium chloride, N-didecydimethylammonium halide, and di-N-alkyl dimethyl ammonium chloride (in amount ranging from 0 to 60%, preferably from 0 to 40%, more preferably from 0 to 15% and most preferably from 0 to 5% of the weight of the composition)
• at least one non-ionic surfactant, amphoteric, zwitterionic, or anionic or a mixture thereof; when a cationic surfactant is present, said composition preferably further comprises an amphoteric and / or nonionic surfactant (the total amount of surfactants can range from 0 to 80%, preferably from 0 to 50%, all especially from 0 to 35% of the weight of the composition)
• if necessary, a pH regulating agent , in an amount to reach, optionally after dilution or dissolution of the composition, a pH of use ranging from 7.5 to 13; the pH-regulating agent can in particular be a buffer system comprising monoethanolamine and / or a beta-aminoalkanol and potentially but preferably alkaline materials "co-buffer" of the ammonia group, C2-C4 alkanolamines, hydroxides of alkalis, silicates, borates, carbonates, bicarbonates and mixtures thereof. Preferred cotampons are alkali hydroxides.
• from 0.5 to 98%, preferably from 25 to 95%, especially from 45 to 90% by weight of water
• a cleaning or degreasing organic solvent , in an amount that may represent from 0 to 60%, preferably from 1 to 45%, especially from 2 to 15% by weight of said composition
• a co-solvent such as monoethanolamine and / or beta-aminoalkanols, in an amount which can represent from 0 to 10%, preferably from 0.05 to 10%, more particularly from 0.05 to 5% by weight of said composition
• a water-soluble organic solvent with little cleaning , in an amount which may represent from 0 to 25%, preferably from 1 to 20%, more particularly from 2 to 15% by weight of said composition
• optionally a bleaching agent, a perfume or other usual additives.

Said alkaline compositions may be in the form of a ready-to-use formula or of a dry or concentrated formula to be diluted in water in particular, before use; they can be diluted 1 to 10,000 times, preferably 1 to 1000 times before use.

• de 0,001 à 1 % en poids de polybétaïne (B)
• de 1 à 10 % en poids de solvant hydrosoluble, l'isopropanol notamment
• de 1 à 5 % en poids de solvant nettoyant ou dégraissant, le butoxypropanol notamment
• de 0,1 à 2 % en poids de monoéthanolamine
• de 0 à 5 % en poids d'au moins un agent tensioactif non cationique, de préférence amphotère ou non-ionique,
• de 0 à 1 % en poids d'au moins un agent tensioactif cationique à propriété désinfectante (notamment mélange de n-alkyl dimethyl ethylbenzyl ammonium chloride et n-alkyl dimethyl benzyl ammonium chloride),
  la quantité totale d'agent(s) tensioactif(s) représentant de 1 à 50 % en poids
• de 0 à 2 % en poids d'un diacide carboxylique comme agent antitartre
• de 0 à 5 % d'un agent de blanchiment
• et de 70 à 98 % en poids d'eau.

Advantageously, a formulation for cleaning kitchens, comprises:

• from 0.001 to 1% by weight of polybetaine (B)
• from 1 to 10% by weight of water-soluble solvent, in particular isopropanol
• from 1 to 5% by weight of cleaning or degreasing solvent, especially butoxypropanol
• from 0.1 to 2% by weight of monoethanolamine
• from 0 to 5% by weight of at least one non-cationic surfactant, preferably amphoteric or nonionic surfactant,
• from 0 to 1% by weight of at least one cationic surfactant with a disinfecting property (in particular a mixture of n-alkyl dimethyl ethylbenzyl ammonium chloride and n-alkyl dimethyl benzyl ammonium chloride),
  the total amount of surfactant (s) representing from 1 to 50% by weight
• from 0 to 2% by weight of a dicarboxylic acid as anti-scale agent
• from 0 to 5% of a bleaching agent
• and from 70 to 98% by weight of water.

The pH of such a formulation is preferably from 7.5 to 13, more preferably from 8 to 12.

Acid-like compositions having a pH of less than 5 are particularly useful for the removal of mineral-type soils; they are particularly well suited for cleaning toilet bowls .

They may comprise from 0.001 to 5%, preferably from 0.01 to 2%, of their weight of polybetaine (B).

• un agent acide minéral ou organique (en quantité allant de 0,1 à 40%, de préférence de 0,5 à 20% et plus préférentiellement de 0,5 à 15% du poids de la composition)
• au moins un agent tensioactif non-ionique, amphotère, zwitterionique, ou anionique ou leur mélange ; (la quantité totale d'agents tensioactifs peut aller de 0,5 à 20%, de préférence de 0,5 à 10 % du poids de la composition)
• éventuellement un biocide ou désinfectant cationique, notamment de type ammonium quaternaire, comme les chlorures de N-alkyl benzyl dimethyl ammonium, chlorure de N-alkyl dimethyl ethylbenzyl ammonium, halogénure de N-didecydimethylammonium, et chlorure de di- N-alkyl dimethyl ammonium (en quantité pouvant aller de 0,01 à 2% de préférence de 0,1 à 1% du poids de la composition)
• éventuellement un agent épaississant (en quantité allant de 0,1 à 3%, du poids de la composition)
• éventuellement un agent de blanchiment (en quantité allant de 1 à 10%, du poids de la composition)
• de 0,5 à 99 %, de préférence de 50 à 98 % en poids d'eau
• un solvant, comme le glycol ou un alcool, (en quantité pouvant aller de 0 à 10% de préférence de 1 à 5% du poids de la composition)
• éventuellement un parfum, un conservateur, un abrasif ou d'autres additifs usuels.

Acidic compositions generally comprise, besides polybetaine (B),

• an inorganic or organic acid agent (in an amount ranging from 0.1 to 40%, preferably from 0.5 to 20% and more preferably from 0.5 to 15% by weight of the composition)
• at least one non-ionic surfactant, amphoteric, zwitterionic, or anionic or a mixture thereof; (the total amount of surfactants can range from 0.5 to 20%, preferably from 0.5 to 10% by weight of the composition)
• optionally a cationic biocide or disinfectant , especially of the quaternary ammonium type, such as N-alkylbenzyl dimethyl ammonium chlorides, N-alkyl dimethyl ethylbenzyl ammonium chloride, N-didecydimethylammonium halide, and di-N-alkyl dimethyl ammonium chloride ( in an amount ranging from 0.01 to 2%, preferably from 0.1 to 1% by weight of the composition)
• optionally a thickening agent (in an amount ranging from 0.1 to 3%, by weight of the composition)
• optionally a bleaching agent (in an amount ranging from 1 to 10%, by weight of the composition)
• from 0.5 to 99%, preferably from 50 to 98% by weight of water
• a solvent, such as glycol or an alcohol, (in an amount ranging from 0 to 10%, preferably from 1 to 5% by weight of the composition)
• optionally a perfume, a preservative, an abrasive or other usual additives.

Said acid compositions are preferably in the form of a ready-to-use formula.

• de 0,05 à 5%, de préférence de 0,01 à 2% en poids de polybétaïne (B)
• une quantité d'agent acide nettoyant telle que le pH final de la composition soit de 0,5 à 4, de préférence de 1 à 4 ; cette quantité est généralement de 0,1 à environ 40 %, et de préférence entre 0,5 et environ 15 % en poids par rapport au poids de la composition ; l'agent acide peut être notamment un acide minéral tel que l'acide phosphorique, sulfamique, chlorhydrique, fluorhydrique, sulfurique, nitrique, chromique et des mélanges de ceux-ci ou un acide organique, notamment l'acide acétique, hydroxyacétique, adipique, citrique, formique, fumarique, gluconique, glutarique, glycolique, malique, maléique, lactique, malonique, oxalique, succinique et tartrique ainsi que des mélanges de ceux-ci, des sels d'acides tels que le bisulfate de sodium et des mélanges de ceux-ci ; la quantité préférée dépend du type du nettoyant acide utilisé : par exemple avec l'acide sulfamique, elle est comprise entre 0,2 et 10%, avec l'acide chlorhydrique entre 1 et 15 %, avec l'acide citrique entre 2 et 15 %, avec l'acide formique, entre 5 et 15 % et avec l'acide phosphorique, entre 2 et 30 % en poids.
• de 0,5 à 10% en poids d'au moins un agent tensioactif, de préférence anionique ou non-ionique
• éventuellement de 0,1 à 2 % en poids d'au moins un agent tensioactif cationique à propriété désinfectante (notamment mélange de n-alkyl dimethyl ethylbenzyl ammonium chloride et n-alkyl dimethyl benzyl ammonium chloride)
• éventuellement un agent épaississant (en quantité allant de 0,1 à 3%, du poids de composition), de type gomme, notamment une gomme xanthane ou un succinoglycane (Rheozan)
• éventuellement un agent de blanchiment (en quantité allant de 1 à 10%, du poids de composition)
• éventuellement un conservateur, un colorant, un parfum ou un abrasif
• et de 50 à 95 % en poids d'eau.

Advantageously, a formulation for cleaning the toilet bowls , comprises:

• from 0.05 to 5%, preferably from 0.01 to 2% by weight of polybetaine (B)
• a quantity of cleaning acidic agent such that the final pH of the composition is from 0.5 to 4, preferably from 1 to 4; this amount is generally from 0.1 to about 40%, and preferably from 0.5 to about 15% by weight based on the weight of the composition; the acidic agent may in particular be a mineral acid such as phosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, chromic acid and mixtures thereof or an organic acid, especially acetic, hydroxyacetic or adipic acid, citric, formic, fumaric, gluconic, glutaric, glycolic, malic, maleic, lactic, malonic, oxalic, succinic and tartaric, as well as mixtures thereof, acid salts such as sodium bisulfate and mixtures thereof; the preferred amount depends on the type of acid cleaner used: for example with sulfamic acid, it is between 0.2 and 10%, with hydrochloric acid between 1 and 15%, with citric acid between 2 and 15 %, with formic acid, between 5 and 15% and with phosphoric acid, between 2 and 30% by weight.
• from 0.5 to 10% by weight of at least one surfactant, preferably anionic or nonionic
• optionally from 0.1 to 2% by weight of at least one cationic surfactant with a disinfecting property (in particular a mixture of n-alkyl dimethyl ethylbenzyl ammonium chloride and n-alkyl dimethyl benzyl ammonium chloride)
• optionally a thickening agent (in an amount ranging from 0.1 to 3%, weight of composition), of the gum type, in particular a xanthan gum or a succinoglycan (Rheozan)
• optionally a bleaching agent (in an amount ranging from 1 to 10%, the weight of the composition)
• possibly a preservative, a dye, a perfume or an abrasive
• and from 50 to 95% by weight of water.

