EP2340299B1 - Copolymer for surface processing or modification - Google Patents

Description

The present invention relates to the use of a composition for the treatment and / or modification of hard surfaces. The composition comprises a synthetic copolymer comprising cationic units and nonionic units.

The subject of the present invention is in particular the use of a cleaning or rinsing composition intended for the treatment of industrial, domestic or community hard surfaces, in particular of the ceramic, tile, glass, metal, melamine, formica or plastic type, intended to confer these include improved drying properties, and / or anti-deposition and / or anti-adhesion properties of the stains; the composition can further provide them 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 leurs sels métalliques
• au dépôt de composés d'origine végétales de type hydrocolloides ou polysaccharides.

The invention more particularly relates to the use of a cleaning or rinsing composition for the treatment of a hard surface, a composition which is capable of imparting to it improved drying properties and / or residual properties of hydrophilic, anti-deposition and / or anti-adhesion of soils, 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 cleaners or housewares are effective for cleaning the soiled hard surface but do not prevent or limit its future fouling, or even to promote its subsequent cleaning.

For the treatment and / or the modification of hard surfaces, especially for the cleaning of hard surfaces, it is known to use compositions comprising synthetic polymers.

It has thus been proposed to use linear polymers or copolymers to hydrophilize hard surfaces, for example copolymers derived from cationic monomers, acrylic acid and possibly other monomers such as acrylamide. Such applications and such compositions are described in particular in the documents EP-A-1196527 , EP-A-1196528 and EP-A-1196523 .
EP 1 911 778 relates to detergent compositions comprising a copolymer, to improve the silky texture of the skin or hair or to facilitate the disentangling of hair. WO 03/039499 relates to cleansing compositions for personal care , while WO 01/57171 relates to compositions for cleaning and / or rinsing laundry , comprising at least one surfactant and a copolymer.

In many cleaning operations, water or an aqueous composition is applied to the object to be cleaned, it is optionally rinsed and then allowed to dry. This is the case for example when cleaning dishes by hand, or when cleaning dishes automatically using a dishwasher. The drying phase may take a certain time and / or may leave traces of water-soluble or water-dispersible materials (for example traces of mineral matter contained in the water) and / or traces of dirt, generally oily, originating from the water. object to clean.

It is known to add poly (vinyl-pyrrolidone) (PVP) in certain hard surface cleaning compositions, especially in tiled surface cleaning compositions or in cleaning compositions of the surface of the toilet tanks. On these ceramic surfaces, the PVP allows a fast drying, and perceptible: we can observe the composition leave gradually the surface, and observe a front of composition to move on the surface like the ebb of a wave. We often speak of progressive dewetting, it is a discharge of water by flow rather than by evaporation. This is appreciated by the consumer who perceives the effect of the composition, and / or who perceives an effective drying. The drying obtained following the application of a composition comprising PVP is indeed rapid. The evacuation by flow also makes it possible to limit the traces.

However, PVP is of limited application: it can not be formulated in certain compositions, especially in dishwashing compositions, or only with difficulty in very narrow formulation windows. In dishwashing compositions, generally significantly charged with surfactants, it is indeed poorly dispersible, and / or of low stability in these compositions. In particular, it can affect the transparency of the compositions, whereas transparency is a quality sought by consumers.

The quality of the drying following the application of a dishwashing composition in particular remains to be improved. There is a need for surface treatment and / or modification compositions, especially hard surfaces, especially dishwashing compositions having improved drying properties. There is a need for compounds which can provide such improvements and which can be formulated easily in surface treatment and / or modification compositions.

In general, there remains a need for new compositions for treating and / or modifying surfaces and / or for new uses of synthetic polymers, in particular to provide compositions that perform better for certain functions, and / or compositions that exhibit new properties, and / or less expensive compositions, and / or compositions comprising lower amounts of active ingredient.

• les unités A comprennent au moins un groupe ammonium quaternaire ou un groupe inium, et
• les unités B sont des unités dérivant d'un monomère de formule suivante:
  
          CH₂=CR¹-CO-X-R²-OH
  
  où
  • R¹ est un atome d'hydrogène ou un groupe méthyle
  • X = -O- ou -NH-
  • R² est un groupe alkyle divalent un C₁-C₄, de préférence en C₂.

A composition for treating and / or modifying surfaces, comprising a copolymer comprising cationic units A, and other units B, characterized in that:

• the units A comprise at least one quaternary ammonium group or an inium group, and
• units B are units derived from a monomer of the following formula:
  
  CH ₂ = CR ¹ -CO-XR ² -OH
  
  or
  • R ¹ is a hydrogen atom or a methyl group
  • X = -O- or -NH-
  • R ² is a divalent alkyl group C ₁ -C ₄ , preferably C ₂ .

In the following, the copolymer is designated "copolymer of the invention".

• les unités A comprennent au moins un groupe ammonium quaternaire ou un groupe inium, et
• les unités B sont des unités dérivant d'un monomère de formule suivante :
  
          CH₂=CR¹-CO-X-R²-OH
  
  où
  • R¹ est un atome d'hydrogène ou un groupe méthyle,
  • X = -O- ou -NH-,
  • R² est un groupe alkyle divalent en C₁-C₄, de préférence en C₂,
  • et les unités A et B représentent de 50 à 100%, en moles des unités du copolymère.

The present invention relates to the use of a composition for treating and / or modifying hard surfaces, said composition comprising a copolymer comprising cationic units A and other units B, characterized in that:

• the units A comprise at least one quaternary ammonium group or an inium group, and
• units B are units derived from a monomer of the following formula:
  
  CH ₂ = CR ¹ -CO-XR ² -OH
  
  or
  • R ¹ is a hydrogen atom or a methyl group,
  • X = -O- or -NH-,
  • R ² is a divalent C ₁ -C ₄ , preferably C ₂ , alkyl group
  • and units A and B represent from 50 to 100%, in moles of the units of the copolymer.

• amélioration des propriétés antidéposition et/ou antiadhésion des salissures susceptibles de se déposer sur lesdites surfaces, et/ou
• amélioration du séchage.

The copolymer of the invention may in particular provide the following advantages

• improvement of the anti-deposition and / or anti-adhesion properties of soils liable to deposit on said surfaces, and / or
• improved drying.

• facilité de formulation de la composition,
• modularité et/ou adaptabilité à un grand nombre de compositions,
• conservation de la transparence de la composition,
• démouillage progressif, de préférence perceptible et/ou évitant des traces,
• séchage accéléré,
• traces laissées au séchage exemptes ou diminuées,
• séchage perceptible par le consommateur, notamment par observation,
• combinaison d'au moins deux de ces avantages.

The copolymer of the invention may in particular provide the following advantages, in particular for example in a dishwashing composition:

• ease of formulation of the composition,
• modularity and / or adaptability to a large number of compositions,
• preserving the transparency of the composition,
• progressive dewetting, preferably perceptible and / or avoiding traces,
• accelerated drying,
• traces left on drying, free or diminished,
• perceptible drying by the consumer, especially by observation,
• combination of at least two of these benefits.

These advantages are particularly interesting in the context of the cleaning of transparent objects, in particular transparent tableware objects, in particular made of glass or crystal. These advantages and / or the perception of these advantages can be usefully communicated, in relation with the copolymer or simply in relation to the composition by any means of communication related to the product, for example on the label, in an advertisement, via a consumer service, a website.

The copolymer of the invention is preferably used or is present in said composition in an amount effective to provide said surfaces with improved drying, and / or anti-deposition and / or anti-adhesion properties of soils deposited on said surfaces. The composition may in particular have a slow dewetting and / or rapid drying and / or without trace.

