EP1966305A1 - Composition for treating and/or modifying hard surfaces, containing a synthetic polymer - Google Patents

Abstract

The present invention provides a composition for treating and/or modifying hard surfaces that comprises a synthetic microgel polymer. The composition allows in particular the hydrophilicization of the hard surfaces, useful in particular in cleaning or rinsing operations.

Description

 Composition for the treatment and / or modification of hard surfaces, comprising a synthetic polymer

The present invention relates to a composition for the treatment and / or modification of hard surfaces, comprising a synthetic polymer microgel type.

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

The subject of the invention is more particularly a cleaning or rinsing composition intended for the treatment of a hard surface, a composition which is capable of conferring on it residual properties of hydrophilicity, anti-deposition and / or anti-adhesion of soiling, so as to to avoid the subsequent presence of traces due in particular: to the drying of drops of water deposited on said surface (for example deposit of 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)

- Deposition of soaps and their metal salts - the deposition of plant origin compounds hydrocolloides or polysaccharides type.

Commercial detergent formulations can effectively clean industrial, domestic or community hard surfaces. They generally consist of an aqueous solution of surfactants, especially nonionic and anionic surfactants, or nonionic and cationic surfactants, solvents, alcohol (s) to facilitate drying, and optionally sequestering agents and bases or acids to adjust the pH. A frequent disadvantage of these detergent formulations is that the subsequent contact of the hard surface with water leads to the formation of traces during drying. In addition, the treatment with these formulations is, for most of them, only purely curative and non-preventive. Thus, industrial or household cleaners are effective for cleaning the soiled hard surface but do not allow prevent or limit its future fouling, or even 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 especially described in EP-A-1 196527, EP-A-1 196528 and EP-A-1 196523.

However, there is a need for new compositions for treating and / or modifying surfaces and / or for new uses of synthetic polymers, in particular to propose compositions that perform better for certain functions, and / or compositions presenting new properties, and / or less expensive compositions, and / or compositions comprising lower amounts of active material.

The present invention meets at least one of the requirements expressed above, by providing a composition for the treatment and / or modification of hard surfaces, comprising a synthetic polymer, characterized in that the polymer is a microgel comprising:

a chemically crosslinked polymer core comprising C units derived from a core monomer C and crosslinking units R derived from a crosslinking monomer R, and possibly macromolecular branches at the periphery of the core.

The present invention also relates to the use of microgel in a composition for the treatment and / or modification of hard surfaces, especially in a cleaning composition or rinsing hard surfaces. In particular, the microgel can contribute to:

hydrophilization of hard surfaces,

- facilitate the cleaning of hard surfaces, and / or

- facilitate the subsequent cleaning of hard surfaces.

Thus the microgel can provide in particular antideposition and / or antiadhesive properties of soils may deposit on said surfaces.

The treatment and / or the modification can in particular confer residual properties on the hard surfaces. Definitions

In the present application, the term microqel means a macromolecular compound, copolymer, comprising a core and optionally at the periphery of the core of the macromolecular branches, linked to the heart. These are architectures more or less complex, which are known to those skilled in the art. The term "star copolymer" is sometimes also used to designate microgels comprising the macromolecular branches at the periphery of the core. The terms "star copolymer" and "microgel" overlap partially, the common part being compounds comprising a chemically crosslinked polymeric core comprising macromolecular branches at the periphery. In the present application, the term "arm" is also used in place of "branches" and covers the same notion. The number of branches is generally related to the nature of the core and / or the microgel preparation process. In the present application, there is "Heart C" a microel comprising a polymer core chemically crosslinked, but not comprising macromolecular branches on the periphery of the heart. Such cores C can be obtained by copolymerization of a core monomer C having a single polymerizable group and a crosslinking monomer R having at least two polymerizable groups (crosslinking monomer), in the absence of a surfactant, or in the presence of a a small amount of surfactant (for example less than 10% by weight, preferably less than 5% by weight, or even less than 1% by weight). In particular, they are distinguished from "nanolatex" polymers obtained by emulsion polymerization in the presence of high amounts of surfactants at thermodynamic equilibrium or near. Nanolatex are polymers exhibiting different behavior of C-cores when introduced into an aqueous composition.

In the present application we note "C-branches" a microgel comprising a chemically crosslinked polymer core and macromolecular branches a periphery of the heart. Such a microgel may in particular be prepared by an "arm-first" method or by a "heart-first" type process. In the latter case, the microgel can be obtained by growth of macromolecular branches on the periphery of a core C as defined below. Methods and microgels are described below. The C-branch microgels are different from nanolatex, in particular by the presence of macromolecular branches.

In the present application, the unit derived from a monomer denotes a unit that 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) -.

Typically, the theoretical average molar mass M _b ι _O c or M _breche of a block or of a branch (in the case of a Mikto microgel) is calculated according to the following formula:

M block or branch ₁ ^ 2- JVL ι precursor where M ₁ is the molar mass of a monomer i, n, is the number of moles of the monomer i, n _pre cu _r N _r is the number of moles of functional groups which will bound the macromolecular chain of the block or branch. The functions can come from a transfer agent (or a transfer group) or an initiator, a previous block, a heart etc. If it is a previous block or a core, the number of moles can be considered as the number of moles of a compound to which the macromolecular chain of said previous block or core has been bonded, for example an agent transfer (or a transfer group) or an initiator.

The measured molar masses of branches are number-average molar masses, measured by steric exclusion chromatography (SEC), before assembly of the branches with a heart, or before formation of a heart. The molar masses measured in a block are number-average molar masses, measured by steric exclusion chromatography (SEC), after formation of the block, to which the measured molar mass of a previously formed block is optionally subtracted.

The theoretical branches generating coefficient is given by the formula r = n _Rdlfun ct / n _pre cursor, where n _dlfun ct is the number of moles of monomer moles of a crosslinking monomer R _dlfUn ct diethylenically unsaturated. The higher this coefficient, in the case of C-branch microgels, the higher the number of branches. It is mentioned that the actual number of branches of the microgel is generally not equal to this coefficient. It is mentioned that this coefficient is generally modulated according to the microgel preparation process: for a real or measured number of branches identical, it is generally for a method of the type "heart first" than for a method of type "arm first".

The measured molar mass of a microgel M _star is a weight-average molar mass measured by static light scattering experiments, using Zimm curves.

The number of branches measured n _arms for a crosslinked polymeric organic core copolymer is given by the formula: M _star = M _w ^* n _arm where M _w is the mass average molar mass measured by light scattering experiments in static using Zimm curves on a block copolymer obtained in the same manner as the star copolymer but without the use of R. cross-linking monomer.