Hereinafter are explained some other particular embodiments and application of the composition of the invention.

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

The amount of polybetaine (B) introduced will generally be such that, when using the cleaning composition, after optional dilution, the concentration of polybetaine (B) is between 0.001 g / l and 2 g / l, preferably of 0.005 g / l and 0.5 g / l.

• de 0,001 à 10 %, de préférence 0,005 à 3 % en poids d'au moins une polybétaïne (B) ;
• de 0,005 à 20 %, de préférence de 0,5 à 10 % en poids d'au moins un agent tensioactif non-ionique (par exemple un amine oxyde ou un alkyl polyglucoside) et/ou anionique ; et
• le reste étant formé d'eau et/ou d'additifs divers usuels dans le domaine.

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

• from 0.001 to 10%, preferably from 0.005 to 3% by weight of at least one polybetaine (B);
• from 0.005 to 20%, preferably from 0.5 to 10% by weight, of at least one nonionic surfactant (for example an amine oxide or an alkyl polyglucoside) and / or anionic surfactant; and
• the remainder being water and / or various additives customary in the field.

• de 0 à 10%, avantageusement de 0,5 à 5 % de tensioactif amphotère,
• de 0 à 30 %, avantageusement de 0,5 à 15 % de solvant tels que des alcools, et
• le reste étant constitué par de l'eau et des additifs usuels (parfums notamment).

The glass cleaning formulations comprising said polymer may also contain:

• from 0 to 10%, advantageously from 0.5 to 5% of amphoteric surfactant,
• from 0 to 30%, advantageously from 0.5 to 15% of solvent such as alcohols, and
• the rest being water and usual additives (especially perfumes).

The pH of the composition is advantageously between 6 and 11.

The composition of the invention is also interesting for the easy cleaning of the dishes in automatic machine. The composition may be either a detergent (cleaning) formula used in the wash cycle or a rinse formula.

The dishwashing detergent compositions in automatic dishwashers according to the invention preferably comprise from 0.01 to 5%, preferably 0.1 to 3% by weight of polybetaine (B).

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

• jusqu'à 90% en poids, d'au moins un adjuvant de détergence ("builder") de type silicate ou tripolyphosphate de sodium
• jusqu'à 10%, de préférence de 1 à 10%, tout particulièrement de 2 à 8% en poids, d'au moins un agent auxiliaire de nettoyage, un copolymère d'acide acrylique et d'acide méthyl propane sulfonique (AMPS) de préférence
• jusqu'à 30% en poids d'au moins un agent de blanchiment, de préférence perborate ou percarbonate, associé ou non à un activateur de blanchiment
• jusqu'à 50% en poids d'au moins une charge, de préférence sulfate de sodium ou chlorure de sodium

So they can further understand

• up to 90% by weight of at least one sodium silicate or tripolyphosphate builder
• up to 10%, preferably from 1 to 10%, most preferably from 2 to 8% by weight, of at least one cleaning auxiliary agent, a copolymer of acrylic acid and methyl propane sulfonic acid (AMPS) preferably
• up to 30% by weight of at least one bleaching agent, preferably perborate or percarbonate, associated or not with a bleach activator
• up to 50% by weight of at least one filler, preferably sodium sulfate or sodium chloride

The pH is advantageously between 8 and 13.

The compositions for easy rinsing of the automatic dishwashing machine according to the invention may advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5% by weight of polybetaine (B) relative to the weight. total of the composition.

Said compositions may also comprise from 0.1 to 20%, preferably from 0.2 to 15% by weight relative to the total weight of said composition of a surfactant, preferably a nonionic surfactant.

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

Said compositions may furthermore comprise from 0 to 10%, preferably from 0.5 to 5% by weight relative to the total weight of the composition of an organic acid sequestering calcium, preferably citric acid.

They may also comprise a copolymer auxiliary agent of acrylic acid and maleic anhydride or homopolymers of acrylic acid in a proportion of 0 to 15%, preferably 0.5 to 10% by weight relative to the weight total of said composition.

The pH is advantageously between 4 and 7.

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

Preferred detergent formulations of this type comprise from 0.1 to 10 parts by weight of polybetaine (B) per 100 parts by weight of said composition and contain from 3 to 50, preferably from 10 to 40 parts by weight of, at least a surfactant, preferably anionic, chosen in particular from sulphates of saturated C ₅ -C ₂₄ , preferably C ₈ -C ₁₆ , aliphatic alcohols, optionally condensed with approximately 0.5 to 30, preferably 0.5 to 30, preferably 8, in particular 0.5 to 5 moles of ethylene oxide, in acid form or in the form of a salt, in particular alkaline (sodium), alkaline earth (calcium, magnesium) ...

Preferentially, it is a foamy liquid detergent aqueous formulations for the hand-washed washing of dishes.

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

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

• nonionic surfactants such as amine oxides, alkylglucamides, alkyl polyglucosides, oxyalkylenated derivatives of fatty alcohols, alkylamides, alkanolamides, amphoteric or zwitterionic surfactants.
• non-cationic bactericidal or disinfectant agents such as triclosan
• synthetic cationic polymers
• polymers for controlling the viscosity of the mixture and / or the stability of foams formed upon use
• hydrotropic agents
• moisturizing or humectant or skin-protecting agents
• dyes, perfumes, preservatives, divalent salts (especially magnesium) ...

The pH of the composition is advantageously between 5 and 9.

Another particular embodiment of the invention consists of an easy external cleaning composition , in particular of the bodywork, of motorized vehicles (cars, trucks, buses, trains, planes, etc.).

In this case also, it may be a cleaning composition itself or a rinse composition.

• des agents tensioactifs non ioniques (à raison de 0 à 30%, de préférence de 0,1 à 15 % de la formulation),
• des agents tensioactifs amphotères et/ou zwitterioniques (à raison de 0 à 30%, de préférence de 0,01 à 10 % de la formulation)
• des agents tensioactifs cationiques (à raison de 0 à 30%, de préférence de 0,05 à 15 % de la formulation);
• des agents tensioactifs anioniques (à raison de 0 à 30%, de préférence de 0,1 à 15 % de la formulation);
• des adjuvants de détergence ("builders") (à raison de 1 à 99%, de préférence de 40 à 98 % de la formulation);
• des agents hydrotropes
• des charges, des agents régulant le pH ...

The cleaning composition for motor vehicles advantageously comprises from 0.005 to 10% by weight of polybetaine (B) relative to the total weight of said composition, as well as:

• nonionic surfactants (from 0 to 30%, preferably from 0.1 to 15% of the formulation),
• amphoteric and / or zwitterionic surfactants (at a level of 0 to 30%, preferably from 0.01 to 10% of the formulation)
• cationic surfactants (from 0 to 30%, preferably from 0.05 to 15% of the formulation);
• anionic surfactants (from 0 to 30%, preferably from 0.1 to 15% of the formulation);
• builders (builders) (1 to 99%, preferably 40 to 98% of the formulation);
• hydrotropic agents
• fillers, pH-regulating agents ...

The minimum amount of surfactant present in the composition type is preferably at least 0.5% of the formulation.

The pH of the composition is advantageously between 8 and 13.

The composition of the invention is also particularly suitable for easy cleaning of ceramic- type hard surfaces (tiles, bathtubs, washbasins, etc.), especially for bathrooms .

The cleaning formulation advantageously comprises from 0.02 to 5% by weight of polybetaine (B) relative to the total weight of said composition and at least one surfactant.

As surface-active agents, nonionic surfactants are preferred, in particular compounds produced by condensation of alkylene oxide groups of a hydrophilic nature with a hydrophobic organic compound which may be of aliphatic or alkylaromatic nature.

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

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

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

It is also possible but not mandatory to add amphoteric, cationic or zwitterionic detergents.

The total amount of surfactant compounds used in this type of composition is generally between 0.5 and 50%, preferably between 1 and 30% by weight, and more particularly between 2 and 20% by weight relative to the total weight of the composition. composition.

• des adjuvants de détergence ("builders") tels que mentionnés précédemment (en quantité pouvant être comprise entre 0,1 et 25 % en poids par rapport au poids total de la composition)
• un agent de régulation de la mousse, tel que mentionné ci-dessus, notamment de type savon (en quantité généralement d'au moins 0,005 % en poids, de préférence de 0,5 % à 2 % en poids par rapport au poids total de la composition)
• des agents de régulation du pH, des colorants, des brillanteurs optiques, des agents de suspension des salissures, des enzymes détersives, des agents de blanchiment compatibles, des agents de régulation de la formation de gel, des stabilisateurs de congélation-décongélation, des bactéricides, des conservateurs, des solvants, des fongicides, des répulsifs pour insectes, des agents hydrotropes, des parfums et des opacifiants ou perlescents.

The cleaning composition may also include other minority ingredients, such as:

• detergency builders ("builders") as mentioned above (in an amount that may be between 0.1 and 25% by weight relative to the total weight of the composition)
• a regulating agent for the foam, as mentioned above, in particular of soap type (in an amount generally of at least 0.005% by weight, preferably from 0.5% to 2% by weight relative to the total weight of the composition)
• pH-regulating agents, dyes, optical brighteners, soil-suspending agents, detergent enzymes, compatible bleaching agents, gel-forming control agents, freeze-thawing stabilizers, bactericides preservatives, solvents, fungicides, insect repellents, hydrotropic agents, perfumes and opacifiers or pearls.