The use of the copolymer in treatment compositions and / or surface modifications is described. It may in particular be used as an agent for promoting dewetting, for example progressive and / or noticeable dewetting and / or rapid drying and / or without trace.

The invention also relates to a method for treating and / or modifying the surfaces, by applying the copolymer of the invention to the surface, preferably in the composition of the invention, said composition being optionally diluted in water with prior. The invention also relates to the surfaces thus treated and / or modified.

Definitions

In the present application, the unit derived from a monomer , for the different units of the _precursor units A, denotes a unit which can be obtained directly from said monomer by polymerization. Thus, for example, a unit derived from an acrylic or methacrylic acid ester does not cover a unit of the formula -CH ₂ -CH (COOH) -, -CH ₂ -C (CH ₃ ) (COOH) -, - CH ₂ -CH (OH) -, respectively, obtained for example by polymerizing an ester of acrylic or methacrylic acid, or vinyl acetate, respectively, and then hydrolyzing. A unit derived from acrylic or methacrylic acid for example covers a unit obtained by polymerizing a monomer (for example an acrylic or methacrylic acid ester), then reacting (for example by hydrolysis) the polymer obtained so as to obtain units of formula -CH ₂ -CH (COOH) -, or -CH ₂ -C (CH ₃ ) (COOH) -. A unit derived from a vinyl alcohol for example covers a unit obtained by polymerizing a monomer (for example a vinyl ester), then reacting (for example by hydrolysis) the polymer obtained so as to obtain units of formula -CH ₂ -CH (OH) -. Units derived from a monomer A may for example have been obtained by polymerization of monomers A _precursors and then post-polymerization reaction to obtain units comprising the betaine group. A units are not considered to be units derived from _precursor A monomers that do not include a betaine group.

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

In the present application, unless otherwise indicated, the amounts and proportions are indicated as active ingredient (as opposed to the diluted or dispersed material), and by weight.

copolymer

The copolymer of the invention comprises cationic units A and other units B. The units A comprise at least one quaternary ammonium group or an inium group. The units B are units derived from a vinyl-lactam. The A units are typically derived from monomer A comprising ethylenic unsaturation.

It is preferably a linear random copolymer. It is noted that the positive charge carried by a nitrogen atom is typically located in a group lateral to the macromolecular chain that constitutes the copolymer. The macromolecular chain is typically a polyethylenic chain (from unsaturations of the monomers), with cationic groups and lateral lactam groups.

Cationic units

• ammonium quaternaire (de formule -N⁺R₃ où R, identique ou différent, est un groupe différent de l'atome d'hydrogène, par exemple un groupe hydrocarboné, éventuellement substitué, le cas échéant interrompu par des hétéroatomes, par exemple un groupe alkyle linéaire ou branché en C₁-C₂₂, par exemple un groupe méthyle), ou
• inium (de formule =N⁺R₂ où R, identique ou différent, est un groupe différent de l'atome d'hydrogène, dont l'un fait le cas échéant partie d'un cycle relié à la double liaison, ledit cycle étant le cas échéant aromatique, au moins un des groupes R pouvant être par exemple un groupe hydrocarboné, éventuellement substitué, le cas échéant interrompu par des hétéroatomes, par exemple un groupe alkyle linéaire ou branché en C₁-C₂₂, par exemple un groupe méthyle).

A units are cationic units. They include cationic groups, including a quaternary ammonium group or an inium group. In the present application, the cationic groups do not cover cationic groups, of weak base type, which may become cationic by addition of a proton such as primary amines, secondary amines or even amide groups. The cationic groups can in particular be groups of type:

• quaternary ammonium (of formula -N ⁺ R ₃ where R, identical or different, is a group different from the hydrogen atom, for example a hydrocarbon-based group, optionally substituted, optionally interrupted by heteroatoms, for example a group linear or branched C ₁ -C ₂₂ alkyl, for example a methyl group), or
• inium (of formula = N ⁺ R ₂ where R, identical or different, is a group different from the hydrogen atom, one of which is optionally part of a ring connected to the double bond, said ring being if necessary aromatic, at least one of the groups R possibly being, for example, an optionally substituted hydrocarbon-based group, optionally interrupted by heteroatoms, for example a linear or branched C ₁ -C ₂₂ alkyl group, for example a methyl group. ).

In the case of quaternary ammonium groups, it may in particular be a trimethylammonium group.

In the case of inium groups, it may especially be a pyridinium group, preferably an alkylpyridinium group, preferably a methylpyridinium group.

The cationic group may be associated with a counter ion (anion). It may especially be a chloride, bromide, iodide, methylsulfate or ethylsulfate ion. It is noted that the anionic or potentially anionic groups of part A may constitute all or part of the counter ions associated with the cationic group. It is mentioned that the cationic units are not zwitterionic units comprising both a cationic group and an anionic or potentially anionic group (they would then be of generally zero charge). In other words, the groups R mentioned above do not include anionic substituent.

• le chlorure de triméthylammoniumpropylméthacrylate,
• le chlorure ou le bromure de triméthylammoniuméthylacrylamide ou méthacrylamide,
• le méthylsulfate de triméthylammoniumbutylacrylamide ou méthacrylamide,
• le méthylsulfate de triméthylammoniumpropylméthacrylamide (MAPTA MeS),
• le chlorure de (3-méthacrylamidopropyl)triméthylammonium (MAPTAC),
• le chlorure de (3-acrylamidopropyl)triméthylammonium (APTAC),
• le chlorure ou le méthylsulfate de méthacryloyloxyéthyl triméthylammonium,
• les sels d'acryloyloxyéthyl triméthylammonium (ADAMQUAT),
• le chlorure de N,N-diméthyldiallylammonium (DADMAC) ;
• le chlorure de diméthylaminopropylméthacrylamide,N-(3-chloro-2-hydroxypropyl) triméthylammonium (DIQUAT) ;
• le monomère de formule
  
  où X^- est un anion, de préférence chlorure ou méthylsulfate,
• le bromure, chlorure ou méthylsulfate de 1-éthyl 2-vinylpyridinium, ou de 1-éthyl 4-vinylpyridinium,
• leurs mélanges ou associations.

As examples of monomers A from which A units can be derived, mention may be made of:

• trimethylammoniumpropylmethacrylate chloride,
• trimethylammoniumethylacrylamide chloride or bromide or methacrylamide,
• trimethylammoniumbutylacrylamide methylsulfate or methacrylamide,
• trimethylammoniumpropylmethacrylamide methylsulfate (MAPTA MeS),
• (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC),
• (3-acrylamidopropyl) trimethylammonium chloride (APTAC),
• methacryloyloxyethyltrimethylammonium chloride or methylsulfate,
• acryloyloxyethyltrimethylammonium salts (ADAMQUAT),
• N, N-dimethyldiallylammonium chloride (DADMAC);
• dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT);
• the monomer of formula
  
  where X ^- is an anion, preferably chloride or methylsulfate,
• 1-ethyl-2-vinylpyridinium bromide, chloride or methylsulfate, or 1-ethyl-4-vinylpyridinium bromide,
• their mixtures or associations.

The units A can in particular be obtained by copolymerization, of monomers comprising the monomers A, mixed with other monomers). They can also be obtained by polymerization, in order to form _precursor A units, monomers comprising precursor monomers of A units (mixed with other monomers), leading to precursor units of A units, and then chemical modification of the precursor units. in order to obtain the units A. Such modifications are known. It may for example be quaternizations, for example using quaternary dimethyl sulphate or haloalkylammonium or quaternary haloalkylhydroxyalkylammonium.