In the present application, the term "hydrophobic" is used in its usual sense of "which has no affinity for water"; this means that the organic polymer of which it is made, taken alone (of the same composition and of the same molar mass), would form a two-phase macroscopic solution in 25% distilled water at a concentration greater than 1% by weight.

In the present application, the term "hydrophilic" is also used in its usual sense of "which has affinity for water", that is to say is not likely to form a two-phase macroscopic solution in 25% distilled water at a concentration greater than 1% by weight.

In the present application, the hydrophilicity (resp. Hydrophobicity) of a block or a branch refers to the hydrophilic quality that would have a macromolecular chain of the same composition and the same molar mass as the block or branch without being bound to the heart and / or other blocks.

By cationic or potentially cationic units are meant units which comprise a cationic or potentially cationic group. Cationic units or groups are units or groups that have at least one positive charge (usually associated with one or more anions such as chloride ion, bromide ion, sulfate group, methylsulfate group), regardless of pH the medium in which the microgel is introduced. The potentially cationic units or groups are units or groups that can be neutral or have at least one positive charge depending on the pH of the medium the microgel is introduced. In this case, we will speak of potentially cationic units in neutral form or in cationic form. By extension we can speak of cationic or potentially cationic monomers.

By anionic or potentially anionic units are meant units which comprise an anionic or potentially anionic group. Units or groups anionic units or units which have at least one negative charge (generally associated with one or more cations such as cations of alkaline or alkaline-earth compounds, for example sodium, or with one or more cationic compounds such as ammonium), whatever the pH of the medium where the microgel is present. The potentially anionic units or groups are units or groups that can be neutral or have at least one negative charge depending on the pH of the medium where the microgel is present. In this case we will speak of potentially anionic units in neutral form or in anionic form. By extension we can speak of anionic or potentially anionic monomers. Neutral units are units that do not have a charge, regardless of the pH of the medium in which the microgel is present.

By "anti-deposition and / or non-sticking properties" is meant that the treated surface retains these properties over time, even after subsequent contacts with soiling (eg rain water, water from the distribution network, added rinse water or not rinsing products, splashing oils, soaps ...). This property of remanence can be observed beyond a dozen rinsing cycles, or even in some particular cases where the rinses are numerous (eg toilets), beyond 100 cycles of rinsing. The above expression "to give the surface antideposition properties" means more particularly that the treated surface, brought into contact with a soiling in a predominantly aqueous medium, will not tend to "capture" said soiling, which significantly decreases the deposit of dirt on the surface.

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

When it is said that the presence of the microgel allows to "improve the cleaning capacity" of a formulation, it means that for the same amount of cleaning formulation (including a dishwashing formulation by hand), the formulation containing the microgel makes it possible to clean a larger number of soiled objects than a formulation that is free of them. In addition, the deposition on a hard surface of the microgel makes it possible to add antistatic properties to this surface; this property is particularly interesting in the case of synthetic surfaces.

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

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

The term "hard surfaces" is to be taken broadly; these are non-textile surfaces, which can be household, community or industrial. They may be of any material, in particular of the type: - ceramics (surfaces such as washbasins, baths, wall or floor tiles, toilet bowls, etc.) glass (surfaces such as interior and exterior windows of buildings or vehicles, mirrors, metal (surfaces such as internal or external walls of reactors, blades, panels, pipes, etc.) synthetic resins (for example bodies or interior surfaces of motorized vehicles (cars, trucks, buses, trains, airplanes ...) melamine or formica surfaces for offices, kitchens, etc.)) - plastics (for example polyvinyl chloride, polyamide, for the interior of vehicles, cars in particular)

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

Some details about the microgels for the invention, some of their characteristics and methods useful for their preparation, and the compositions themselves are given below.

Microgel Details of the microgels for the invention and methods useful for their preparation are given below. The microgel comprises:

a chemically crosslinked polymer core comprising C units derived from a core monomer C and crosslinking units R derived from a crosslinking monomer R, and

possibly macromolecular branches on the periphery of the heart. In the case where the microgel does not include the macromolecular branches at the periphery of the core, the microgel is in fact a simple microgel, not having a star architecture, designated "heart C". Details are given in the "Heart C" section below.

In the case where the microgel comprises the macromolecular branches in preperiphery of the heart, the microgel has a star architecture (chemically cross-linked polymeric core), designated by "C-branches". Details are given in the "C-branches" section below.

In both cases, the microgel is preferably capable of being obtained by a process implementing a controlled radical polymerization process, as explained below.

The microgel may in particular be different from a star copolymer (C-branchSioc microgel) comprising a core C and at the periphery of the core of the macromolecular branches each comprising: an intermediate block A bonded to the core or at least partly comprised in the core, and

a peripheral block B linked to block A,

the blocks A and B being such that:

block A is hydrophilic and block B is hydrophobic, or block A is hydrophilic and block B is cationic or potentially cationic hydrophilic.

Heart C

The core C is a chemically crosslinked copolymer capable of being obtained by polymerization, preferably by controlled radical polymerization, of a monomer mixture comprising:

at least one core monomer C comprising a single polymerizable group, preferably a monoethylenically unsaturated monomer, and

at least one crosslinking monomer R comprising at least two polymerizable groups, preferably a multiethylenically unsaturated monomer.

According to a particular embodiment, the molar ratio between the core monomer C and the crosslinking monomer R is greater than or equal to 1. According to a particular embodiment:

the core C is obtained by controlled radical polymerization using a "precursor" control or transfer agent, in the presence of a source of free radicals,

the crosslinking monomer R is a diethylenically unsaturated monomer R _dlfUn ct, and the theoretical _branching coefficient r is greater than or equal to 0.25. It is mentioned that the preparation of a core C may correspond to the first step (step a)) of a process for preparing a C-branch microgel by an "arm-first" method. Such a method is detailed below.

Thus Heart C includes:

heart units C which can derive from the core monomer C, and

crosslinking units R which can be derived from the crosslinking monomer R.

Of course, it is not excluded that the units C and the monomers C comprise several different units or are derived from several different monomers.

Microαel C-branches

The C-branch microgel architectures are known. Architectes that can be used, as well as useful methods, are described in particular in documents WO 99/58588, EP 1 123332, WO 2004/014535, WO 2005/1 16097. Thus the microgel C-Branches can be chosen from microgels. following:

- C-branches _H0m o, where each branch is of identical chemical nature, comprising at least 90 mol% of identical units,

- C-branchSbioc, where each branch is of identical chemical nature, each comprising at least one block A comprising units A and at least one block B comprising units B, block B being different from block A,

- C-Branch _stat , where each branch is of identical chemical nature, each comprising less than 90 mol% of A units and less than 90 mol% of different B units of the A units, statistically or gradient distributed,

C-Branches _M ικτo, comprising at least one branch A comprising units A, and at least one branch B comprising units B different from units A, branch A and branch B being of different chemical natures.