The pH of the composition is advantageously between 2 and 12.

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

The aqueous shower wall rinsing compositions comprise from 0.02% to 5% by weight, preferably from 0.05% to 1% polybetaine (B). The other main active components of the aqueous shower rinse compositions of the present invention are at least one surfactant present in an amount ranging from 0.5 to 5% by weight and optionally a chelating agent of metals as mentioned above, present in an amount of from 0.01 to 5% by weight.

The aqueous shower rinse compositions advantageously contain water with optionally at least one lower alcohol in major proportion and additives in a minor proportion (between about 0.1 and about 5% by weight, more preferably between about 0.5% and about 3% by weight, and even more preferably between about 1% and about 2% by weight).

Certain surfactants which can be used in this type of application are described in the patents US5,536,452 and 5587022 whose contents are incorporated by reference in the present description.

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

The pH of the composition is advantageously between 7 and 11.

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

• 0,01 à 5 % en poids de polybétaïne (B);
• 0,1 à 1 % en poids d'un épaississant tel qu'une gomme xanthane ;
• 10 à 60 % en poids d'un agent abrasif tel que le carbonate de calcium ou la silice ;
• 0 à 7 % en poids d'un solvant tel que le butyldiglycol ;
• 1 à 10 % en poids d'un agent tensioactif non ionique ; et
• éventuellement des agents d'alcalinisation ou des séquestrants.

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

• 0.01 to 5% by weight of polybetaine (B);
• 0.1 to 1% by weight of a thickener such as xanthan gum;
• 10 to 60% by weight of an abrasive agent such as calcium carbonate or silica;
• 0 to 7% by weight of a solvent such as butyldiglycol;
• 1 to 10% by weight of a nonionic surfactant; and
• optionally alkalizing agents or sequestering agents.

The pH of the composition is advantageously between 7 and 12.

As mentioned above, the composition according to the invention can also be used in the field of industrial cleaning, in particular for easy cleaning of reactors .

• de 0,02 à 5 % en poids de polybétaïne (B);
• de 1 à 50 % en poids de sels alcalins (phosphates, carbonates, silicates de sodium ou potassium);
• de 1 à 30 % en poids d'un mélange d'agents tensioactifs, notamment d'agents tensioactifs non-ioniques comme les alcools gras éthoxylés et les agents tensioactifs anioniques comme le lauryl benzène sulfonate ;
• de 0 à 30% en poids d'un solvant comme le diisobutyl ester.

Advantageously, said compositions comprise:

• from 0.02 to 5% by weight of polybetaine (B);
• from 1 to 50% by weight of alkali metal salts (phosphates, carbonates, sodium or potassium silicates);
• from 1 to 30% by weight of a mixture of surfactants, especially nonionic surfactants such as ethoxylated fatty alcohols and anionic surfactants such as lauryl benzene sulfonate;
• from 0 to 30% by weight of a solvent such as diisobutyl ester.

The pH of such a composition is generally 8 to 14.

A second object of the invention is the use, in a composition comprising at least one surfactant for cleaning or rinsing in aqueous or aqueous-alcoholic medium of the hard surfaces, of at least one polybetaine (B) as defined in the claims as an agent for providing said surfaces with anti-deposition and / or anti-adhesion properties of soils that may deposit on said surfaces.

A third subject of the invention consists of a process for improving the properties of compositions comprising at least one surfactant for cleaning or rinsing in aqueous or aqueous-alcoholic medium of the hard surfaces, by adding to said compositions at least one polybetaine (B ) as defined in the claims.

A fourth subject of the invention consists of a process for facilitating the cleaning or rinsing of hard surfaces, by bringing said surfaces into contact with a composition in an aqueous or aqueous-alcoholic medium, comprising at least one surfactant and at least one polybetaine (B), said polybetaine (B) as defined in the claims.

The polybetaine (B) is used or is present in said composition in an amount effective to provide said surfaces with anti-deposition and / or anti-adhesion properties soils may be deposited on said surfaces.

The nature and amounts of the polybetaine (B) present or implemented in said composition, as well as the other additives and different modes of application of said composition have already been mentioned above.

The following examples are given for illustrative purposes.

B1

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate), « poly(SPE) », de masse molaire moyenne en masse (M_w) absolue de 35 000 g/mol

B2

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate) de masse molaire moyenne en masse (M_w) absolue de 55 000 g/mol

B3

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate) de masse molaire moyenne en masse (M_w) absolue de 110 000 g/mol

B4

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate) de masse molaire moyenne en masse (M_w) absolue de 450 000 g/mol

B5

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate) de masse molaire moyenne en masse (M_w) absolue de 1 200 000 g/mol

B6

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate) de masse molaire moyenne en masse (M_w) absolue de 1 800 000 g/mol

B7

Poly(sulfopropyl diméthylammonium propyl méthacrylamide), « poly(SPP) », de masse molaire moyenne en masse (M_w) absolue de 55 000 g/mol

B8

Poly(sulfohydroxypropyl diméthylammonium propyl méthacrylamide), « poly(SHPP) », de masse molaire moyenne en masse (M_w) absolue de 60 000 g/mol

C1

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate-co-acide méthacrylique), « poly(SPE/AMA) de masse molaire moyenne en masse (M_w) absolue de 50 000 g/mol, présentant un rapport molaire SPE/AMA de 95/5

C2

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate-co-acide méthacrylique) de masse molaire moyenne en masse (M_w) absolue de 50 000 g/mol, présentant un rapport molaire SPE/AMA de 851/5

C3

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate-co-acide méthacrylique) de masse molaire moyenne en masse (M_w) absolue de 50 000 g/mol, présentant un rapport molaire SPE/AMA de 66/34

C4

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate-co-acide méthacrylique) de masse molaire moyenne en masse (M_w) absolue de 50 000 g/mol, présentant un rapport molaire SPE/AMA de 60/40

C5

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate-co-acide méthacrylique) de masse molaire moyenne en masse (M_w) absolue de 50 000 g/mol, présentant un rapport molaire SPE/AMA de 49/51

C6

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate-co-acide méthacrylique) de masse molaire moyenne en masse (M_w) absolue de 50 000 g/mol, présentant un rapport molaire SPE/AMA de 40/60

C7

Poly(propylsulfonate diméthyl ammonium éthyl méthacrylate-co-acide méthacrylique) de masse molaire moyenne en masse (M_w) absolue de 50 000 g/mol, présentant un rapport molaire SPE/AMA de 25/75

The following homopolysulfobetaines B1 to B8 and the following C1 to C7 copolysulphobetaines, the performance of which will be tested in the following examples, are prepared in the laboratory using a radical solution polymerization method well known to those skilled in the art. .

B1

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate), "poly (SPE)", with an average molecular weight ( _Mw ) of 35,000 g / mol

B2

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate) with an average molecular weight ( _Mw ) of 55,000 g / mol

B3

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate) with an average molecular weight ( _Mw ) of 110,000 g / mol

B4

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate) with an average molecular weight ( _Mw ) of 450,000 g / mol

B5

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate) with an average molecular weight ( _Mw ) of 1,200,000 g / mol

B6

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate) with an average molecular weight ( _Mw ) of 1,800,000 g / mol

B7

Poly (sulfopropyl dimethylammonium propyl methacrylamide), "poly (SPP)", with an average molecular weight ( _Mw ) of 55,000 g / mol

B8

Poly (sulfohydroxypropyl dimethylammonium propyl methacrylamide), "poly (SHPP)" average molar mass weight (M _w) Absolute 60 000 g / mol

C1

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate-co-methacrylic acid), "poly (SPE / AMA) with an average molecular weight by mass ( _Mw ) of 50,000 g / mol absolute, having an SPE / AMA molar ratio of 95/5

C2

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate-co-methacrylic acid) with an average mass by weight ( _Mw ) of 50,000 g / mol, having an SPE / AMA molar ratio of 851/5

C3

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate-co-methacrylic acid) with an average mass by mass ( _Mw ) of 50,000 g / mol, having a molar ratio of SPE / AMA of 66/34

C4

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate-co-methacrylic acid) with an average mass by mass ( _Mw ) of 50,000 g / mol, having a SPE / AMA molar ratio of 60/40

C5

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate-co-methacrylic acid) with an average mass by mass (M _w ) of 50,000 g / mol, having an SPE / AMA molar ratio of 49/51

C6

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate-co-methacrylic acid) with an average molecular weight by mass ( _Mw ) of 50,000 g / mol, having an SPE / AMA molar ratio of 40/60

C7

Poly (propylsulfonate dimethyl ammonium ethyl methacrylate-co-methacrylic acid) with an average mass by mass ( _Mw ) of 50,000 g / mol, having a SPE / AMA molar ratio of 25/75

The molar masses mentioned are absolute mass average molar masses, measured by GPC aqueous gel permeation chromatography by MALLS light scattering, according to the following conditions: Eluent : Millipore water 18 MΩ, NO ₃ NH ₄ 1M, N ₃ Na 1/10 000 Debit : 1 ml / min Olume injected : 100 .mu.l Calibration : Nil, the mass is established by MALLS Columns : 2 columns GPC (SB806MHQ Shodex OH Pack 30cm, 5μm) Detectors : Refractometer : RI Waters 410 DDL : Wyatt laser scattering light scattering MALLS, 633nm laser

Preliminary Example 1 : Intrinsic Anti-Adhesion Properties of B1 to B8 and C1 to C7 Betaines Polymers or Copolymers (Visual Tests)

The betaine polymers B1 to B8 tested are respectively used in the form of a solution at a concentration of 200 mg / l in a water / ethanol mixture containing 5% by volume of ethanol (in order to facilitate the drying of the deposited solution. on the surface to be treated); the solution is brought to pH 3 by adding hydrochloric acid

• en l'absence de polymère bétaïne B1 à B8
• en présence d'un agent tensioactif zwitterionique (ZwSurf) de type cocoamidopropyle hydroxysultaïne (Mirataine CBS de Rhodia), mis en oeuvre sous forme d'une solution à une concentration de 200mg/l dans un mélange eau/éthanol contenant 5 % en volume d'éthanol ; la solution est amenée à pH 3 par addition d'acide chlorhydrique

The intrinsic performances of betaine polymers B1 to B8 according to the invention are visually tested and compared with those obtained.