Units B

• R¹ est un atome d'hydrogène ou un groupe méthyle
• X = -O- ou -NH-
• R² est un groupe alkyle divalent un C₁-C₄, de préférence en C₂.

Units B are units derived from a monomer of the following formula:

CH ₂ = CR ¹ -CO-XR ² -OH

or

• R ¹ is a hydrogen atom or a methyl group
• X = -O- or -NH-
• R ² is a divalent alkyl group C ₁ -C ₄ , preferably C ₂ .

According to a preferred embodiment, R ¹ is a hydrogen atom. Such a mode can in particular facilitate the possibility of introducing the copolymer into a large number of formulations (better compatibility).

According to a particular embodiment, it is a monomer of (meth) acrylate type, where -X- = -O-.

According to a preferred embodiment R ¹ = is a hydrogen atom, X = -O-, and R ² is a divalent C ₂ alkyl. It is then the monomer hydroxyethylacrylate (HEA).

Special compositions of the copolymer

The copolymer of the invention may comprise _other units C, optional, different from the units A and B mentioned above. Units A and B represent from 50 to 100%, preferably from 75 to 100, mol% of the units of the copolymer.

• de 1 à 25% en moles des unités A, de préférence de 3 à 13%,
• de 50 à 99% en moles des unités B, de préférence de 87 à 97%, et
• éventuellement d'autres unités, le total de toutes les unités étant égal à 100% en moles.

According to a particular embodiment, the copolymer comprises:

• from 1 to 25 mol% of the A units, preferably from 3 to 13%,
• from 50 to 99 mol% of the B units, preferably from 87 to 97%, and
• possibly other units, the total of all the units being equal to 100% in moles.

According to a particular embodiment, the molar ratio between the units A and the units B is between 1/99 and 25/75, preferably between 5/95 and 15/85.

• des unités C_N non ioniques, hydrophiles ou hydrophobes, et/ou
• des unités C_A anioniques ou potentiellement anioniques, et/ou
• des unités C_C cationiques ou potentiellement cationiques, différentes des unités A, et/ou
• des unités C_Z zwitterioniques.

The copolymer may in particular comprise, as _other C units:

• nonionic, hydrophilic or hydrophobic C _N units, and / or
• anionic or potentially anionic C _A units, and / or
• _C cationic or potentially cationic units C, different from units A, and / or
• Zwitterionic C _Z units.

The units C _N may for example be chosen from units derived from a vinyl lactam, preferably vinylpyrrolidone. It is specified that it is preferably N-vinyl-pyrrolidone.

• de 1 à 25% en moles des unités A, de préférence de 3 à 13%,
• de 50 à 98% en moles des unités B, de préférence de 55 à 96%, et
• de 1 à 49% en moles d'unités dérivant d'un vinyl-lactame, de préférence de 5 à 35%, le total de toutes les unités étant égal à 100% en moles.

The copolymer may for example comprise:

• from 1 to 25 mol% of the A units, preferably from 3 to 13%,
• from 50 to 98 mol% of the B units, preferably from 55 to 96%, and
• from 1 to 49 mol% of units derived from a vinyl lactam, preferably from 5 to 35%, the total of all units being equal to 100 mol%.

In an advantageous embodiment, the copolymer does not comprise more than 50%, preferably 35%, preferably 25% in total, of such units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 50%, preferably 35%, preferably 25% by moles in total of C _N units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 25 mol% in total of C _A units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 25 mol% in total of C _C units, preferably not at all. According to an advantageous embodiment, the copolymer comprises no more than 25 mol% in total of units _Z C, preferably not at all.

• les unités C_C, et/ou
• les unités C_N choisies parmi
  • les unités alcoxylées de formule suivante:
    
            -CH₂-CHR⁶[-X²-(CH₂-CH₂-O)_n-R⁷]-
    
    dans laquelle:
    • R⁶ est un atome d'hydrogène ou un groupe méthyle,
    • X² est un groupe de formule -CO-O-, -CO-NH- ou -C₆H₄-CH₂-
    • n est un nombre entier ou moyen supérieur ou égale à 1,
    • R⁷ est un atome d'hydrogène, un groupe alkyle ou un groupe tristyrylphenyl, et/ou
  • les unités hydroxylées de formule suivante:
    
            -CH₂-CHR⁶[-X²-R⁸]-
    
    dans laquelle:
    • R⁶ est un atome d'hydrogène ou un groupe méthyle,
    • X² est un groupe de formule -CO-O-, -CO-NH- ou -C₆H₄-CH₂-
    • R⁸ est un groupe hydrocarboné à au moins deux atomes de carbone, comprenant au moins deux groupes -OH, de préférence sur deux atomes de carbone consécutifs, et/ou
  • les unités acrylates ou méthacrylates d'hydroxyalkyle.
  • les unités C_N hydrophobes, et/ou
• les unités C_Z comprenant un groupe sulfobétaïne, de préférence toutes les unités C_Z zwitterioniques.

Ainsi, selon un mode de réalisation particulier:

• le copolymère est substantiellement dénué d'unités zwitterioniques, et
• le copolymère est substantiellement dénué d'unités anioniques ou potentiellement anioniques.

According to particular embodiments, the copolymer is substantially free (it comprises less than 1 mol%, preferably less than 0.5%, preferably not at all) of the following units:

• C _C units, and / or
• the C _N units chosen from
  • the alkoxylated units of the following formula:
    
    -CH ₂ -CHR ⁶ [-X ² - (CH ₂ -CH ₂ -O) _n -R ⁷ ] -
    
    in which:
    • R ⁶ is a hydrogen atom or a methyl group,
    • X ² is a group of formula -CO-O-, -CO-NH- or -C ₆ H ₄ -CH ₂ -
    • n is an integer or average greater than or equal to 1,
    • R ⁷ is a hydrogen atom, an alkyl group or a tristyrylphenyl group, and / or
  • the hydroxylated units of the following formula:
    
    -CH ₂ -CHR ⁶ [-X ² -R ⁸ ] -
    
    in which:
    • R ⁶ is a hydrogen atom or a methyl group,
    • X ² is a group of formula -CO-O-, -CO-NH- or -C ₆ H ₄ -CH ₂ -
    • R ⁸ is a hydrocarbon group having at least two carbon atoms, comprising at least two -OH groups, preferably two consecutive carbon atoms, and / or
  • acrylate or hydroxyalkyl methacrylate units.
  • hydrophobic C _N units, and / or
• C _Z units comprising a sulfobetaine group, preferably all zwitterionic C _Z units.

Thus, according to a particular embodiment:

• the copolymer is substantially free of zwitterionic units, and
• the copolymer is substantially free of anionic or potentially anionic units.

• de 1 à 25% en moles, de préférence de 3 à 13%, d'unités A dérivant de chlorure de N,N-diméthyldiallylammonium (DADMAC), et
• de 75 à 99% en moles, de préférence de 87 à 97%, d'unités B dérivant d'hydroxyehtylacrylate (HEA).

According to a particularly useful embodiment, A units are derived from N, N-dimethyldiallylammonium chloride (DADMAC) and the B units are derived from hydroxylethylacrylate (HEA). The following copolymers are particularly useful: copolymers comprising:

• from 1 to 25 mol%, preferably from 3 to 13%, of A units derived from N, N-dimethyldiallylammonium chloride (DADMAC), and
• from 75 to 99 mol%, preferably from 87 to 97%, of B units derived from hydroxylethyl acrylate (HEA).