In the case where the microgel is a microgel C-branches _b ι _O c, the block A is conventionally defined as an intermediate block connected to the core, and the block B is conventionally defined as a peripheral block connected to the block A.

The macromolecular branches at the periphery of the heart are linked to the heart, by A and / or B units for the C-branches _Hθ mo, C-branches _sta , or C-branches microgels. branchesMiKTo, by units A of block A, for microgels C-branches _b | _O c- macromolecular branches at the periphery of the heart may constitute at least a portion of the heart. Units A and / or B for microgels C-branches _Hθm o, C-branches _sta , or C-branches _M ικτo or block A for microgels C-branches _b | _O c in this case are at least partly included in the heart. That is to say that the core C may comprise, as core units C, units identical to those of the branches: A and / or B units for the C-branches microgels _H0 mo, C-branches _sta , or C-branches _M ικτo or A units for microgels C-branches _b | _O c-

Such microgels can be obtained by methods known to those skilled in the art, including in particular the so-called "core first" method, the so-called "arm first" method ("arm"). first ") and methods for chemical crosslinking of micelles. These methods are detailed below ("useful methods"). These processes can implement controlled or living polymerization processes, using an agent or a transfer group, for example by a controlled or living radical polymerization process. In the case of microspheres C-Branches _M ικτo the "arm-first" type process is particularly suitable.

Microgels obtained by a "heart first" method may have a transfer group or a group residue at the end of the branches. Copolymers obtained by an "arm first" method may have a transfer group or a group residue in the core.

Composition of microqels - nature of units

The microgel, whether it is a C core or a C-branch microgel, comprises polymerized units. All the units mentioned below are possible, as well as their combinations in different parts of the microgel (in the heart, in the branches, in the blocks, etc.). Certain combinations are the subject of particular embodiments. For these particular modes, the combinations among all the units mentioned below are to be understood as being limited to combinations compatible with these particular modes.

According to an advantageous embodiment, the microgel comprises cationic or potentially cationic units or zwitterionic units, in the heart, and / or in the macromolecular branches at the periphery of the core. Thus these units can be included in a core C, or in a microgel C-branches. They may be core units C and / or units in macromolecular branches on the periphery of a core. The heart C units can in particular be:

cationic or potentially cationic units C _cat or zwitterionic units C ₂

anionic or potentially anionic units C _A , or neutral, hydrophilic or hydrophobic C _N units.

The crosslinking units R are preferably units derived from a crosslinking monomer R comprising at least two polymerizable groups, preferably multiethylenically unsaturated, more preferably diethylenically unsaturated R _{dlfUn ct-}

A units can be:

cationic or potentially cationic units A _cat or zwitterionic units A ₂

anionic or potentially anionic units A _A , or

neutral units A _N , hydrophilic or hydrophobic.

The B units can be:

cationic or potentially cationic units B _cat or zwitterionic units B ₂

anionic or potentially anionic units B _A , or neutral B _N units, hydrophilic or hydrophobic.

According to a particular embodiment, the microgel is a C-branchSbbc microgel where

block A is a hydrophilic intermediate block bound to the heart or at least partly comprised in the heart,

block B is a block bound to block A, comprising cationic or potentially cationic units B _cat or zwitterionic units B _z .

In this mode, preferably:

the core C comprises neutral hydrophilic core units C _Nphl ie, the intermediate block A comprises hydrophilic neutral units A _Nphl ie, and

the peripheral block B comprises cationic or potentially cationic units B _cat or zwitterionic units B _z .

According to another particular embodiment, the microgel is a microgel C-brancheBiococ where block A is an intermediate block linked to the heart or at least partly comprised in the core, comprising cationic or potentially cationic A _cat units or zwitterionic A ₂ units, and

block B is a hydrophilic peripheral block bound to block A. In this mode, preferably:

the core comprises neutral hydrophilic core units C _Nphl ie,

the intermediate block A comprises cationic or potentially cationic units A _cat , and

the peripheral block B comprises neutral hydrophilic units B _Nphl | _e .

According to another particular embodiment, the microgel is a microgel C-branchesMiKTo where:

the branches A are hydrophilic branches, and

the branches B comprise cationic or potentially cationic units B _ca , or zwitterionic units B _z .

In this mode, preferably:

the core comprises neutral hydrophilic core units C _Np hιie,

the branches A comprise neutral hydrophilic units A _Nphl ie, and

the branches B comprise cationic or potentially cationic units B _cat or zwitterionic units B ₂ .

According to another particular embodiment, the microgel is a microgel C-branches _stat where the branches comprise:

anionic or potentially anionic units A _A and / or hydrophilic or hydrophobic neutral units A _n

cationic or potentially cationic units B _cat or zwitterionic units B _z .

In this mode, preferably:

the heart comprises neutral hydrophilic core units C _Np hιie, the branches comprise

anionic or potentially anionic units A _A ,

cationic units B _cat , and

potentially cationic units B _cat and / or hydrophilic neutral units

BNphile By way of examples of potentially cationic monomers A _{n '} and / or B _cat and / or C _{cat from} which the potentially cationic units A _Cat and / or B _cat and / or C _ca can be derived, mention may be made of:

The N, N (dialkylaminoalkyl) amides of monoethylenically unsaturated α-β carboxylic acids such as N, N-dimethylaminomethyl

-acrylamide or methacrylamide, 2 (N, N-dimethylamino) ethyl acrylamide or methacrylamide, 3 (N, N-dimethylamino) propyl acrylamide or

-methacrylamide, 4 (N, N-dimethylamino) butyl acrylamide or

methacrylamide: α-β monoethylenically unsaturated amino esters such as 2 (dimethylamino) ethyl acrylate (ADAM), 2 (dimethylamino) ethyl methacrylate (DMAM or MADAM), 3 (dimethylamino) propyl methacrylate, 2 (tert-butylamino) ethyl methacrylate, 2 (dipentylamino) ethyl methacrylate, 2 (diethylamino) ethyl methacrylate • vinylpyridines

• the amino vinyl

• vinylimidazolines

Amine precursor monomers such as N-vinyl formamide, N-vinyl acetamide, which generate primary amine functions by simple acid or basic hydrolysis.