• in the absence of betaine polymer B1 to B8
• in the presence of a zwitterionic surfactant (ZwSurf) of the cocoamidopropyl hydroxysultaine type (Mirataine CBS from Rhodia), used in the form of a solution at a concentration of 200 mg / l in a water / ethanol mixture containing 5% by volume of ethanol; the solution is brought to pH 3 by adding hydrochloric acid

Test

A black ceramic plate 25cm x 25cm in size, previously worked with ethanol, is used, the surface of which is divided into 10 equal parallel fractions F, F ', F1, F2, F3, F4, F5. , F6, F7 and F8. The operative protocol is the following

1. treatment

• The first fraction, F, of the plate is left as it is
• On the whole of the second fraction, F ', is deposited, using a film-puller, 2.5 mg / m ² of zwitterionic surfactant (solution in the water / ethanol mixture, pH 3)
• Over all of the fractions F1 to F8, 2.5 mg / m ² of polymer B1 to B8 (solutions in the water / ethanol mixture, pH 3) are deposited with the aid of a film puller.

2. dirt deposit

15 g of the following model dirt are deposited on the entire rinsed plate and allowed to air dry for 24 hours.

• 75% en poids d'eau
• 10% en poids de cellulose
• 7,5% de sels minéraux (phosphate de calcium, phosphate de fer)
• 5% en poids de cholestérol
• 2,5% en poids d'huile alimentaire (olive, ricin)
  • 1. rinçage
    la plaque salie est ensuite rinçée à l'aide d'un litre d'eau dure de ville et laissée sécher.

The stain model, of white color, implemented consists of

• 75% by weight of water
• 10% by weight of cellulose
• 7.5% of mineral salts (calcium phosphate, iron phosphate)
• 5% by weight of cholesterol
• 2.5% by weight of edible oil (olive, castor)
  • 1. rinse
    the soiled plaque is then rinsed with a liter of hard water and left to dry.

The plate is visually analyzed by a set of 20 testers.

• 1 : surface très sale
• 5 : surface propre

The results are noted as follows

• 1: very dirty surface
• 5: clean surface

The test described above is also carried out by replacing the polymers B1 to B8 by the copolymers C1 to C7.

The overall results are given below: Treatment with (Mw) in g / mol Performance None (reference) - 1 ZwSurf - 2.1 B1 poly (SPE) 35,000 4.9 B2 poly (SPE) 55,500 4.6 B3 poly (SPE) 110,000 4.2 B4 poly (SPE) 450,000 3.9 B5 poly (SPE) 1,200,000 2.2 B6 poly (SPE) 1,800,000 2.1 B7 poly (SPP) 55,000 4.7 B8 Poly (SHPP) 60,000 4.6 C1 poly (SPE / AMA) 95/5 50,000 4.6 C2 poly (SPE / AMA) 85/15 50,000 4.5 C3 poly (SPE / AMA) 66/34 50,000 4.4 C4 poly (SPE / AMA) 60/40 50,000 4.4 C5 poly (SPE / AMA) 49/51 50,000 4.2 C6 poly (SPE / AMA) 40/60 50,000 4.2 C7 poly (SPE / AMA) 25/75 50,000 4.1

It is found that betaine polymers B1 to B8 and C1 to C7 facilitate the removal of dirt. Polymers B1 to B4, B7 and B8, as well as C1 to C7, of Mw less than 500,000 g / mol, are very efficient, especially those of Mw less than 150,000 g / mol. The SPE / AMA molar ratio of the copolymers C1 to C7 has little impact in this test.

Preliminary Example 2 : Intrinsic Properties of Remanence (after 200 Rinses) and Anti-Adhesion of Soiling of Betaine Polymers B1, B5, B7, C1, C2, C4 and C6 (Visual Tests)

The betaine polymers B1, B5, B7, C1, C2, C4 and C6 tested are used in the form of solutions at a concentration of 200 mg / l in a water / ethanol mixture containing 5% by volume of ethanol (in order to facilitate the drying of the solution deposited on the surface to be treated); the solutions are brought to pH 3 by adding hydrochloric acid.

• en l'absence de polymère bétaïne B1, B5, B7, C1, C2, C4 ou C6
• en présence d'un agent tensioactif zwitterionique (ZwSurf) de type cocoamidopropyle hydroxysultaïne (Mirataine CBS de Rhodia), mis en oeuvre sous forme d'une solution à une concentration de 200mg/l dans un mélange eau/éthanol contenant 5 % en volume d'éthanol ; la solution est amenée à pH 3 par addition d'acide chlorhydrique

The intrinsic performances of betaine polymers B1, B5, B7, C1, C2, C4 and C6, according to the invention, are visually tested and compared with those obtained.

• in the absence of betaine polymer B1, B5, B7, C1, C2, C4 or C6
• in the presence of a zwitterionic surfactant (ZwSurf) of the cocoamidopropyl hydroxysultaine type (Mirataine CBS from Rhodia), used in the form of a solution at a concentration of 200 mg / l in a water / ethanol mixture containing 5% by volume of ethanol; the solution is brought to pH 3 by adding hydrochloric acid

Test

A 20cm x 20cm black ceramic plate, previously cleaned with ethanol, whose surface is divided into 3 equal parallel fractions, is used.

The operative protocol is the following

1. treatment

• The first fraction of the plate is left as it is
• On the whole of the second fraction is deposited, using a film puller, 2.5 mg / m ² of zwitterionic surfactant (solution in the water / ethanol mixture, pH 3)
• On the whole of the third fraction, using a film puller, 2.5 mg / m ² of polymer B1, B5, B7, C1, C2, C4 or C6 (solution in the mixture are deposited water / ethanol, pH 3)

2. rinse

The treated plate is subjected to 200 rinsing cycles using 200 x 1 liter of water

3. dirt deposit

• 15 g of the following model dirt are deposited on the entire rinsed plate and allowed to air dry for 24 hours.

• 75% en poids d'eau
• 10% en poids de cellulose
• 7,5% de sels minéraux (phosphate de calcium, phosphate de fer)
• 5% en poids de cholestérol
• 2,5% en poids d'huile alimentaire (olive, ricin)
  • 1. rinçage final
    la plaque salie est ensuite rinçée à l'aide d'un litre d'eau dure de ville et laissée sécher à l'air pendant 30 minutes.

The stain model, of white color, implemented consists of

• 75% by weight of water
• 10% by weight of cellulose
• 7.5% of mineral salts (calcium phosphate, iron phosphate)
• 5% by weight of cholesterol
• 2.5% by weight of edible oil (olive, castor)
  • 1. final rinse
    the soiled plaque is then rinsed with a liter of hard water and left to air dry for 30 minutes.

The plate is visually analyzed by a set of 20 testers.

• 1 : surface très sale
• 5 : surface propre

Traitement à l'aide de (Mw) en g/mol Performance Aucun (référence) - 1 ZwSurf - 1 B1 35 000 4,1 B5 1 200 000 1,9 B7 55 000 4,2 C1 poly(SPE/AMA) 95/5 50 000 3,9 C2 poly(SPE/AMA) 85/15 50 000 3,8 C4 poly(SPE/AMA) 60/40 50 000 2,5 C6 poly(SPE/AMA) 40/60 50 000 1,2 The results are noted as follows

• 1: very dirty surface
• 5: clean surface

Treatment with (Mw) in g / mol Performance None (reference) - 1 ZwSurf - 1 B1 35,000 4.1 B5 1,200,000 1.9 B7 55,000 4.2 C1 poly (SPE / AMA) 95/5 50,000 3.9 C2 poly (SPE / AMA) 85/15 50,000 3.8 C4 poly (SPE / AMA) 60/40 50,000 2.5 C6 poly (SPE / AMA) 40/60 50,000 1.2

It is found that the betaine polymers, especially the polymers B1, B7, C1 and C2, unlike a simple zwitterionic surfactant, remain on the surface for at least 200 rinsing cycles; the polymers of the invention are substantive of the surface.

The polymers do not leave at the same time as the dirt; without being linked to any mechanism, it is assumed that the anti-sticking mechanism of soiling is not "sacrificial".

Example 1: Compatibility of Polymer B1 and Copolymer C1 with Conventional Detergents.

• 0 mg/l, 50 mg/l, 100 mg/l et 200 mg/l de polymère B1 ou C1
• 10 g/l et 50 g/l d'un des tensioactifs suivants :
  • non ionique, Rhodasurf ID/060 de Rhodia,
  • anionique LaurylAlkylBenzene Sulfonate (Nansa ex Rhodia),
  • cationique Rhodaquat RP 50 de Rhodia
• et dont le pH est ajusté à 3, par l'ajout d'acide sulfurique à 0,01 molaire.

4 x 6 detergent solutions containing respectively

• 0 mg / l, 50 mg / l, 100 mg / l and 200 mg / l polymer B1 or C1
• 10 g / l and 50 g / l of one of the following surfactants:
  • Rhodia's non-ionic Rhodasurf ID / 060,
  • anionic LaurylAlkylBenzene Sulfonate (Nansa ex Rhodia),
  • cationic Rhodaquat RP 50 from Rhodia
• and whose pH is adjusted to 3, by the addition of sulfuric acid at 0.01 molar.

The transmittance of the 24 solutions is measured using a photometer. The transmittance of the 24 solutions is identical and comparable to that of a water solution at pH 3.

Polymers B1 and C1 are therefore compatible with all types of surfactants commonly used in detergency; they can therefore be formulated in any type of commercial formulation, without the risk of causing phase separation or instability over time.