It is mentioned that the copolymer may be in any convenient form, for example in solid, dry or vectorized form, for example in the form of a solution or of an emulsion or a suspension, in particular in the form of a aqueous solution. The vectorized form, for example an aqueous solution, can in particular comprising from 5 to 50% by weight of the copolymer, for example from 10 to 30% by weight. The aqueous solution can in particular be a solution obtained by a method of preparation in the aqueous phase, in particular a radical polymerization process.

The polymer of the invention may in particular have a molar mass ranging from 20,000 g / mol to 1,000,000 g / mol, preferably from 100,000 to 400,000 g / mol.

Process for preparing the copolymer

The copolymer of the invention may be prepared by any suitable method. The process will generally comprise a radical polymerization (copolymerization) step, where monomers are brought together, and a source of free radicals.

According to one embodiment, a mixture of monomers A _precursor and vinyl-lactam in the presence of a source of free radicals is polymerized (copolymerization) to obtain a copolymer comprising units B and units derived from the monomers A _precursor , and then chemically modifies these units to obtain A units (post-polymerization modification). Modifications may in particular be quaternizations of monomeric derivative A _{precursor units} comprising a ternary amine group.

• d'un monomère A (ou A_précurseur), comprenant un groupe éthylèniquement insaturé et un groupe cationique,
• de vinyle-lactame, et
• d'une source de radicaux libres.

According to a preferred embodiment, the process comprises a step of copolymerization by bringing together:

• a monomer A (or A _precursor), comprising an ethylenically unsaturated group and a cationic group,
• vinyl-lactam, and
• from a source of free radicals.

Radical polymerization processes are known to those skilled in the art. In particular, the source of free radicals, the quantity of free radicals, the introduction phases of the various compounds (monomers, source of radical pounds, etc.), the polymerization temperature, and other parameters or conditions can be varied. in a known and appropriate manner. Some details or indications are given below.

The processes can be batch type processes ("batch" in English), semi-batch type ("semi-batch" in English) or even continuous type. A semi-continuous type process typically comprises a phase of gradual introduction of at least one monomer (comonomer), preferably of all the monomers (comonomers), into a reactor, without continuous output of the reaction product, the product of reaction, comprising the polymer, being recovered at once at the end of the reaction.

It is noted that the polymerization can advantageously be carried out in aqueous solution.

Any source of free radicals can be used. In particular, free radicals can be generated spontaneously, for example by raising the temperature, with appropriate monomers such as styrene. Free radicals can be generated by irradiation, especially by UV irradiation, preferably in the presence of appropriate UV-sensitive initiators. It is possible to use initiators (or "initiators") or initiator systems, of radical type or redox type. The free radical source may be water soluble or not. It is preferable to use water-soluble or at least partially water-soluble initiators (for example water-soluble at least 50% by weight).

In general, the higher the amount of free radicals, the easier the polymerization is initiated (it is favored), but the lower the molecular weights of the copolymers obtained.

• les peroxydes d'hydrogène tels que : l'hydroperoxyde de butyle tertiaire, l'hydroperoxyde de cumène, le t-butyl-peroxyacétate, le t-butyl-peroxybenzoate, le t-butylperoxyoctoate, le t-butylperoxynéodécanoate, le t-butylperoxyisobutarate, le peroxyde de lauroyle, le t-amylperoxypivalte, le t-butylperoxypivalate, le peroxyde de dicumyl, le peroxyde de benzoyle, le persulfate de potassium, le persulfate d'ammonium,
• les composés azoïques tels que : le 2-2'-azobis(isobutyronitrile), le 2,2'-azobis(2-butanenitrile), le 4,4'-azobis(4-acide pentanoïque), le 1,1'-azobis(cyclohexane-carbonitrile), le 2-(t-butylazo)-2-cyanopropane, le 2,2'-azobis[2-méthyl-N-(1,1)-bis(hydroxyméthyl)-2-hydroxyéthyl] propionamide, le 2,2'-azobis(2-méthyl-N-hydroxyéthyl]-propionamide, le dichlorure de 2,2'-azobis(N,N'-diméthylèneisobutyramidine), le dichlorure de 2,2'-azobis (2-amidinopropane), le 2,2'-azobis (N,N'-diméthylèneisobutyramide), le 2,2'-azobis(2-méthyl-N-[1,1-bis (hydroxyméthyl)-2-hydroxyéthyl] propionamide), le 2,2'-azobis(2-méthyl-N-[1,1-bis (hydroxyméthyl)éthyl] propionamide), le 2,2'-azobis[2-méthyl-N-(2-hydroxyéthyl) propionamide], le 2,2'-azobis(isobutyramide) dihydrate,
• les systèmes redox comportant des combinaisons telles que :
• les mélanges de peroxyde d'hydrogène, d'alkyle, peresters, percarbonates et similaires et de n'importe lequel des sels de fer, des sels titaneux, formaldéhyde sulfoxylate de zinc ou formaldéhyde sulfoxylate de sodium, et des sucres réducteurs,
• les persulfates, perborate ou perchlorate de métaux alcalins ou d'ammonium en association avec un bisulfite de métal alcalin, tel que le métabisulfite de sodium, et des sucres réducteurs, et
• les persulfates de métal alcalin en association avec un acide arylphosphinique, tel que l'acide benzène phosphonique et autres similaires, et des sucres réducteurs.

In particular, the following initiators can be used:

• hydrogen peroxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butylperoxyoctoate, t-butylperoxynéodécanoate, t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate,
• azo compounds such as: 2-2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1,1'- azobis (cyclohexane-carbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) -2-hydroxyethyl] propionamide , 2,2'-azobis (2-methyl-N-hydroxyethyl) -propionamide, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dichloride, 2,2'-azobis dichloride (2- amidinopropane), 2,2'-azobis (N, N'-dimethyleneisobutyramide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (isobutyramide) dihydrate,
• redox systems with combinations such as:
• mixtures of hydrogen peroxide, alkyl, peresters, percarbonates and the like and any of the iron salts, titanium salts, zinc formaldehyde sulfoxylate or sodium formaldehyde sulfoxylate, and reducing sugars,
• persulfates, perborate or perchlorate of alkali metals or ammonium in combination with an alkali metal bisulfite, such as sodium metabisulphite, and reducing sugars, and
• alkali metal persulfates in combination with an arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.

The polymerization temperature may especially be between 25 ° C and 95 ° C. The temperature may depend on the source of free radicals. If it is not a UV initiator type source, it will be preferred to operate between 50 ° C and 95 ° C, more preferably between 60 ° C and 80 ° C. In general, the higher the temperature, the easier the polymerization is initiated (it is favored), but the lower the molecular weights of the copolymers obtained.

Composition and uses

The composition of the invention may be in various forms. It can in particular be in a liquid form. It can then comprise a liquid application vector, for example water, an alcohol or a hydro-alcoholic mixture.

The composition of the invention most often comprises at least one surfactant.

According to another embodiment, the aforementioned treatment is preferably a hard surface cleaning. Hard surfaces and their treatments and / or modifications include in the present invention the dishes and its cleaning and / or rinsing. The treatment can be a dishwashing, automatic or by hand. The treatment may be cleaning transparent walls such as glass panes or plastic, preferably vertical or inclined.