As examples of cationic monomers Ar, _at and / or B _cat and / or C _{cat from} which the potentially cationic units A _Cat and / or B _cat and / or C _cat may be derived, mention may be made of: - ammoniumacryloyl or acryloyloxy monomers as

the trimethylammoniumpropylmethacrylate salts, in particular chloride

trimethylammoniumethylacrylamide chloride or bromide or methacrylamide,

trimethylammoniumbutylacrylamide methylsulfate or methacrylamide, trimethylammoniumpropylmethacrylamide methylsulfate (MAPTA MeS),

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

- (3-acrylamidopropyl) trimethylammonium chloride or methylsulfate (APTAC or APTA MeS),

methacryloyloxyethyltrimethylammonium chloride or methylsulfate, acryloyloxyethyltrimethylammonium salts (ADAMQUAT) such as acryloyloxyethyltrimethylammonium chloride; or acryloyloxyethyltrimethylammonium methylsulfate (ADAMQUAT Cl or ADAMQUAT MeS),

methyldiethylammonium methyl ethyl acrylate (ADAEQUAT MeS), benzyldimethylammonium ethyl acrylate chloride or methyl sulfate (ADAMQUAT BZ 80),

1-ethyl-2-vinylpyridinium bromide, chloride or methylsulfate, of 1-ethyl-4-vinylpyridinium; N, N-dialkyldiallylamine monomers such as N, N-dimethyldiallylammonium chloride (DADMAC);

dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium chloride (DIQUAT chloride), dimethylaminopropylmethacrylamide methylsulphate, N- (3-methylsulfate-2-hydroxypropyl) trimethylammonium (DIQUAT methylsulfate) - the monomer of formula

where X ^' is an anion, preferably chloride or methylsulfate.

Examples of hydrophilic neutral monomers A hιiP _Np and / or B _NPHL ie and / or C _Np hιie which may be derived neutral hydrophilic units A _NPHL ie and / or B _NPHL ie and / or C _Np hιie there may be mentioned: we can mention:

Hydroxyalkyl esters of α-β ethylenically unsaturated acids such as hydroxyethyl acrylate, hydroxypropyl acrylate and methacrylate, glycerol monomethacrylate, etc. α-β ethylenically unsaturated amides, such as acrylamide, methacrylamide and N, N dimethyl methacrylamide, N-methylolacrylamide ...

Ethylenically unsaturated α-β monomers bearing a water-soluble polyoxyalkylene segment of the polyethylene oxide type, such as polyethylene oxide α-methacrylates (BISOMER S20W, S10W, ... from LAPORTE) or α, ω-dimethacrylates, SIPOMER RHODIA BEM (polyoxyethylene mét-behenyl methacrylate), the

SIPOMER SEM-25 from RHODIA (oxy-tristyrylphenyl polyoxyethylene methacrylate) ...

• vinyl alcohol, Α-β ethylenically unsaturated monomers precursors of hydrophilic units or segments such as vinyl acetate which, once polymerized, can be hydrolysed to generate vinyl alcohol units or polyvinyl alcohol segments vinylpyrrolidones

Α-β-ethylenically unsaturated monomers of the ureido type and in particular 2-imidazolidinone ethyl methacrylamido (Sipomer WAM II from RHODIA)

Nonethylene glycol methyl ether acrylate or nonethylene glycol methyl ether methacrylate

As examples of hydrophilic neutral monomers from which hydrophobic neutral units may be derived, mention may be made of:

Vinylaromatic monomers such as styrene, alpha-methylstyrene, vinyltoluene, etc.

• vinyl or vinylidene halides, such as vinyl chloride, vinylidene chloride

C ₁ -C ₁₂ alkyl esters of α-β monoethylenically unsaturated acids such as methyl, ethyl, butyl acrylates and methacrylates, 2-ethylhexyl acrylate, etc. • vinyl or allyl esters of carboxylic acids saturated such as acetates, propionates, versatates, stearates ... vinyl or allyl

Α-β monoethylenically unsaturated nitriles containing from 3 to 12 carbon atoms, such as acrylonitrile, methacrylonitrile, etc.

Α-olefins such as ethylene ... conjugated dienes, such as butadiene, isoprene, chloroprene,

Monomers capable of generating polydimethylsiloxane (PDMS) chains. Thus part B may be a silicone, for example a polydimethylsiloxane chain or a copolymer comprising dimethylsiloxy units,

Diethyleneglycolethyletheracrylate or diethyleneglycolethylethermethacrylate.

As examples of anionic or potentially anionic monomers A _A and / or B _A and / or C _A , from which anionic or potentially anionic units may be derived, mention may be made of:

Monomers possessing at least one carboxylic function, such as the α-β ethylenically unsaturated carboxylic acids or the corresponding anhydrides, such as acrylic, methacrylic, maleic or fumaric acids or anhydrides, itaconic acid, N-methacrylalanine, N-acryloylglycine and their water-soluble salts

Monomers precursors of carboxylate functions, such as tert-butyl acrylate, which generate, after polymerization, carboxylic functions by hydrolysis.

Monomers having at least one sulphate or sulphonate function, such as 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulphonic acid, sulphoethyl acrylate or methacrylate, acrylate or sulfopropyl methacrylate and their water-soluble salts • monomers having at least one phosphonate or phosphate function, such as vinylphosphonic acid, ... esters of ethylenically unsaturated phosphates such as phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 RHODIA) and those derived from polyoxyalkylene methacrylates and their water-soluble salts.

By way of examples of zwitterionic monomers A _z and / or B _z and / or C _{z from} which zwitterionic units A _z and / or B _z and / or C _z may be derived, mention may be made of:

monomers carrying a carboxybetaine group,

monomers bearing a sulphobetaine group, for example sulphopropyl dimethyl ammonium ethyl methacrylate (SPE), sulphoethyl dimethyl ammonium ethyl methacrylate, sulphobutyl dimethyl ammonium ethyl methacrylate, sulphohydroxypropyl dimethyl ammonium ethyl methacrylate (SHPE), sulphopropyl dimethylammonium propyl acrylamide, sulfopropyl dimethylammonium propyl methacrylamide (SPP), sulfohydroxypropyl dimethyl ammonium propyl methacrylamido (SHPP), sulfopropyl diethyl ammonium ethyl methacrylate, or sulfohydroxypropyl diethyl ammonium ethyl methacrylate,

monomers carrying a phosphobetaines group, such as phosphatoethyl trimethylammonium ethyl methacrylate.