• 75% en poids d'eau
• 10% en poids de cellulose
• 5% en poids de cholestérol
• 2,5% en poids d'huile alimentaire (olive, ricin)
• 7,5% de sels minéraux (phosphate de calcium, phosphate de fer)

Each aqueous solution is sprayed onto a black ceramic tile and then wiped with a commercially available cellulose cloth. The staining model implemented consists of

• 75% by weight of water
• 10% by weight of cellulose
• 5% by weight of cholesterol
• 2.5% by weight of edible oil (olive, castor)
• 7.5% of mineral salts (calcium phosphate, iron phosphate)

It is applied to the surface thus prepared and is allowed to dry for 24 hours. Tap water is then sprayed onto the surface.

It is evaluated by image analysis, what is the percentage of the soil deposited that has not remained on the surface.

The results obtained are given in the following tables: Percentage of soil deposited that did not remain on the surface B1 Surfactant Nonionic anionic cationic Mg / l 10g / l 50g / l 10g / l 50g / l 10g / l 50g / l 0 20 15 10 18 20 22 50 60 87 25 27 63 80 100 95 89 55 30 81 82 200 100 99 65 65 90 84 C1 Surfactant Nonionic anionic cationic Mg / l 10g / l 50g / l 10g / l 50g / l 10g / l 50g / l 0 20 15 10 18 20 22 50 60 85 23 25 60 78 100 95 88 53 30 80 79 200 100 100 60 58 88 82

It is found that a detergent composition containing the polymer B1 or C1 according to the invention facilitates the removal of toilet-type stains on ceramics.

The polymer B1 or C1 is particularly effective in the presence of nonionic or cationic surfactant at pH 3.

Example 2: Formulations for easy cleaning of windows

The table below reports the composition of four cleaning formulations (two comparative, A and B) used for window cleaning. Formulation components A comp. (in weight) B (by weight) C (by weight) D (by weight) Isopropylic alcohol 7 7 7 7 alkylpolyglucoside 0 0.3 0 0.3 Sodium dodecylbenzene sulphonate 0.4 0 0.4 0 Ammonium hydroxide 0.3 0.3 0.3 0.3 Monomethyl ether of dipropylene glycol 3 3 3 3 Polymer B2 0 0 0.05 0.05 Water Qs 100 qs 100 qs 100 Qs 100 PH of the formula 7 7 7 7 Immediate aspect 5 5 5 5 Appearance after 1 week 4 4 5 5 2 weeks 3 4 5 5 4 weeks 2 3 5 5 6 weeks 1 3 5 4 8 weeks 1 2 4 4

Four exterior windows of 1 m ² located side by side are treated as follows, with respectively formulations A, B, C and D.

Each formulation was sprayed onto the respective glass at a rate of 5 ml per m ² of surface, and then is directly wiped with a commercial cellulose cloth.

After treatment, we note in time, the appearance of the glass, exposed to the weather for 8 weeks.

An observer panel notes on a scale of 1 to 5 the cleanliness of the windows (possible traces, gloss, carbon residues).

A score of 1 corresponds to a very dirty glass, 5 corresponds to the initial appearance, just after cleaning.

This test clearly demonstrates that B2 polybetaine provides a residual anti-fouling property for at least 6 weeks.

Example 3 : Cleaning formulations for linoleum floors

The formulations tested are shown in the following table: components formulations A (by weight) B (by weight) Alkyl ether sulfate (2EO) 7 7 Polyglucoside alkyl 3 3 Glycol ether 1 1 Citrate 1 1 Polymer B7 0 1 Water qs 100 Qs 100 Drying time 180 seconds 120 seconds

Formulations A and B are diluted before use, at the rate of 10 g of formulation in 1 liter of water. One half of the soil is treated with Formulation A and the other is treated with Formulation B additive.

The floor is in linoleum.

The user notes how fast the soil becomes dry by passing his hand over it.

Example A is given for comparison. The drying rate results of formulas A and B show that the polymer provides in the formula a marked improvement in the drying speed for the consumer.

With the additive formulation, the drying time is reduced by about 30%. The user also notes that the polymer B7 provides gloss properties during drying.

Furthermore, the part of the soil treated with the formulation B is significantly less slippery than the portion treated with the formulation A, thus giving the treated surface anti-slip properties.

After two weeks of use, the operator is asked to clean the soil with Formulation A.

It appears that the removal of soil soot and black carbon is facilitated on the part of the soil having been previously treated with the formulation B. Thus the polymer B7 gives the treated surfaces anti-adhesion properties of dirt.

Example 4: Detergent formulas for automatic dishwashers

Glasses are placed in an automatic dishwasher and the powdered detergent formula, whose composition is given in the following table, is placed in the tank provided for this purpose, with a dosage of 32 g.

No rinse aid is used in this test.

These glasses are washed with the "normal" program which gives a maximum washing temperature of 65 ° C.

During the wash cycle, an open container containing a mixture of egg, oil, cream, cheese and ketchup is simultaneously introduced into the dishwasher.

At the end of washing, the dishwasher is kept closed for 3 hours.

After the washing cycle, the performance of the detergent composition is measured in terms of anti-redeposition of dirt on the glass surface (giving rise to a deposit / white haze), as well as the hydrophilicity of the surfaces thus treated.

To do this, the glass is sprayed with a water solution and the time taken by the water film to drain (to flow homogeneously) or to remain on the surface is evaluated visually. constituents Formulation A (by weight) B (by weight) D (by weight) E (by weight) Sodium tripolyphosphate 0 45 0 45 Sodium carbonate 30 20 30 20 Sodium disilicate 15 10 15 10 Sodium citrate 20 0 20 0 Sodium sulphate 12 8 14 10 SOKALAN CP5 from BASF (copolymer of acrylate and sodium maleate) 6 0 6 0 Acusol 587 D 2 2 2 2 Plurafac LF 403 2 2 2 2 Bleach system (perborate, 1H ₂ O + TAED **) 10 10 10 10 Other additives (enzymes, perfume ...) 3 3 3 3 Polymer B1, B7 or C3 2 2 0 0 PH 10.5 10.4 10.5 10.4 "Dirty" appearance - Without polymer 2 3 - with B1 4.5 5 - with B7 4.2 4.4 - with C3 4 4.5 Drainage of water on the surface Yes Yes Yes No ** tetraacetyl-ethylenediamine

• La notation « 1 » correspond à un verre très sale.
• La notation « 5 » correspond à un verre « propre ».

Moreover, after washing, the appearance of the glasses is evaluated.

• The notation "1" corresponds to a very dirty glass.
• The notation "5" corresponds to a "clean" glass.

The results show that, during the wash cycle, the polymer B1 or B7 or the copolymer C3 puts the soil particles in suspension and prevents their deposition on the surface.

Example 5 : automatic dishwasher detergent formulas

Two comparative tests are carried out between two commercial automatic dishwashing cleaning formulations (formulations D and E) and two similar formulations (A and B) containing the polymer B1 or C3.

The composition of the formulations A, B, D and E is given in the table of Example 4 above

1 ^st comparative test

We have 4 automatic dishwashers.

Each of them is placed in a Pyrex® glass dish and, respectively, 22 g of a detergent formulation chosen from formulations A, B, D, and E.

The dishes are prewashed with the "normal" program at 55 ° C.

• P_A traité avec la formulation A
• P_B traité avec la formulation B
• P_D traité avec la formulation D
• P_E traité avec la formulation E

The dishes P thus treated are denominated as follows:

• P _A treated with Formulation A
• P _B treated with formulation B
• P _D treated with formulation D
• P _E treated with formulation E

Each dish is then cooked in a "gratin" type preparation. After being emptied of their contents, the dishes P _A and P _D are washed (1 dish per dishwasher) for 3 consecutive cycles, using the formulation D (without polybetaine)

After being emptied of their contents, the dishes P _B and P _E are washed (1 dish per dishwasher) for 3 consecutive cycles, using the formulation E (without polybetaine)

After washing, the dishes are taken out of the dishwashers and their appearance is compared. Formulation Removal of dirt (%) A (by weight) B (by weight) D (by weight) E (by weight) Without polybetaine 67 72 With B1 79 81 With C3 75 78

It is found that the soils adhere less to the prewashed dishes with the formulations A or B.

2 ^th test comparative

We have 4 automatic dishwashers.

Each of them is placed in a batch of plates and, respectively, 22 g of a detergent formulation chosen from formulations A, B, D, and E.

The batches are prewashed with the "normal" program at 55 ° C.

• L_A traité avec la formulation A
• L_B traité avec la formulation B
• L_D traité avec la formulation D
• L_E traité avec la formulation E

The lots L thus treated are called as follows:

• L _A treated with Formulation A
• L _B treated with formulation B
• L _D treated with formulation D
• _E treated with formulation E

The 4 batches of prewashed plates are stained with a model stain containing egg, beef meat, vegetable fat and proteins. It is allowed to dry for 1 hour at 60.degree.

The batches L _A and L _D are washed (1 batch per dishwasher) for 3 consecutive cycles, using the formulation D (without polybetaine).

Batches L _B and L _E are washed (1 batch per dishwasher) for 3 consecutive cycles, using the formulation E (without polybetaine).

After washing, the batches of plates are taken out of the dishwashers and their appearance is compared. Formulation Removal of dirt (%) A (by weight) B (by weight) D (by weight) E (by weight) Without polybetaine 55 65 With B1 64 79 With C3 61 78

The polymers B1 and C3 thus improve the ability of the formulations to prevent the adhesion of dirt in automatic dishwashers.

Example 6 Anti-redeposition of phosphates and calcium carbonate on articles washed in the dishwasher.

The polymer B1 or the copolymer C3 is introduced into an automatic dishwashing formulation containing or not containing sodium tripolyphosphate.

The filming is forced (formation of a white veil by depositing calcium mineral salts on the surface) by the addition of 2 grams of orthophosphate (NaHPO4) at the beginning of each cycle in the dishwasher.