• 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, et/ou d'améliorer le séchage, en particulier pour des vitres ou miroirs verticaux ou inclinés.
  • de la vaisselle, à la main ou à l'aide d'une machine automatique ; ladite composition permet, d'observer un séchage amélioré
  • de l'extérieur de véhicules.
• 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 is particularly likely to provide the hard surfaces to be treated antideposition and / or antiadhesive properties of stains and / or improved drying properties. It can be for example:

• 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 the 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, and / or to improve drying, in particular for vertical or inclined panes or mirrors.
  • dishes, by hand or with the help of an automatic machine; said composition makes it possible to observe improved drying
  • from the outside of vehicles.
• 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

• 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.

The composition according to the invention can be in any form and can be used in many ways.
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, the copolymer of the invention is present in the composition subject of the invention in an amount effective to modify and / or treat the surface. It may for example be an amount effective to provide said surfaces with anti-deposition and / or anti-adhesion properties soils may deposit on said surfaces, and / or to provide improved drying.

Said composition subject of the invention may contain, according to its application, from 0.001 to 10% of its weight of the copolymer of the invention.

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. The extreme pH are conventional in industrial or community cleaning type 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.

The cleaning or rinsing composition according to the invention preferably further comprises at least one surfactant. This may be nonionic, anionic, amphoteric, zwitterionic or cationic. It may also be a mixture or combination of surfactants.

• 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 alkaline cation (sodium, potassium, lithium), ammonium substituted or unsubstituted (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...). Mention may in particular be made of methyl ester sulphonates whose R radical is C ₁₄ -C ₁₆ ;
• 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 ...).

• 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

A description of nonionic surfactants is given in US Patent 4,287,080 and US Patent 4,470,923 . Alkylene oxide condensates, especially ethylene oxide and optionally propylene condensates with alcohols, polyols, alkylphenols, fatty acid esters, 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 ).
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 solubilising anion such as halide (e.g. chloride, bromide, iodide), sulfate or alkylsulfate (methylsulfate), carboxylate (acetate, propionate, benzoate), alkyl or arylsulfonate.

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 "Surface Active Agents" manuals, Volume I by Schwartz and Perry and "Surface Active Agents and Detergents", Volume II by Schwartz, Perry. and Berch.

The surfactants may 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 copolymer / surfactant (s) is between 1/1 and 1/1000, advantageously 1/2 and 1/200.

The composition, preferably cleaning or rinsing according to the invention, may further comprise at least one other additive, in particular chosen from the usual addites present in the cleaning or rinsing compositions of the 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 BRIQUEST^® 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 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 [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'alkyle 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(R20)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 possèdant 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 BRIQUEST ^® 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; it may be amorphous silicates or lamellar silicates 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 with acetylated bleaching activators such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED) or chloroisocyanurate-type chlorinated products, or chlorinated products of the type; 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 [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, sulphamic acid, hydrochloric acid, hydrofluoric acid, sulfuric, nitric, chromic), carboxylic or polycarboxylic acids (acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid, lactic acid, malonic acid, oxalic acid, succinic acid and tartaric acid) or salts thereof 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 fatty alkyl 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, R1O (R20) mH wherein R1 is an alkyl group having from 3 to 8 carbons and each R2 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 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.

• 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 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 may comprise from 0.001 to 5%, preferably from 0.005 to 2%, of their weight of the copolymer of the invention.
The alkaline compositions generally comprise, in addition to the copolymer, at least one additive selected 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, in particular quaternary ammonium, such as chlorides of N-alkyl dimethyl benzyl ammonium chloride, N-alkyl dimethyl ethylbenzyl ammonium halide, N-didecydimethylammonium, chloride and di- N-alkyl dimethyl ammonium (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, alkali hydroxides, 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 du copolymère de l'invention
• 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.

Le pH d'une telle formulation est de préférence de 7,5 à 13, plus préférentiellement de 8 à 12.Advantageously, a formulation for cleaning kitchens, comprises:

• from 0.001 to 1% by weight of the copolymer of the invention
• 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.

• 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.

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 the copolymer of the invention.
The acidic compositions generally comprise, in addition to the copolymer of the invention,

• 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 an alcohol or glycol (in an amount of from 0 to 10% preferably 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 du copolymère de l'invention
• 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 the copolymer of the invention
• 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 be in particular a mineral acid such as the acid phosphoric, sulfamic, hydrochloric, hydrofluoric, sulfuric, nitric, chromic and mixtures thereof or an organic acid, especially acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid lactic, malonic, oxalic, succinic and tartaric acid 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 copolymer of the invention introduced will generally be such that, when using the cleaning composition, after optional dilution, the copolymer concentration of the invention is between 0.001 g / l and 2 g / l, preferably 0.005 g / l and 0.5 g / l.

• de 0,001 à 10 %, de préférence 0,005 à 3 % en poids du copolymère de l'invention;
• 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 the copolymer of the invention;
• 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).
  Le pH de la composition est avantageusement compris entre 6 et 11.

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 the copolymer of the invention.

• 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

Le pH est avantageusement compris entre 8 et 13.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. 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 automatic dishwashing dishes according to the invention may advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5% by weight of the copolymer of the invention relative to total weight 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, optionally polyoxyethylenated carboxylic amides .... Said compositions may further 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.

• 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 ...

La quantité minimum d'agent tensioactif présent dans de type de composition est de préférence d'au moins 0,5% de la formulation.
Le pH de la composition est avantageusement compris entre 8 et 13.Another particular embodiment of the invention is the use of an external cleaning composition facilitated, including the body, motorized vehicles (cars, trucks, buses, trains, aircraft ...).
In this case also, it may be a cleaning composition itself or a rinse composition.
The cleaning composition for motor vehicles advantageously comprises from 0.005 to 10% by weight of the copolymer of the invention, 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.

• 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.

Le pH de la composition est avantageusement compris entre 2 et 12.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 the copolymer of the invention, 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 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.
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 rinsing compositions of the shower walls comprise from 0.02% to 5% by weight, advantageously from 0.05% to 1% of the copolymer of the invention.
The other main active components of the aqueous shower rinse compositions of the present invention are at least one surfactant present in an amount 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 .
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.

• 0,01 à 5 % en poids du copolymère de l'invention;
• 0,1 à 1 % en poids d'un épaississant tel qu'une gomme xanthane ;
• 10 à 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.
  Le pH de la composition est avantageusement compris entre 7 et 12 .

The composition according to the invention can also be used for the easy cleaning of vitroceramic plates.
Advantageously, the formulations for the cleaning of vitroceramic plates of the invention comprise:

• 0.01 to 5% by weight of the copolymer of the invention;
• 0.1 to 1% by weight of a thickener such as xanthan gum;
• 10 to 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.

• de 0,02 à 5 % en poids du copolymère de l'invention;
• 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.

Le pH d'une telle composition est généralement de 8 à 14 .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.
Advantageously, said compositions comprise:

• from 0.02 to 5% by weight of the copolymer of the invention;
• 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.

Dishwashing composition

The composition of the invention may especially be a dishwashing composition, automatic or by hand. Such compositions are known. The compositions may in particular comprise at least one surfactant. Compositions for automatic dishwashing generally additionally include a builder agent ("builder").

The dishwashing detergent composition may in particular comprise from 0.01% to 5%, preferably from 0.05 to 3%, preferably from 0.2% to 1.5%, by weight, of the copolymer of the invention.

The dishwashing detergent composition may be in any form, especially in aqueous or non-aqueous liquid form, preferably concentrated in solid form or in gel form.