The crosslinker R monomers from which R cross-linking units may be derived, for example used in the "arm first" process or in the "core first" process, or used for the preparation of a core C, may be chosen from organic compounds comprising at least two ethylenic unsaturations and at most 10 unsaturations and known as reactive radicals. Preferably, these monomers have two or three ethylenic unsaturations. Thus, mention may in particular be made of acrylic, methacrylic, acrylamido, methacrylamido, vinyl ester, vinylether, diene, styrenic, alpha-methylstyrenic and allyl derivatives. These monomers may also contain functional groups other than ethylenic unsaturations, for example hydroxyl, carboxyl, ester, amide, amino or substituted amino, mercapto, silane, epoxy or halogen functions.

The monomers belonging to these families are divinylbenzene and derivatives of divinylbenzene, vinyl methacrylate, methacrylic acid anhydride, allyl methacrylate, ethylene glycol dimethacrylate, phenylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, butanediol 1,3-dimethacrylate, butanediol 1,4-dimethacrylate, 1,6-dimethacrylate hexanediol, dodecanediol 1,12-dimethacrylate, glycerol 1,3-dimethacrylate, diurethane dimethacrylate, trimethylolpropane trimethacrylate. For the family of multifunctional acrylates, there may be mentioned vinyl acrylate, epoxy bisphenol A diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol 600 diacrylate, ethylene glycol diacrylate, diacrylate diethylene glycol, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, aliphatic urethane diacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate ethoxylated, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, aliphatic urethane triacrylate, trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate. As regards the vinyl ethers, there may be mentioned vinyl crotonate, diethylene glycoldivinyl ether, butanediol-1,4-divinyl ether, and triethylene glycol divinyl ether. For the allyl derivatives, there may be mentioned diallyl phthalate, diallyldimethylammonium chloride, diallyl maleate, sodium diallyloxyacetate, diallylphenylphosphine, diallylpyrocarbonate, diallyl succinate, N, N'-diallyltartardiamide, N, N-diallyl- 2,2,2-trifluoroacetamide, allyl ester of diallyloxy acetic acid, 1,3-diallylurea, triallylamine, triallyl trimesate, triallyl cyanurate, triallyl trimellitate, triallyl-1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione. For the acrylamido derivatives, there may be mentioned N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, glyoxal bisacrylamide, diacrylamido acetic acid. As regards the styrenic derivatives, there may be mentioned divinylbenzene and 1,3-diisopropenylbenzene. In the case of diene monomers, there may be mentioned butadiene, chloroprene and isoprene. As multiethylenically unsaturated monomers, N, N'-methylenebisacrylamide, divinylbenzene, ethylene glycol diacrylate, or trimethylolpropane triacrylate are preferred.

These multiethylenically unsaturated monomers can be used alone or in mixtures. Furthermore, they are polymerized preferably in the presence of core monomers, preferably monoethylenically unsaturated.

According to a particular mode,

the microgel comprises: cationic or potentially cationic units A _ca and / or b _ca and / or c _ca t

neutral hydrophilic units A _Nphl ie and / or B _Nphl ie and / or C _Np hιie, and

the weight ratio between the cationic or potentially cationic units and the hydrophilic neutral units is greater than or equal to 1.

Advantageously, the ratio by weight of all the cationic or potentially cationic units, often B _ca units, and the neutral units, often A _N units, is greater than or equal to 1.

The microgel may be presented in particular in the form of a powder, in the form of a dispersion in a liquid or in the form of a solution in a solvent (water or other). The form generally depends on the requirements related to the use of the microgel. It can also be related to the microgel preparation process.

The branched microgel preferably comprises at least 10 branches, and generally at most about 250 branches. The number of branches can be controlled, by choice of the method of preparation, and the type of heart used. This is known to those skilled in the art. A suitable microgel is, for example, a microgel obtained by controlled radical polymerization using a control or transfer agent.

"precursor", in the presence of a source of free radicals, a diiformally unsaturated R crosslinking monomer Rdifunct, with a theoretical branch generation coefficient greater than or equal to 0.25.

The branches may have a molecular weight (theoretical or measured) of between 1000 g / mol and 100000 g / mol. It is preferably between 10,000 g / mol and 30000 g / mol. In these branches the blocks may have a molar mass of between 1000 g / mol and 99000 g / mol, preferably between 2000 g / mol and 28000 g / mol. Useful methods for the preparation of microqel

All methods for preparing microgels as described above can be used.

Particularly advantageous processes involve controlled or living polymerization, using an agent or a transfer group, for example by a controlled or living radical polymerization process. This polymerization makes it possible in particular to prepare cores, macromolecular branches, blocks, block copolymers, in particular by growth of said cores, macromolecular branches, blocks, block copolymers. Numerous controlled or living radical polymerization processes and / or numerous transfer agents or groups have been described. They are known to those skilled in the art. It is mentioned that it is not excluded to use other methods, including ring-opening polymerizations (especially anionic or cationic), anionic or cationic polymerizations, grafting methods. By way of examples of so-called living or controlled polymerization processes, reference may especially be made to:

the processes of the applications WO 98/58974, WO 00/75207 and WO 01/42312 which implement a controlled radical polymerization by xanthate control agents; the radical polymerization process controlled by control agents of the type dithioesters or trithiocarbonates of the application WO 98/01478,

the process described in application WO 02/08307, in particular for obtaining copolymers comprising polyorganosiloxane blocks,

the radical polymerization process controlled by dithiocarbamate type control agents of the application WO 99/31144,

the radical polymerization process controlled by dithiocarbazate type control agents of the application WO 02/26836, the radical polymerization process controlled by dithiophosphoroester type control agents of the application WO 02/10223, (optionally the copolymers with blocks obtained as above by controlled radical polymerization, may undergo a purification reaction of their sulfur chain end, for example by methods of hydrolysis, oxidation, reduction, pyrolysis or substitution type) the process of the application WO 99/03894 which implements a polymerization in the presence of nitroxide precursors, the method of the application WO 96/30421 which uses a radical polymerization by atom transfer (ATRP), the radical polymerization process controlled by iniferters type control agents according to the teaching of Otu et al., Makromol. Chem. Rapid. Commun., 3, 127 (1982), the method of controlled radical polymerization controlled by degenerative transfer of iodine according to the teaching of Tatemoto et al., Jap. 50, 127, 991 (1975), Daikin Kogyo Co

Itd Japan and Matyjaszewski et al., Macromolecules, 28, 2093 (1995),

the method of radical polymerization controlled by tetraphenylethane derivatives, disclosed by D. Braun et al. In Macromol. Symp. 1 1 1, 63 (1996), or the process of radical polymerization controlled by organocobalt complexes described by Wayland et al. In J.Am. Chem. Soc. 16.7973 (1994)

- The radical polymerization process controlled by diphenylethylene (WO 00/39169 or WO 00/37507).