The number of washing cycles (with water at 35 ° TH) necessary for the appearance of a white veil on the glasses is measured. Formulation constituents A (by weight) B (by weight) D (by weight) E (by weight) Sodium tripolyphosphate 0 45 0 45 Sodium carbonate 30 20 30 20 Sodium disilicate 15 10 15 10 Sodium citrate 20 0 20 0 Sodium sulphate 12 8 14 10 SOKALAN CP5 from BASF (copolymer of acrylate and sodium maleate) 6 0 6 0 Plurafac LF 403 2 2 2 2 Bleach system (perborate, 1 H ₂ O + TAED **) 10 10 10 10 Other additives (enzymes, perfume ...) 3 3 3 3 Polymer B1 or C3 3 3 0 0 PH 10.5 10.4 10.5 10.4 Number of cycles - without polymer 4 3 - With B1 > 10 9 - With C3 > 10 8 ** ethylene diamine tetraacetate

These results show that the B1 or C3 polymer prevents (inhibits) the deposition of phosphate and calcium carbonate on the dishes.

This type of polymer is recommended for use in 2-in-1 (washing and rinsing) or even 3-in-1 (softening, washing and rinsing) type dishwashing compositions.

Example 7 : Rinsing formulas for automatic dishwashers

The washing operation described in Example 6 with the formulation D (without sodium tripolyphosphate and without polymer B1) is repeated.

This operation is followed by a rinsing step performed with the formulations F1 to F3 rinsing given in the following table. Formulation constituents F1 F2 F3 In weight In weight in weight Nonionic surfactant C13-3OP-7OE (linear fatty alcohol EO / OP) 12 6 0 Citric acid 3 3 3 Polymer B3 0 1 2 Water Qs to 100 Qs to 100 qsp to 100 PH 5 5 5 Contact angle 25 20 15

The contact angle results obtained on the formulas F2 and F3 show that the polymer B3 provides in the formula a hydrophilization of the glass surface in the dishwasher, which is not found with the formulation F1.

The polymer of the invention advantageously makes it possible to substitute the amount of nonionic surfactant with a polymer providing the treated utensils with gloss properties (especially on glasses).

Example 8: Dishwashing formulation by hand

Two comparative tests were performed between two commercial hand dishwashing formulations (Formulations A and C) and two formulations (B and D) containing Polymer B2. Formulation constituents A% by weight B in weight% C% by weight D in weight% Sodium alkylsulphonate (C14) 20 20 13 13 Alkyl ether sulfate 5 5 0 0 Alkylamidobetaine 2 2 1 1 alkylpolyglucoside 0 0 3.2 3.2 Xylene sulfonate 3.2 3.2 1.6 1.6 Polymer B2 0 4 0 3 Water Qs to 100 Qs to 100 qsp to 100 qsp to 100 PH 7 7 7 7

1 ^st comparative test

In a first sink, a Pyrex® P _A glass dish with formulation A diluted 1000 times in water is hand-pruned.

Similarly, in a second sink, a Pyrex® P _B type glass dish with the formulation B (comprising the betaine polymer B2) is diluted in a second sink and diluted 1000 times in water.

The dishes thus treated with formulations A and B are then dried in the open air. In each dish, for one hour at 180 ° C., a preparation of the gratin type is cooked. They are then emptied of their contents.

The dish P _A is allowed to soak for 1 hour in a first sink filled with formulation A (without polybetaine) diluted a thousand times in water.

The dish P _{B was} allowed to soak for 1 hour in a second sink filled with formulation A (without polybetaine) diluted a thousand times in water.

After an hour of soaking, the dishes come out of the sinks and their appearance is compared.

It is found that the soil adheres much less to the flat P _B pretreated with the formulation B than the flat P _A.

2 ^th test comparative

Two lots of 30 plates each are soiled with a model stain containing egg, beef meat, vegetable fat and protein. It is allowed to dry for 1 hour at 60.degree.

The first batch of 30 plates (called "Lot C") is washed with formulation C (without polybetaine) in 2 liters of tap water; we count the number plates of Lot C that can be cleaned, the quantity counted is 15 plates.

The second batch of 30 plates (called "Lot D") was washed with formulation D (with polybetaine) in 2 liters of tap water; the number of plates in Lot D that can be cleaned is counted, the quantity counted is 22 plates.

The polymer B2 thus improves the cleaning capacity of the formulations for washing the dishes by hand.

Example 9: Bathroom Cleaning Formulations

The formulations used are given in the following table: Formulation constituents A by weight B in weight Sodium alkylsulphonate (C12) 3 3 Ethoxylated fatty alcohol C12 - 6 EO 5 5 Ethanol 4 4 Polymer B2 0 0.5 Water Qs to 100 Qs to 100 PH 7 7 Performance bath 6 days 10 days Wall tile 4 days 8 days

Formulation A (polybetaine-free) was sprayed on the inner surface motility of a fiberglass-reinforced polyester bath and on one half of a tiled wall surface.

Formulation B (with polybetaine) was sprayed on the other motility of the inner surface of the fiberglass-reinforced polyester bath and on the other half of the tiled wall surface.

The surfaces are then rinsed with tap water.

We then ask the user to note after how many days of use of the bathtub, he feels the need to clean "white traces" that appear either on the wall tile or on the bath.

There is a significant effect of the addition of polybetaine to prevent the appearance of spots on pretreated surfaces.

Example 10 : Toilet Bowl Treatment

• agents tensioactifs non-ioniques    0,5% en poids
• agents tensioactifs anioniques    0,5% en poids
• acide citrique    8% en poids
• eau    91% en poids

0.05 part by weight of polybetaine B1, B7, B8 or C1 is added to 100 parts by weight of a commercial formulation of toilet bowl cleaner, based on

• nonionic surfactants 0.5% by weight
• anionic surfactants 0.5% by weight
• citric acid 8% by weight
• water 91% by weight

Half of the surface of the cuvette is treated with the commercial formulation, the other half is treated with commercial polybetaine additive formulation.

The bowl is rinsed with the flush of the flush.

The model stain of the preliminary example 1 is deposited on the entire bowl with a soft brush and allowed to dry for 20 minutes before a new flush stream.

This step of deposition of soil / drying / flush stream ("cycle") is repeated; we note the number of cycles at the end of which we observe a phenomenon of soiling accumulation ("soil build-up").

The results obtained are as follows: Formulation Number of cycles before "soil build-up" commercial 3 Commercial + polybetaine B1 19 Commercial + polybetaine B7 18 Commercial + polybetaine B8 17 Commercial + polybetaine C1 17

The polymer of the invention therefore improves the removal and anti-adhesion of dirt on the toilet bowls.

Example 11: Composition for the residual treatment of car bodywork

The polymer B7 of the invention is impregnated on sodium carbonate, and the two following formulations are prepared: components Formulation Formulation STPP 60 60 Sodium carbonate 35 35 Nonionic surfactant (Rhodoclean MSC) 2 2 Polymer B7 0 3

The powder is then diluted 200 times (i.e. 10 g of powder is dissolved in 2L of water) before being applied to the car using a high pressure jet type Karcher. Half of the car is treated with the reference formulation and the other half with the additive formulation of polymer B7.

After washing, the appearance of both sides of the car is similar. After 1 month of use, the car is rinsed with water without detergent. We then compare the treated and untreated aspect. It is clear that the dust film has been removed from the side of the treated portion with the polymer of the invention.

Example 12: Improved cleaning of kitchen surfaces Preparation of the dirt

• 60g d'huile de tournesol
• 10g d'huile d'olive et
• 20g de pigments d'oxide de fer

sont mélangés sous agitation dans un bécher en plastique à température ambiante pendant 30 minutes.

• 60g of sunflower oil
• 10g of olive oil and
• 20g of iron oxide pigments

are mixed with stirring in a plastic beaker at room temperature for 30 minutes.

In another beaker, a crosslinking agent is prepared by mixing 45 g of Isooctane and 1 g of cobalt naphthenate for 30 minutes.

The final soil that will be applied to the surface is obtained by pouring 20.0 g of the crosslinking agent into the 90 g of soil. The mixture is stirred for 5 hours at room temperature before application.

Materials

We use several series of 8 squares in white Formica®, each of 5cmx5cm side and 1.3 cm thick. Each square is pre-cleaned with 0.1 ml of ethanol and allowed to dry for at least 30 minutes.

Pre-treatment formulation and pre-treatment method

A solution comprising 0.4% B7 polymer, 0.5% cationic surfactant, 4% ethylene glycol monobutyl ether, 5% isopropanol, 1% trimehylamine.

0.1ml of pretreatment solution is sprayed on the surface of each square to be evaluated; allowed to dry at room temperature for 5 minutes. A sponge moistened with water is passed three times on each surface, to ensure the homogeneity of the pretreatment.

The squares are then allowed to dry for 3 hours.

Final cleaning formulation

A formulation comprising 0.5% cationic surfactant, 4% ethylene glycol monobutyl ether, 5% isopropanol, 1% trimehylamine.

Equipment "Scraper"

This is a guide in which the 8 squares of each series are aligned horizontally.

The four squares of the center are numbered 3, 4, 5 and 6; the squares placed at the ends are numbered 1 and 2 on the one hand and 7 and 8 on the other hand.

A metal bar is placed above the squares to allow the passage of a cellulose sponge cut to the size of 4cmx4cm, from one side to the other of the squares; the sponge is likely to be applied to the squares at constant pressure using a screw, and to move from one side to the other of squares 1-8 along the guide.

Paint roller

To apply the dirt on the squares.

Test

1. 1) pre-cleaning
   Each of the 8 squares is pre-cleaned with 0.1 ml of ethanol and allowed to dry for at least 30 minutes.
2. 2) pretreatment
   four of the 8 squares are then pretreated according to the method given above
3. 3) alignment in the scraper
   the 8 squares are aligned in the scraper, the four pretreated squares (numbered 3, 4, 5 and 6) being located in the center of the scraper, the non-pretreated squares (numbered 1 and 2 on the one hand and 7 and 8 on the other hand). other) being located at the ends and serving only to avoid "edge effects".
4. 4) deposition of dirt.
   • Deposit of a "light" stain
     A drop of soil is applied to squares 3 and 5; this dirt is then distributed equitably on the squares 3 to 6 by passage of the paint roll.
     The 8 squares are then placed in an oven at 250 ° C and 50% relative humidity for 24 hours
   • Deposit of a soiling "difficult"
     A drop of soil is applied to squares 3 and 5; this dirt is then distributed equitably on the squares 3 to 6 by passage of the paint roll.
     A drop of soil is applied to squares 4 and 6; this dirt is then distributed equitably on the squares 3 to 6 by passage of the paint roll.
     The 8 squares are then placed in an oven at 250 ° C and 50% relative humidity for 24 hours
5. 5) final cleaning
   0.1 ml x 2 of the final cleaning formulation is applied in two stages using the cellulose sponge on the pretreated tiles 3 to 6.