The dishwashing composition may be susceptible to foaming in an aqueous medium. It preferably comprises at least one surfactant. Surfactants which can be used have been mentioned above. The surfactant may especially be chosen from anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants or mixtures thereof.

The amount of surfactant, expressed in dry, may represent from 0.1 to 99%, preferably from 0.5 to 60% of the total mass of composition.

When the dishwashing composition is a soap bar type solid, the amount of surfactant, expressed as dry, can be up to 99%, preferably up to 95% of the total composition mass; this amount usually represents at least 50% of the total composition mass. The soap bar solids may further contain water and / or a water-compatible solvent in an amount of up to 20% of the mass of said solid.

By total composition mass is meant the mass of the whole composition including, in addition to the copolymer of the invention and optionally the surfactant (S), the other possible constituents (water, solvents, other additives).

Hand dishwashing compositions may further include foam modifying additives, including foam improvers, density, and / or whiteness, agents which increase the shelf life of the foam. foam and / or increasing the amount of foam. In some cases we speak of foam toners ("foam enhancers" or "foam boosters" in English). It may for example be aliphatic alcohols (AA), preferably linear, for example C ₈ -C ₂₂ , preferably C ₁₂ -C ₁₈ , more particularly C ₁₂ -C ₁₆ , or mixtures thereof. , which are described in the document WO 2006/035154 . It can also be (co) polymers, for example described in the documents WO 00/71651 , WO 00/71591 , WO 02/026844 , US 6656900 , EP1180061 , WO 99/27058 , WO 99/27054 , WO 99/27053 , WO 99/27057 , WO 00/71660 , WO 00/71659 , WO 00/71241 , WO 00/71652 , WO 00/71658 .

Preferably, the dishwashing composition further comprises water and / or at least one water-compatible solvent. Water-compatible solvent is understood to mean any solvent which, when mixed with water, forms, at ambient temperature, a single, transparent phase. The water and / or the solvent can represent up to 99.5% of the total mass of said composition; the minimum amount of water and / or solvent compatible with water is usually 1%. When it is a water / solvent mixture, said solvent can represent up to 80% of the weight of said mixture. Said solvent is preferably chosen from C ₂ -C ₈ aliphatic mono or polyalcohols, and their ethers. Examples of solvents that may be mentioned include ethanol, propanol, isopropanol, butanol, 2-butoxyethanol, diethylene glycol, 1-butoxyethanol-2-propanol and diethylene monobutyl ether.

Said dishwashing composition, especially when it is a concentrated liquid composition, may further comprise at least one polymer for controlling the viscosity and / or the stability of the foams, such as polyacrylic acids or their water-soluble salts having a molecular weight of from 1000 to 5,000,000 g / mol, the ethylene oxide-oxide block copolymers propylene of molecular weight by weight up to 30,000 g / mol, polyethylene glycols having a molecular weight of at least 400 g / mol, the biopolymers having a molecular weight of at least 10,000 g / mol; when present, said polymer may represent from 0.01 to 10% of the dry mass of the concentrated liquid composition.

By concentrated composition is meant any composition that can be diluted during use.

• les acides polyacryliques ou leurs sels comme les CARBOPOL de B.F. Goodrich, notamment les CARBOPOL 941, CARBOPOL 801, CARBOPOL 907, CARBOPOL 910, CARBOPOL 934 , CARBOPOL 940
• les copolymères blocs oxyde d'éthylène-oxyde de propylène, comme les ANTAROX de Rhodia, notamment l'ANTAROX F-88
• les biopolymères comme les gommes guar, arabique, xanthane, rhéozan, welan, les carragenanes, les dérivés de cellulose ou de guar (carboxyméthylcellulose, hydroxyéthylcellulose, hydroxypropylguar, carboxy-méthylguar, carboxyméthylhydroxypropyl-guar)

As an example of polymers capable of controlling the viscosity and / or the stability of the foams, mention may be made of

• polyacrylic acids or their salts, such as CARBOPOL from BF Goodrich, in particular CARBOPOL 941, CARBOPOL 801, CARBOPOL 907, CARBOPOL 910, CARBOPOL 934, CARBOPOL 940
• ethylene oxide-propylene oxide block copolymers, such as Rhodia ANTAROX, in particular ANTAROX F-88
• biopolymers such as guar, arabic, xanthan, rheozan, welan, carragenans, cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxy-methylguar, carboxymethylhydroxypropyl-guar)

May also be present bleaching agents, builders, hydrotropic agents, moisturizers, fragrances, biocides, preservatives and other usual additives, depending on the destination of the composition.

• des polymères cationiques synthétiques comme le MIRAPOL A550^®, le MIRAPOL A15^® commercialisés par RHODIA, le MERQUAT 550^® commercialisé par CALGON.
• des agents hydrotropes, comme les alcools courts en C₂-C₈, en particulier l'éthanol, les diols et glycols comme le diéthylène glycol, dipropylène-glycol,
• des agents hydratants ou humectants pour la peau comme le glycérol, l'urée ou des agents protecteurs de la peau, comme les protéines ou hydrolysats de protéines, les polymères cationiques comme les dérivés cationiques du guar (JAGUAR C13S^®, JAGUAR C162^®, HICARE 1000^® commercialisés par la société RHODIA.

In particular, with regard to the compositions for washing dishes by hand:

• synthetic cationic polymers such as Mirapol ^® A550, Mirapol A15 ^® marketed by Rhodia, Merquat 550 sold by Calgon ^®.
• hydrotropic agents, such as short C ₂ -C ₈ alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol,
• hydrating or moisturizing agents for the skin such as glycerol, urea or protective agents to the skin, such as proteins or protein hydrolyzates, cationic polymers such as cationic derivatives of guar (JAGUAR C13S ^®, JAGUAR C162 ^®, Hicare 1000 ^® sold by Rhodia.

It is noted that the compositions can be diluted at the time of their use, they can be diluted 10 to 50 000 times their volume according to their destination. Their surfactant concentration, after dilution, can generally be from 0.0001 to 10%, preferably from 0.001 to 5%, most preferably from 0.005 to 2%.

Use of the dishwashing composition - drying

• Etape a) éventuellement diluer la composition dans de l'eau
• Etape b) mettre en présence l'objet de vaisselle à nettoyer et la composition éventuellement diluée, le cas échéant à l'aide d'un moyen d'application,
• Etape c) généralement frotter la vaisselle à l'aide d'un moyen de frottement,
• Etape d) éventuellement rincer la vaisselle
• Etape e) sécher.

The dishwashing composition can be used in the usual manner. In the context of a manual dishwashing process, for example, it is possible to operate according to a process comprising the following steps:

• Step a) optionally dilute the composition in water
• Step b) bringing the dishwashing object to be cleaned and the optionally diluted composition into presence, if necessary using an application means,
• Step c) generally scrub the dishes using a friction means,
• Step d) possibly rinse the dishes
• Step e) Dry.

Dishwashing processes may vary by individual. Step a) may correspond to the constitution of a dishwashing bath. The dilution ratio can typically be 100 to 2000. This is sometimes referred to as a "full sink" process. In such an embodiment, the copolymer concentration of the invention may especially be from 0.00025% to 0.01%, preferably from 0.0001 to 0.005%. The dilution ratio can be adapted for this purpose. In particular it can be prescribed by any means of communication related to the product, for example on the label, in an advertisement, via a consumer service, a website. Some dilution can be made when applying the composition to a suitable application and / or rubbing means comprising water such as a sponge soaked with water or an aqueous composition, or a nonwoven pad . In such an embodiment, the copolymer concentration of the invention (after dilution) can in particular be from 1 to 100.