The controlled or living radical polymerizations carrying out transfer agents or groups (or control agents) having a group -S-CS- (Xanthates, dithioesters, trithiocarbonates, etc.) are particularly interesting.

A first practical method for the preparation of branched microgels is a "core first" method (or "heart first"). Such a method may comprise the following steps:

step a) polymerization, preferably controlled radical, to obtain a core C (chemically crosslinked polymer), of a composition comprising:

optionally at least one monoethylenically unsaturated monomer of the core (core monomer C), at least one crosslinking monomer R,

- a source of free radicals, and

- a control or transfer agent,

- step b) growth of macromolecular branches microgels C-branches _b ι _O c or C-brancheSstat or C-branches _Hθ mo from monoethylenically unsaturated monomers A and / or B, by polymerization, controlled radical Preferably, to obtain the branches related to the heart. In the context of the preparation of a C-branchSiococ microgel, step b) comprises a step b1) of growth of the intermediate block A from monomers A, to obtain blocks A bound to the core, then a step b2) of growth of a block B from monomers B, to obtain blocks B bound to the A blocks. Step a) of the "core first" process is a step of preparing a core or a statistical microgel. The product obtained is sometimes called a first-generation copolymer or polymer or microgel.

Stage b) of the "core first" process is a stage of growth of macromolecular branches from the core. The product obtained is sometimes called a second-generation copolymer or polymer or microgel.

Step b2) of the "core first" method is a step of growing a second block from the previous block. The product obtained is sometimes called a copolymer or polymer or microgel of the third generation. The monoethylenically unsaturated monomer of the core (core monomer C) may be the same as that of the branches. It can possibly be different.

A second practical method for the preparation of star copolymers is a method of "Arm first" or ("arm first") type. Such a method may comprise the following steps:

step a ') preparation, preferably by controlled radical polymerization, of macromolecular chains which will constitute the branches, comprising A and / or B units, and preferably having a control or transfer group at the end. In the case where the microgel is a microgel C-branches _b | _O c macormoléculaire the chain is a block copolymer, preferably comprising a group of control or transfer at the end of block A.

- step b ') polymerization, on the chains, preferably controlled radical, of a composition comprising:

at least one crosslinking monomer R, preferably multiethylenically unsaturated,

- possibly a source of free radicals,

optionally a core monomer (core monomer C), preferably monoethylenically unsaturated, and

the macromolecular chains of step a ').

Stage a ') of the "arm first" process is sometimes called the preparation of a first generation polymer or copolymer.

Step b ') leads to the star copolymer and is sometimes referred to as obtaining or preparing a second generation copolymer. The monoethylenically unsaturated monomer of the core (core monomer C) may be the same as that of the branches. It can possibly be different. The macromolecular branches of step a ') may be block copolymers, for example obtained by a process comprising the following steps:

step a'1): preparation of the block B by polymerization, preferably controlled radical, of a composition comprising: at least one monoethylenically unsaturated monomer B

- a source of free radicals, and

at least one control agent, it being understood that this process is preferably carried out in the absence of crosslinking monomer R (multiethylenically unsaturated), then step a'2), obtaining the block copolymer by growth of block A on the block B, by polymerization, preferably controlled radical, of a composition comprising:

at least one monoethylenically unsaturated monomer A, and

- Possibly a source of free radicals, it being understood that this process is preferably in the absence of crosslinking monomer R (multiethylenically unsaturated).

Such processes for the preparation of block copolymers are known and have been the subject of numerous publications.

For the steps of formation of the core (step a or b '), the mole fraction of crosslinking monomers R (multiethylenically unsaturated) relative to the monoethylenically unsaturated monomers of the core is advantageously between 0.001 and 1. Preferably the mole fraction is between 0.01 and 1.

The first steps of the processes (step a or more precisely a'1) are carried out in the presence of a source of free radicals. However, for some monomers, such as styrene, the free radicals for initiating the polymerization can be generated by the monoethylenically unsaturated monomer at sufficiently high temperatures generally greater than 100%. In this case, it is not necessary to add a source of additional free radicals.

The useful free radical source is usually a radical polymerization initiator. The radical polymerization initiator may be chosen from initiators conventionally used in radical polymerization. It can be for example one of the following initiators:

hydrogen peroxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butylperoxybenzoate, t-butylperoxybenzoate, 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 (2-amidinopropane) dichloride ), 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, titanous salts, zinc formaldehyde sulfoxylate or sodium formaldehyde sulphoxylate, 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 amount of initiator to be used is preferably determined so that the amount of radicals generated is at most 50 mol%, preferably at most 20 mol%, based on the amount of the agent. control or transfer.

The polymerizations may be carried out in any appropriate physical form, for example in solution in water or in a solvent for example an alcohol or THF, in emulsion in water (so-called "latex" process), in bulk, the case by controlling the temperature and / or the pH in order to render the species liquid and / or soluble or insoluble.

After carrying out the preparation methods described above, it is mentioned that it is possible to deactivate or eliminate or destroy any transfer groups present in the microgel, for example by hydrolysis, ozonolysis, or reaction with amines. It is specified that the microgels are preferably obtained directly after the polymerization and the possible deactivation, elimination or destruction of transfer groups, without the functionalization step of the copolymer after the polymerization.

Composition and uses

The composition is preferably a liquid composition, comprising a liquid application vector, for example water, an alcohol or a mixture. It most often includes a surfactant.

The composition according to the invention is particularly capable of providing the hard surfaces to be treated with antideposition and / or antiadhesive properties of soiling. It can be for example:

- A cleaning or rinsing composition for household use; it can be universal or can be more specific, such as a composition for cleaning or rinsing

- bathroom; said composition prevents in particular the deposition of soap salts around the baths and on the washbasins, prevents the growth and / or deposition of limestone crystals on these surfaces, and delays the appearance of subsequent soap stains.

- of the kitchen ; said composition makes it possible to improve the cleaning of the worktops when they are soiled by unsaturated fatty soils that may crosslink over time; the greasy stains leave the water without rubbing.

- floors (in linoleum, tiles or cement); said composition makes it possible to improve the removal of dust, soils of clay-limestone types (earth, sand, mud, etc.); the tasks on the floor can be cleaned effortlessly by simply sweeping, without brushing; in addition, said composition provides anti-slip properties. toilets ; said composition prevents the adhesion of traces of excrement on the surface; the only flow of flush is enough to remove these traces; the use of a brush is useless. - windows or mirrors; said composition makes it possible to prevent the deposit of particulate mineral or organic dirt on the surface, of the dishes, by hand or with the aid of an automatic machine; said composition makes it possible, in the case of hand washing, to facilitate the removal of residual stains from dry foods, and to wash a greater number of cutlery or utensils with the same volume of bath; the surface of cutlery and utensils still wet is no longer slippery and so does not escape the hands of the user; it was also found a "squeaky clean" effect, namely that the surface "squeaks" under the effect of friction with the finger. In the case of washing or rinsing in dishwashers, said composition allows the anti-redeposition of food stains and insoluble mineral salts of calcium, and brings brilliance to utensils and cutlery; the composition also makes it possible to no longer have to "pre-wash" cutlery or utensils before they are introduced into the dishwasher.