The cellulose sponge is then moved from one side to the other of the squares 1 to 8 along the guide. There is 1 sponge passage when it has passed from square 1 to square 8, or vice versa.

We make 5 round trips (10 passes).

• Une notation de :
  • 0 correspond à aucun enlèvement de salissure
  • 5 correspond à un enlèvement total.

The removal of the dirt is then visually assessed:

• A notation of:
  • 0 corresponds to no dirt removal
  • 5 corresponds to a total removal.

The test is repeated 3 times by changing the squares to evaluate (those numbered from 3 to 6).

The average scores obtained are as follows: for the reference (ie squares only treated with the formulation not containing the polymer B7) Formulation Light stains Dirty "difficult" Reference 1.3 0 Polymer B7 3.5 2

Claims (34)

1. Composition for the cleaning or the rinsing in an aqueous or aqueous/alcoholic medium of hard surfaces comprising at least one surface-active agent and at least one polybetaine (B), with the polybetaine (B)/surface-active agent(s) ratio by weight being between 1/1 and 1/1000, said polybetaine (B) being characterized in that it :

   • exhibits betaine functional groups carried by pendent groups,

   • carries, within a pH range from 1 to 14, a permanent anionic overall charge and a permanent cationic overall charge, each individual betaine unit carrying as many permanent anionic charges as permanent cationic charges,

   ▪ the permanent cationic charge being contributed by one or more onium or inium cations of the phosphorus, sulfur or nitrogen family,

   ▪ the betaine functional groups being represented, in the case of the cations of the nitrogen family, by the following formulae (I) to (V), exhibiting a cationic charge at the center of the functional group and an anionic charge at the end of the functional group, and the formula (VI), exhibiting an anionic charge at the center of the functional group and a cationic charge at the end of the functional group :
   
           -N⁽⁺⁾(R¹)(R²)-R-A-O^(-)     (I)
   
           -(R³)C=N⁽⁺⁾(R⁴)-R-A-O^(-)     (II)
   
           -(R³)(R)C-N⁽⁺⁾(R⁴)(R⁵)-R-A-O^(-)     (III)
   
           -N⁽⁺⁾(=R⁶)-R-A-O^(-)     (IV)
   
           -N⁽⁺⁾(R¹)(R²)-R-W^(-)     (V)
   
           -R-A'(-O^(-))-R-N⁽⁺⁾(R¹)(R²)(R⁷)     (VI)
   
   

   

   in which formulae (I) to (IV)

   - the symbols R¹ , R² and R⁵, which are alike or different, represent an alkyl radical comprising from 1 to 7 carbon atoms, preferably from 1 to 2 carbon atoms,

   - the symbols R³ and R⁴ represent hydrocarbon radicals which form, with the nitrogen atom, a nitrogenous heterocycle optionally comprising one or more other heteroatoms, in particular nitrogen heteroatoms,

   - the symbol R⁶ represents a hydrocarbon radical which forms, with the nitrogen atom, a saturated or unsaturated nitrogenous heterocycle optionally comprising one or more other heteroatoms, in particular nitrogen heteroatoms,

   - the symbol R represents a linear or branched alkylene radical comprising from 1 to 15 carbon atoms, preferably from 2 to 4 carbon atoms, which is optionally substituted by one or more hydroxyl groups, or a benzylene radical,

   - the symbol A represents S(=O)(=O), OP(=O)(=O), OP(=O)(OR'), P(=O)(OR') or P(=O)(R'), where R' represents an alkyl radical comprising from 1 to 7 carbon atoms or a phenyl radical,

   

   in which formula (V)

   - the symbols R¹, R² and R have the definitions given above

   - the symbol W represents an ethenolate functional group of formula
   
           O-C(O^(-))=C(C≡N)₂
   
           O-C(O)-C^(-)(C≡N)₂
   
           O-C(O)-C(-C≡N)(=C=N^(-))
   
   

   

   in which formula (VI)

   - the symbols R¹ and R² have the definitions given above,

   - the symbol R⁷, which is identical to or different from R¹ or R², represents an alkyl radical comprising from 1 to 7 carbon atoms, preferably from 1 to 2 carbon atoms,

   - the symbol A' represents -O-P(=O)-O-,

   • and exhibits an absolute weight-average molar mass (M_w) ranging from 5000 to 3 000 000 g/mol, preferably from 8000 to 1 000 000 g/mol, very particularly between 10 000 and 500 000 g/mol,

   characterized in that the polybetaine (B) is chosen from :

   • homopolymers formed of betaine units chosen from those of following formulae (-SPE-), (-SPP-), (-SHPE-) and (-SHPP-)

   

   

   

   

   • homopolymers of sulfobetaine which is derived from 2-vinylpyridine of formula

   

   • copolymers formed of betaine units, at least two of which are different and are chosen from those of formulae (-SPE-), (-SPP-), (-SHPE-) and (-SHPP-) above,

   • copolymers formed of identical or different betaine units chosen from those of formulae (-SPE-), (-SPP-), (-SHPE-) and (-SHPP-) above and of methacrylic acid units, the amount of methacrylic acid units representing less than 50 mol %, preferably less than 30 mol %, of said copolymers,

   with said polybetaine (B) comprising less than 50 % by weight of monomer units which are nonionic, noniogenic, anionic or potentially anionic at the pH of the composition or at the pH of use of the composition.
2. Composition according to Claim 1), characterized in that the polybetaine (B) comprises less than 30 mol % of monomer units which are nonionic, noniogenic, anionic or potentially anionic at the pH of the composition or at the pH of use of the composition.
3. Composition according to any either of Claims 1) and 2), characterized in that the polybetaine (B) does not comprise monomer units other than betaine units carrying as many permanent anionic charges as permanent cationic charges at a pH ranging from 1 to 14, or else less than 50 mol %, preferably less than 30 mol %, of other potentially anionic units.
4. Composition according to Claim 1), characterized in that the polybetaine (B) is chosen from the homopolymers or copolymers formed of or comprising betaine units chosen from those of formulae (-SPE-), (-SPP-), (-SHPE-) and (-SHPP-) exhibiting an absolute weight-average molar mass (M_w) ranging from 10 000 to 150 000 g/mol.
5. Composition according to any one of the preceding claims, characterized in that the polybetaine (B) represents from 0.001 to 10 % of the weight of said composition.
6. Composition according to any one of the preceding claims, characterized in that the surface-active agent or agents represent from 0.005 to 60 %, preferably from 0.5 to 40 %, of the weight of said composition.
7. Composition according to any one of the preceding claims, characterized in that it additionally comprises at least one additive chosen from chelating agents, sequestering or scale-inhibiting agents, inorganic detergency adjuvants (builders), bleaching agents, fillers, bleaching catalysts, agents which influence the pH, polymers capable of controlling the viscosity of the mixture and/or the stability of the foams, hydrotropic agents, hydrating or moisturizing agents, biocides or disinfectants, solvents with a cleaning or degreasing activity, industrial cleaners, water-soluble organic solvents with little cleaning effect, cosolvents, antifoaming agents, abrasives, enzymes, fragrances, colorants or agents which inhibit the corrosion of metals.
8. Composition according to any one of Claims 1) to 7), characterized in that it exhibits a pH of at least 7.5 and comprises from 0.001 to 5 %, preferably from 0.005 to 2 %, by weight of polybetaine (B).
9. Composition according to Claim 8), characterized in that it additionally comprises at least one additive chosen from sequestering or scale-inhibiting agents, cationic biocides or disinfectants, surface-active agents, pH modifiers, water, cleaning or degreasing organic solvents, cosolvents, water-soluble organic solvents with little cleaning effect, bleaching agents and fragrances.
10. Composition according to Claim 8) or 9), characterized in that it is intended for the cleaning of kitchens, in that it comprises :

    • from 0.001 to 1 % by weight of polybetaine (B),

    • from 1 to 10 % by weight of water-soluble solvent, in particular isopropanol,

    • from 1 to 5 % by weight of cleaning or degreasing solvent, in particular butoxypropanol,

    • from 0.1 to 2 % by weight of monoethanolamine,

    • from 0 to 5 % by weight of at least one noncationic surface-active agent, preferably an amphoteric or nonionic surface-active agent,

    • from 0 to 1 % by weight of at least one cationic surface-active agent with a disinfecting property (in particular mixture of (n-alkyl)dimethyl(ethylbenzyl)-ammonium chloride and (n-alkyl)dimethylbenzylammonium chloride),
    the total amount of surface-active agent(s) representing from 1 to 50 % by weight,

    • from 0 to 2 % by weight of a dicarboxylic acid as scale-inhibiting agent,

    • from 0 to 5 % of a bleaching agent,

    • and from 70 to 98 % by weight of water,

    and in that it exhibits a pH preferably of 7.5 to 13, preferably of 8 to 12.
11. Composition according to any one of Claims 1) to 7), characterized in that it exhibits a pH of less than 5 and in that it comprises an inorganic or organic acidic agent and from 0.001 to 5 %, preferably from 0.01 to 2 %, of its weight of polybetaine (B).
12. Composition according to Claim 11), characterized in that it additionally comprises at least one additive chosen from nonionic, amphoteric, zwitterionic or anionic surface-active agents or their mixtures, cationic biocides or disinfectants, thickening agents, bleaching agents, water, solvents, fragrances or abrasives.
13. Composition according to Claim 11) or 12), characterized in that it is intended for the cleaning of toilet bowls, in that it comprises :