Step b) may in particular be performed by quenching the dishware object in a dishwashing bath. In another embodiment the composition is applied directly to the dishware object, for example by pressure on a flexible or semi-flexible container comprising the composition or with the aid of a pump, or by simple gravity. According to another mode, the composition is applied to an application means such as a sponge, a pad, a brush or the fingers of the person operating the dishes, possibly protected by gloves, and the means of application is put in contact of the dishware object. For these last two modes, we often talk about a process by direct application. It is noted that a certain dilution can then occur, step a) and step b) being then simultaneous and / or confused.

The direct application type process may be preferred and provide a more significant drying improvement. In particular it can be prescribed by any means of communication related to the product, for example on the label, in an advertisement, via a consumer service, a website.

In particular, the friction step c) can be carried out in a conventional manner by circular movements and / or reciprocating movements of the friction means on the dishware object. The friction means may be for example a sponge, a pad, a brush or the fingers of the person operating the dishes, possibly protected by gloves. It can also act on the means of application of step b). It is possible to operate the contacting while rubbing, step b) and step c) are then merged.

Step d) is generally recommended. It can be operated in a conventional manner, for example by quenching in clean water (the dishware is then removed), or by passing under a jet of water.

Step e) can be operated in a conventional manner. During this step, simply let the dishes dry, if necessary on a drainer or a cloth or other device promoting the evacuation and / or absorption of water.

Other details or advantages of the invention may appear in light of the examples which follow, without being limiting in nature.

In the examples, the letter C indicates that it is a comparative example.

Example 1 - Preparation of copolymers Example 1.1C Preparation of a copolymer VP / DADMAC 90 mol% / 10 mol%

In a glass reactor having a 1-liter jacket equipped with mechanical agitation, a refrigerant and a temperature control by a cryothermostat are added 233 g of water. Under nitrogen sweep, the temperature of the reaction medium is brought to 75 ° C. 75 ° C. are then added 76 mg of 2,2'-azobis (2-methylpropionamidine) dichloride and then 38.5 g of 65% DADMAC in water over 3 hours and 310 g of 50% n-vinylpyrrolidone in the mixture are added. water over 4 hours and 0.68 g of 2,2'-azobis (2-methylpropionamidine) dichloride in 20 g of water over 5 hours. At the end of the additions the temperature is lowered to 65 ° C. At 65 ° C. are added 1.26 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride at 25% in water. The temperature is maintained at 65 ° C for 5h. The reaction medium is then cooled to room temperature.

Example 1.2 Preparation of a copolymer HEA / DADMAC 90 mol% / 10 mol% - 08DBT034

In a glass reactor having a 1.5 liter double jacket equipped with mechanical agitation, a refrigerant and a temperature control by a cryothermostat are added 390g of water. Under nitrogen sweep, the temperature of the reaction medium is brought to 75 ° C. At 75 ° C., 0.10 g of initiator V-50 (2,2'-azobis (2-methylpropionamidine dichloride)) solubilized in 0.57 g of water are added. Then, a mixture of monomers (41.3 g of 65% DADMAC in water with 173.1 g of 2-hydroxyethyl acrylate) is added continuously over 3 hours. Simultaneously, 0.80 g of V-50 initiator in 39.2 g of water is added over 4 hours. At the end of addition of initiator, the reaction mixture is maintained at 75 ° C. for 1 hour. Subsequently, 0.50 g of solubilized V-50 initiator in 2.80 g of water is added in one go, then the reaction mixture is maintained at 75 ° C. for 1 hour. 0.50 g of solubilized V-50 initiator in 2.80 g of water are then added in one go, and the reaction mixture is then maintained at 75 ° C. for 90 minutes. The reaction medium is then cooled to room temperature.

Example 1.3 Preparation of a copolymer HEA / VP / DADMAC 80 mol% / 10 mol% / 10 mol% - 08DBT033

In a glass reactor with a 1.5-liter jacket equipped with a mechanical stirrer, a refrigerant and a temperature control by a cryothermostat are added 509 g of water. Under nitrogen sweep, the temperature of the reaction medium is brought to 75 ° C. At 75 ° C., 0.13 g of initiator V-50 (2,2'-azobis (2-methylpropionamidine dichloride)) solubilized in 0.73 g of water are added. Next, a monomer mixture (54.0 g of 65% DADMAC in water, 48.1 g of 50% n-vinylpyrrolidone in water and 200.9 g of 2-hydroxyethylacrylate - this reaction mixture has a pH ~7 adjusted with 1.5g of 10% NaOH in water) is added continuously over 3h. Simultaneously, 1.04 g of V-50 initiator solubilized in 51.0 g of water is added over 4 hours. At the end of addition of initiator, the reaction mixture is maintained at 75 ° C. for 1 hour. 0.65 g of V-50 initiator solubilized in 3.70 g of water are then added all at once, and the reaction mixture is then maintained at 75 ° C. for 1 hour. 0.65 g of solubilized V-50 initiator in 3.70 g of water are then added in one go, and the reaction mixture is then maintained at 75 ° C. for 90 minutes. The reaction medium is then cooled to room temperature.

Example 1.4 Preparation of a copolymer HEA / VP / DADMAC 60 mol% / 30 mol% / 10 mol% - 08DBT019 or 08DBT032

In a glass reactor with a 1.5-liter jacket equipped with a mechanical stirrer, a refrigerant and a temperature control by a cryothermostat are added 509 g of water. Under nitrogen sweep, the temperature of the reaction medium is brought to 75 ° C. At 75 ° C., 0.10 g of initiator V-50 (2,2'-azobis (2-methylpropionamidine dichloride)) solubilized in 0.57 g of water are added. Next, a mixture of monomers (41.85g of 65% DADMAC in water, 111.8g of 50% n-vinylpyrrolidone in water and 116.9g of 2-hydroxyethylacrylate - this reaction mixture has a pH ~7 adjusted with 0.5 g of 10% NaOH in water) is added continuously over 3 hours. At the same time, 0.80 g of V-50 initiator solubilized in 39.2 g of water is added over 4 hours. At the end of addition of initiator, the reaction mixture is maintained at 75 ° C. for 1 hour. Subsequently, 0.50 g of solubilized V-50 initiator in 2.80 g of water is added in one go, then the reaction mixture is maintained at 75 ° C. for 1 hour. Subsequently, 0.50 g of solubilized V-50 initiator in 2.80 g of water is added in one go, then the reaction mixture is maintained at 75 ° C. for 1 hour. 0.50 g of solubilized V-50 initiator in 2.80 g of water are then added in one go, and the reaction mixture is then maintained at 75 ° C. for 90 minutes. The reaction medium is then cooled to room temperature.

Example 2 - Use of the copolymer in a dishwashing liquid by hand and evaluation of the drying rate Evaluation Protocol

Objective : To estimate the drying quality of a kitchen glass that comes out of a basin of rinse water.

Principle : A kitchen glass is washed by hand using the formulation to be evaluated, rinsed and soaked in a basin of water, at 40 ° C. In order to facilitate the visualization of traces of persistent water after complete drying of the glass, this dipping is carried out in water of very high hardness. For convenience, we use Contrex® brand commercial mineral water.

The glass loaded with water, at the outlet of the basin, is placed on a support placed on a scale.

The mass of the glass is recorded while the water is flowing to obtain the mass of water remaining on the glass as a function of time, and therefore the drying profile of said glass.

Device: A metal support rod (2), whose upper end is slightly beveled, is placed on the scale (4).