- A cleaning or rinsing composition for industrial or community use; it can be universal or more specific, like a composition for cleaning - reactors, steel blades, sinks, vats, dishes

- exterior or interior surfaces of buildings

- windows of buildings and buildings

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

• a gelled liquid or not, to dilute in water (possibly added another solvent) before being applied on the surface to be treated

• a liquid that is gelled 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 microgel 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 antideposition and / or antiadhesion properties soils may be deposited on said surfaces. Said composition which is the subject of the invention may contain, according to its application, from 0.001 to 10% of its weight of the microgel.

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 an amount such 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 also comprises at least one surfactant. This may be nonionic, anionic, amphoteric, zwitterionic or cationic. It may also be a mixture or combination of surfactants.

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

the alkyl ester sulfonates of formula R-CH (SO ₃ M) -COOR ', in which R represents a C ₈ alkyl radical. ₂₀ , preferably C ₁₀ -C ₁₆ , R 'is a C ₁ -C ₆ , preferably C ₁ -C _3, alkyl, and M is an alkaline (sodium, potassium, lithium), substituted or unsubstituted ammonium methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine, etc.). Mention may in particular be made of methyl ester sulphonates whose R radical is C ₁₄ -C ₁₆ ; the alkyl sulphates of formula ROSO ₃ M, in which R represents a C ₅ -C ₂₄ or preferably C ₁₀ -C ₁₈ alkyl or hydroxyalkyl radical (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 10 EO and / or OP units;

the alkylamide sulphates of formula RCONHR'OSO ₃ M OÙ R represents a C ₂ -C ₂₂ , preferably C ₆ -C ₂₀ , alkyl radical; R 'represents a C ₂ -C ₃ alkyl radical, M represents a C ₂ -C ₃ alkyl radical; 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 alkylsulfonates, C ₈ -C ₂₂ , alkylglycerol sulfonates, sulfonated polycarboxylic acids disclosed in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates, sulphate monoglycerides, and fatty acid chloride condensates with hydroxyalkylsulfonates; the cation can be an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine ...). alkylphosphates, alkylated or alkylarylated ester phosphates, such as Rhodafac RA600, Rhodafac PA15 or Rhodafac PA23 marketed by Rhodia; the cation can be an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine ...).

A description of nonionic surfactants is given in US-A-4,287,080 and US-A-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

- aliphatic carboxylic acids, C ₈ -C ₈ polyoxyalkylene containing 2 to 50 oxyalkylene (oxyethylene and / or oxypropylene), especially -C ₂

(average) or Cl ₈ (average) aliphatic alcohols polyoxyalkylenated C ₆ -C ₂₄ containing from 2 to 50 oxyalkylene (oxyethylene and / or oxypropylene), especially C _i2 (average) or Cl ₈ (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

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 in which the alkyl group contains from 6 to 20 carbon atoms, such as the Miranol C2M Conc NP marketed by RHODIA, the amphoteric derivatives of alkylpolyamines, such as AMPHIONIC XL® sold by RHODIA, AMPHOLAC 7T / X® and AMPHOLAC 7C / X® marketed by BEROL NOBEL.

Among the zwitterionic surfactants, those described in U.S. 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 disclosed in US-A-4,287,080, and in US-A-4,557,853.

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 ^" where

1 2 3

R, R and R, 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 with one or more hydroxyl function (s), or together with the nitrogen atom N ⁺ may form at least one aromatic or heterocyclic ring

4

R represents a C8-C22 alkyl or alkenyl group, preferably a C12-C22 alkyl group, an aryl or benzyl group, and

X ^" is a solubilizing anion such as halide (for example chloride, bromide, iodide), sulphate or alkyl sulphate (methyl sulphate), carboxylate (acetate, propionate, benzoate), alkyl or aryl sulphonate. There may be mentioned in particular bromides of dodecyltrimethylammonium, tetradecyltrimethylammonium, cetyltrimethylammonium, stearyl pyridinium chloride, RHODAQUAT ® TFR and RHODAMINE ® C15 marketed by RHODIA, cetyltrimethylammonium chloride (Dehyquart ACA and / or AOR from Cognis), cocobis (2-hydroxyethyl) ethylammonium chloride (Ethoquad C12 from Akso Nobel).

Other cationic surfactants, such as:

The quaternary ammonium salts of the formula

R ¹ 'R ² ' R ³ 'R ⁴ ' N ⁺ X ^" where

R 2 and R 3, which may be 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 can form together with the nitrogen atom N ⁺ a heterocyclic ring

3 '4' - R and R represent a C8-C22 alkyl or alkenyl group, preferably

C10-C22, ^{September 1 rou} P ^{e ar the} Y ^or benzyl, 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, and in particular: dialkyldimethyl ammonium chlorides such as ditallow dimethylammonium chloride or methylsulphate ..., alkylbenzyldimethylammonium chlorides; C- [0-C] alkylimidazolium salts, such as methylcellulose sulphates;

Alkylimidazolinium • substituted polyamine salts such as N-tallow-N, N ', N', triethanol-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 the well-known "Surface Active Agents" manuals, Volume I by Schwartz and Perry and "Surface Active Agents and Detergents", Volume II by Schwartz, Perry and Berch.

The surfactants may 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 microgel / surfactant (s) weight ratio 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.