    • from 0.05 to 5 %, preferably from 0.01 to 2 %, by weight of polybetaine (B),

    • from 0.1 to approximately 40 % and preferably between 0.5 and approximately 15 % by weight of at least one acidic cleaning agent,

    • from 0.5 to 10 % by weight of at least one surface-active agent, preferably an anionic or nonionic surface-active agent,

    • optionally from 0.1 to 2 % by weight of at least one cationic surface-active agent with a disinfecting property, preferably a mixture of (n-alkyl)dimethyl-(ethylbenzyl)ammonium chloride and of (n-alkyl)dimethylbenzylammonium chloride,

    • optionally from 0.1 to 3 % by weight of at least one thickening agent, preferably a gum, very particularly a xanthan gum or a succinoglycan,

    • optionally from 1 to 10 % by weight of at least one bleaching agent,

    • optionally a preservative, a colorant, a fragrance or an abrasive,

    • and from 50 to 95 % by weight of water,

    and in that it exhibits a pH of 0.5 to 4, preferably of 1 to 4.
14. Composition according to any one of Claims 1) to 7), characterized in that it is intended for the cleaning of windows, in that it comprises :

    • from 0.001 to 10 %, preferably from 0.005 to 3 %, by weight of at least one polybetaine (B),

    • from 0.005 to 20 %, preferably from 0.5 to 10 %, by weight of at least one nonionic and/or anionic surface-active agent,

    • from 0 to 10 %, preferably from 0.5 to 5 %, by weight of at least one amphoteric surface-active agent,

    • water,

    • from 0 to 30 %, preferably from 0.5 to 15 %, by weight of at least one solvent, preferably an alcohol,

    and in that it exhibits a pH of 6 to 11.
15. Composition according to any one of Claims 1) to 9), characterized in that it is intended for the washing of dishes in automatic dishwashers, in that it comprises :

    • from 0.01 to 5 %, advantageously from 0.1 to 3 %, by weight of at least one polybetaine (B),

    • from 0.2 to 10 %, advantageously from 0.5 to 5 %, by weight of at least one surface-active agent, preferably a nonionic surface-active agent, and optionally

    • up to 90 % by weight of at least one detergency adjuvant (builder),

    • up to 10 %, preferably from 1 to 10 %, very particularly from 2 to 8 %, by weight of at least one auxiliary cleaning agent, preferably a copolymer of acrylic acid and of methylpropanesulfonic acid,

    • up to 30 % by weight of at least one bleaching agent, preferably perborate or percarbonate, which may or may not be combined with a bleaching activator,

    • up to 50 % by weight of at least one filler, preferably sodium sulfate or sodium chloride,

    and in that it exhibits a pH of 8 to 13.
16. Composition according to any one of Claims 1) to 7), characterized in that it is intended for the rinsing of dishes in automatic dishwashers, in that it comprises :

    • from 0.02 to 10 %, preferably from 0.1 to 5 %, by weight of at least one polybetaine (B),

    • from 0.1 to 20 %, advantageously from 0.2 to 15 %, by weight of at least one surface-active agent, preferably a nonionic surface-active agent,

    • from 0 to 10 %, advantageously from 0.5 to 5 %, by weight of at least one calcium-sequestering organic acid, preferably citric acid,

    • from 0 to 15 %, advantageously from 0.5 to 10 %, by weight of at least one auxiliary detergency agent, preferably a copolymer of acrylic acid and of maleic anhydride and acrylic acid homopolymers,

    and in that it exhibits a pH of 4 to 7.
17. Composition according to any one of Claims 1) to 7), characterized in that it is intended for the washing of dishes by hand, in that it comprises :

    • from 0.1 to 10 % by weight of at least one polybetaine (B),

    • from 3 to 50 %, advantageously from 10 to 40 %, by weight of at least one surface-active agent, preferably an anionic surface-active agent, and optionally

    • at least one nonionic surface-active agent,

    • at least one noncationic bactericide or disinfectant, preferably triclosan,

    • at least one synthetic cationic polymer agent,

    • at least one polymer capable of controlling the viscosity of the mixture and/or the stability of the foams,

    • at least one hydrotropic agent,

    • at least one hydrating or moisturizing agent or agent for protecting the skin,

    and in that it exhibits a pH of 5 to 9.
18. Composition according to any one of Claims 1) to 9), characterized in that it is intended for the exterior washing of motorized vehicles, in that it comprises :

    • from 0.005 to 10 % by weight of at least one polybetaine (B),

    • from 0 to 30 %, preferably from 0.1 to 15 %, by weight of at least one nonionic surface-active agent,

    • from 0 to 30 %, preferably from 0.1 to 15 %, by weight of at least one anionic surface-active agent,

    • from 0 to 30 %, preferably from 0.01 to 10 %, by weight of at least one amphoteric and/or zwitterionic surface-active agent,

    • from 0 to 30 %, preferably from 0.05 to 15 %, by weight of at least one cationic surface-active agent,
    the minimum amount of surface-active agent being at least 0.5 % by weight,

    • from 0 to 99 %, preferably from 40 to 98 %, by weight of at least one detergency adjuvant (builder),

    • optionally a hydrotropic agent, fillers or pH modifiers,

    and in that it exhibits a pH of 8 to 13.
19. Composition according to any one of Claims 1) to 7), characterized in that it is intended for the cleaning of ceramic surfaces, in particular of bathrooms, and in that it comprises :

    • from 0.02 to 5 % by weight of at least one polybetaine (B),

    • from 0 to 30 %, preferably from 0 to 20 %, by weight of at least one nonionic surface-active agent,

    • from 0 to 30 %, preferably from 0 to 20 %, by weight of at least one anionic surface-active agent,
    the total amount of surface-active agent representing from 0.5 to 50 %, preferably from 1 to 30 %, more particularly from 2 to 20 %, by weight,

    • from 0 to 25 %, preferably from 0.1 to 25 %, by weight of at least one detergency adjuvant (builder),

    • from 0 to 2 %, preferably from 0.005 to 2 %, very particularly from 0.5 to 2 %, by weight of a foam modifier,

    and in that it exhibits a pH of 2 to 12.
20. Composition according to any one of Claims 1) to 7), characterized in that it is intended for the rinsing of shower walls, in that it comprises :

    • from 0.02 to 5 %, preferably from 0.05 to 1 %, by weight of at least one polybetaine (B),

    • from 0.5 to 5 % by weight of at least one nonionic surface-active agent, preferably a polyethoxylated fatty acid ester,

    • water,

    • optionally at least one lower alcohol,

    • optionally from 0.01 to 5 % by weight of at least one metal-chelating agent,

    and in that it exhibits a pH of 7 to 11.
21. Composition according to any one of Claims 1) to 7), characterized in that it is intended for the cleaning of glass-ceramic sheets, in that it comprises :

    • from 0.01 to 5 % by weight of at least one polybetaine (B),

    • from 0.1 to 1 % by weight of at least one thickening agent, preferably xanthan gum,

    • from 10 to 60 % by weight of at least one abrasive agent, preferably calcium carbonate or silica,

    • from 1 to 10 % by weight of at least one nonionic surface-active agent,

    • from 0 to 7 % by weight of at least one solvent, preferably butyl diglycol,

    • optionally basifying or sequestering agents,

    and in that it exhibits a pH of 7 to 12.
22. Composition according to any one of Claims 1) to 7), characterized in that it is intended for the cleaning of reactors, in that it comprises :

    • from 0.02 to 5 % by weight of at least one polybetaine (B),

    • from 1 to 50 % by weight of at least one alkali metal salt, preferably a sodium or potassium phosphate, carbonate or silicate,

    • from 1 to 30 % by weight of a mixture of surface-active agents, preferably nonionic and anionic surface-active agents, very particularly of ethoxylated fatty alcohols and of laurylbenzenesulfonate,

    • from 0 to 30 % by weight of at least one solvent, preferably diisobutyl ether,

    and in that it exhibits a pH of 8 to 14.
23. Use, in a composition comprising at least one surface-active agent for cleaning or rinsing hard surfaces in an aqueous or aqueous/alcoholic medium, of at least one polybetaine (B) as defined in one of Claims 1) to 4),
    as agent which makes it possible to contribute to said surfaces antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on said surfaces.
24. Use according to Claim 23), characterized in that said polybetaine (B) is employed in a proportion of 0.001 to 10 % of the weight of said composition.
25. Use according to either one of Claims 23) and 24), characterized in that said polybetaine (B) is employed in a composition as defined in any one of Claims 6) to 22).
26. Method for improving the properties of compositions comprising at least one surface-active agent for cleaning or rinsing hard surfaces in an aqueous or aqueous/alcoholic medium by addition to said compositions of at least one polybetaine (B) as defined in one of Claims 1) to 4).
27. Method according to Claim 26), characterized in that said polybetaine (B) is added in an amount sufficient to contribute to said surfaces antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on said surfaces.
28. Method according to either one of Claims 26) and 27), characterized in that said polybetaine (B) is employed in a proportion of 0.001 to 10 % of the weight of said composition.
29. Method according to any one of Claims 26) to 28), characterized in that said polybetaine (B) is employed in a composition as defined in any one of Claims 6) to 22).
30. Method for facilitating the cleaning or rinsing of hard surfaces by bringing said surfaces into contact with a composition in an aqueous or aqueous/alcoholic medium comprising at least one surface-active agent and at least one polybetaine (B), said polybetaine (B) being as defined in one of Claims 1) to 4).
31. Method according to Claim 30), characterized in that said polybetaine (B) is present in an amount sufficient to contribute to said surfaces antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on said surfaces.
32. Method according to either one of Claims 30) and 31), characterized in that said polybetaine (B) is employed in a proportion of 0.001 to 10 % of the weight of said composition.
33. Method according to any one of Claims 30) to 32), characterized in that said polybetaine (B) is employed in a composition as defined in any one of Claims 6) to 22).
34. Method according to any one of Claims 30) to 33), characterized in that said composition is employed in an amount such that, after optional rinsing and after drying, the amount of polybetaine (B) deposited on the surface is from 0.0001 to 10 mg/m², preferably from 0.001 to 1 mg/m², of surface treated.