A large funnel (3), turned over, covers the scale without touching the tray. The stem passes through the tube of the funnel.

The kitchen glass (1) will be placed upside down on the end of the support rod.

The only point of contact is on the bottom of the glass, inside. The end being beveled, the glass leans so as to facilitate the flow of water at one point. Water flows on the funnel. The scale measures the mass loss of the glass.

The acquisition of the measurements is done automatically (connection of the scale on a computer by an RS232 port), by a Microsoft® Excel routine. In general, one reading per second is carried out for a period of about 200 seconds.

The figure 4 presents a diagram of the device.

Operating mode:

Put on laboratory gloves.

Take a new drink.

Tare the scales.

Place the glass on the support rod.

Determine its mass: "dry glass".

Put 3 liters of Contrex® water to be heated in a thermostatic bath (40 ° C).

Cut out a piece of sponge (about 4cm sides)

Run tap water at 40 ° C.

Wet the sponge then wring it out.

Place the formulation to be evaluated on it (1 ml).

Squeeze the sponge several times in the hand to lather thoroughly. Rub the glass on all sides with the sponge full of foam.

Rinse with hot water (40 ° C). Rinse the gloves well.

Immerse in Contrex® water at 40 ° C.

Tare the scales.

Trigger the acquisition and take the glass out of the thermostat bath to place it on the stem, simultaneously.

• Arrêter l'acquisition.
• Essuyer l'eau sur le fond et les bords du verre.
• Tarer la balance sans le verre.
• Mesurer la « masse finale » du verre.

The edges of the glass should not touch the funnel so as not to distort the weighing. At 180 seconds:

• Stop the acquisition.
• Wipe the water off the bottom and edges of the glass.
• Tare the scales without the glass.
• Measure the "final mass" of the glass.

Exploitation of results:

It is necessary to subtract, from recorded mass measurements, the mass of the dry glass and the mass of water wiped (mass at 180s - final mass). Indeed, the water remaining on the top of the glass did not have the opportunity to flow because of the near-horizontal of this surface, and the water remaining on the lower edge of the glass would have elapsed if the glass had been laid flat on a commonly used surface (dish drainer, dish towel ...). We evaluate the amount of residual water on the vertical walls of the glass.

A curve of water loss as a function of time is obtained.

Formulations tested

A quantity of a copolymer of Example 1 (copolymer and quantity specified in Table 1) is added to 100 g of a commercial formulation specified in Table 1.

The curve of the loss of water is plotted against time.

In some cases observations are made: Figures 1 to 3 are photographs of glasses after drying. In the absence of copolymer ( figure 1 ), we observe a dull glass with traces of drying. With the comparative copolymer of Example 1.1C, the transparency of the glass is greatly improved, but there are still some traces of dried drops. With the comparative copolymer of Example 1.2, the transparency of the glass is greatly improved and no trace of dried drops remains.

Claims (17)

1. Use of a composition for the treatment and/or modification of hard surfaces, said composition comprising a copolymer comprising cationic units A and other units B, characterised in that:

   - the units A comprise at least one quaternary ammonium group or an inium group and

   - the units B are units deriving from a monomer of following formula:
   
           CH₂=CR¹-CO-X-R²-OH
   
   wherein

   - R¹ is a hydrogen atom or a methyl group

   - X=-O- or -NH-

   - R² is a bivalent alkyl group of C₁-C₄, preferably of C₂,

   - and the units A and B constitute from 50 to 100 %, in terms of moles, of the units of the copolymer.
2. Use according to the preceding claim, characterised in that the copolymer is a linear statistical copolymer.
3. Use according to one of the preceding claims, characterised in that the units A and B constitute from 75 to 100 %, in terms of moles, of the units of the copolymer.
4. Use according to one of the preceding claims, characterised in that the copolymer comprises:

   - from 1 to 25 %, in terms of moles, of units A, preferably from 3 to 13 %,

   - from 50 to 99 %, in terms of moles, of units B, preferably from 87 to 97 %, and

   - optionally, other units, the total of all units being 100 % in terms of moles.
5. Use according to one of the preceding claims, characterised in that the molar ratio between units A and units B is from 1/99 to 25/75, preferably from 5/95 to 15/85.
6. Use according to one of the preceding claims, characterised in that the copolymer further comprises:

   - nonionic, hydrophilic or hydrophobic units C_N, and/or

   - anionic or potentially anionic units C_A, and/or

   - cationic or potentially cationic units C_C which are different from units A, and/or

   - zwitterionic units C_Z.
7. Use according to claim 6, characterised in that the copolymer further comprises units C_N selected from units deriving from a vinyl lactam, preferably vinyl pyrrolidone.
8. Use according to claim 7, characterised in that the copolymer comprises

   - from 1 to 25 %, in terms of moles, of units A, preferably from 3 to 13 %,

   - from 50 to 98 %, in terms of moles, of units B, preferably from 55 to 96 %, and

   - from 1 to 49 %, in terms of moles, of units deriving from a vinyl lactam, preferably from 5 to 35 %, the total of all units being 100 % in terms of moles.
9. Use according to one of claims 1 to 8, characterised in that:

   - the copolymer is substantially devoid of zwitterionic units and

   - the copolymer is substantially devoid of anionic or potentially anionic units.
10. Use according to one of the preceding claims, characterised in that - R¹ is a hydrogen atom
    
            - X = -O-
    
    - R² is a bivalent alkyl group of C₁-C₄, preferably of C₂.
11. Use according to one of the preceding claims, characterised in that the units A are selected from among the units deriving from the following cationic monomers A:

    - trimethylammonium propylmethacrylate chloride,

    - trimethylammonium ethylacrylamide or methacrylamide chloride or bromide,

    - trimethylammonium butylacrylamide or methacrylamide methylsulfate,

    - trimethylammonium propylmethacrylamide methylsulfate (MAPTA MeS),

    - (3-methacrylamidopropyl)trimethylammonium chloride (MAPTAC),

    - (3-acrylamidopropyl)trimethylammonium chloride (APTAC),

    - methacryloyloxyethyl trimethylammonium chloride or methylsulfate,

    - salts of acryloyloxyethyl trimethylammonium (ADAMQUAT),

    - the bromide, chloride or methylsulfate of 1-ethyl 2-vinylpyridinium or of 1-ethyl 4-vinylpyridinium;

    - N,N-dimethyldiallylammonium chloride (DADMAC);

    - dimethylaminopropylmethacrylamide chloride,
    N-(3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT);

    - the monomer of formula

    

    wherein X^- is an anion, preferably chloride or methylsulfate,

    - the bromide, chloride or methylsulfate of 1-ethyl 2-vinylpyridinium or of 1-ethyl 4-vinylpyridinium, and

    - mixtures or associations thereof.
12. Use according to one of the preceding claims, characterised in that the units A derive from N,N-dimethyldiallylammonium chloride (DADMAC) and the units B derive from hydroxyethylacrylate (HEA).
13. Use according to one of the preceding claims, characterised in that the composition comprises at least one surfactant.
14. Use according to one of the preceding claims, characterised in that the composition comprises at least one liquid vector, preferably an aqueous, alcoholic or hydroalcoholic vector.
15. Use according to one of the preceding claims, characterised in that the treatment is hard-surface cleaning.
16. Use according to one of the preceding claims, characterised in that the treatment is automatic or manual dish-washing.
17. Method of treatment and/or modification of hard surfaces, comprising a step of applying to the surface a composition as defined in one of claims 1 to 14, said composition optionally having been diluted with water beforehand.

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