These include: * chelating agents, especially of the organic phosphonate type and water-soluble aminophosphonates such as ethane 1-hydroxy-1, 1-diphosphonates, aminotri (methylene diphosphonate)

- vinyldiphosphonates - salts of oligomers or polymers of vinylphosphonic or vinyldiphosphonic acid salts of co-oligomers or random copolymers of vinylphosphonic or vinyldiphosphonic acid and acrylic acid and / or maleic anhydride and / or vinylsulfonic acid and / or acrylamidomethylpropanesulphonic acid - phosphonated polyacrylate-containing polycarboxylic acid salts with phosphonate-terminus (s)

salts of cotelomers of vinylphosphonic acid or vinyldiphosphonic acid and of acrylic acid, such as those of the BRIQUEST® or MIRAPOL A300 or 400 range 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 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 - polyaspartic or polyglutamic acid salts 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 35 from Rhodia and Sokalan CP5 from BASF (from 0 to 10%, of the total weight of said cleaning composition);

Sulphonated polyvinylstirenes or their copolymers with acrylic acid, methacrylic acid (at the rate of 0 to 10%, of the total weight of cleaning composition);

* "builders" (detergency builders improving the surface properties of surfactants) mineral type:

• Polyphosphates of alkali metals, ammonium or alkanolamines such as

RHODIAPHOS HD7 marketed by Rhodia, (from 0 to 70% of the total weight of cleaning composition);

• alkaline pyrophosphates

Alkali metal silicates, with SiO ₂ / M ₂ O ratio ranging from 1 to 4, preferably from 1.5 to 3.5, especially from 1.7 to 2.8; they may be amorphous silicates or layered silicates, such as the D and D phases of D Na ₂ Si ₂ O ₅ , sold under the references NaSKS-5, NaSKS-7, NaSKS-1 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); • cogranules 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, such as NABION® sold 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'-tetraacetylethylenediamine (TAED) or chloroisocyanurate-type chlorinated products, or chlorinated products of the same 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 sodium sulphate, sodium chloride, sodium carbonate or calcium carbonate, kaolin, silica, at 0 to 50% of the total weight of said composition; 4 transition metal-containing bleach catalysts, especially iron, manganese and cobalt complexes, such as those of the type [Mn ^ιv ₂ (OD) ₃ (Me ₃ TACN) ₂ ] (PFe) ₂ , [Fe "(MeN ₄ py) (MeCN) (CIO ₄ ) ₂ ,

[(Co '") (NH ₃ ) ₅ (OAc)] (OAc) ₂ , described in US-A-4,728,455, 5,1 14,606, 5,280,17, EP-A-909,809, US-A-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) 4 agents affecting the pH of the composition, soluble in the cleaning or rinsing medium, in particular

alkalizing additives alkali metal phosphates, carbonates, perborates, alkali metal hydroxides) or acidifying additives, such as mineral acids (phosphoric acid, polyphosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, chromic acid), carboxylic acids or polycarboxylic (acetic, hydroxyacetic, adipic, citric, formic, fumaric, gluconic, glutaric, glycolic, malic, maleic, lactic, malonic, oxalic, succinic and tartaric acids) or salts of acids such as sodium bisulfate, bicarbonates and sesquicarbonates of alkali metals.

Polymers used to control the viscosity of the mixture and / or the stability of foams formed in use, such as cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar, etc.), xanthan gum, succinoglycan (RHEOZAN® marketed by RHODIA), carob gum, carrageenan (at a level of 0 to 2% of the total weight of said cleaning composition)

* Hydrotrophic 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 10g for

100 g of said cleaning composition) 4 moisturizing agents or humectants for the skin such as glycerol, urea or skin-protecting agents, such as protein or protein hydrolysates, vegetable oils such as soybean oil, polymers cationic derivatives such as cationic derivatives of guar (Jaguar C13S®, Jaguar C162®, Hicare 1000® marketed by the company Rhodia, (at a rate of 0 to 40% of the total weight of said cleaning composition) 4 biocides or disinfectants as • biocides cationic, for example

^* quaternary monoammonium salts such as coco-alkyl benzyl dimethylammonium chlorides, C- | 2-Ci 4 alkyl benzyl dimethylammonium, coco-alkyl dichlorobenzyl dimethylammonium, tetradecyl benzyl dimethylammonium, didecyl dimethylammonium, dioctyl dimethylammonium bromide - myristyl trimethylammonium bromide, cetyltrimethylammonium

^* Heterocyclic amine salts such as chlorides monoquaternary laurylpyridinium, cetylpyridinium, of C12-C-14 alkyl benzyl imidazolium

^* triphenyl phosphonium alkyl fatty salts such as myristyl triphenyl phosphonium bromide ^* polymeric biocides, such as those derived from the reaction of 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 hydrochlorides of biguanidine polymer, such as VANTOCIL IB

Amphoteric biocides, such as derivatives of N- (N'-C8-C-8alkyl-3-aminopropyl) glycine, of N- (N '- (N "-Cs-C 1-8 alkyl-2-aminoethyl) -2 amino-glycine, N, N-bis (N'-C8-C8alkyl-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 polyalkyl or aryl phenols, cresols or resorcinols, such as o-phenylphenol or p-tert-butylphenol. , 6-n-amyl-m-cresol, alkyl and / or aryl chloro or bromophenols, such as o-benzyl-p-chlorophenol and 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 before a good cleaning or degreasing activity, such as octyl benzene alkylbenzenes, olefins having a boiling point of at least 100 ^° C., such as alpha-olefins, preferably 1-decene or 1-dodecene; glycol ethers of the general formula, R 1 O (R 2 O) m H wherein R 1 is an alkyl group having 3 to 8 carbons and each R 2 is either ethylene or propylene and m is a number ranging from 1 to 3; mention may be made of monopropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, monopropylene glycol monobutyl ether, diethylene glycol monohexyl ether, monoethylene glycol monohexyl ether, monoethylene glycol monobutyl ether and mixtures thereof. diols having from 6 to 16 carbon atoms in their molecular structure; diols are particularly interesting because in addition to their degreasing properties, they can help eliminate calcium salts

(soaps); diols containing from 8 to 12 carbon atoms are preferred, most preferably 2,2,4-trimethyl-1,3-pentanediol. other solvents such as pine oil, orange terpenes, benzyl alcohol, n-hexanol, phatlic esters of alcohols having 1 to 4 carbon atoms, butoxy propanol, butyl carbitol and the like. (2-n-butoxy-

1-methylethoxy) propan-2-ol also called butoxy propoxy propanol or dipropylene glycol monobutyl ether, diglycol hexyl (Hexyl Carbitol), butyl triglycol, diols such as 2,2,4-trimethyl-1,3-pentanediol, and their mixtures. (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)

4 water-soluble organic solvents with low cleaning properties, such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and mixtures thereof (from 0 to

40% of the total weight of said cleaning composition)

co-solvents such as monoethanolamide and / or beta-aminoalkanols, which are particularly useful in compositions with a pH greater than 1 1, in particular greater than 11.7, since they help to reduce the formation of films and traces on surfaces hard (they can be implemented at a rate of 0.05 to 5% 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 or pearling agents, etc.

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.

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 1 1.5) 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 microgel.

The alkaline compositions generally comprise, in addition to the microgel, at least one additive selected from

an agent segregating or anti-scaling (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% of the weight of the composition)

a cationic biocide or disinfectant, in particular 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 to 60%, preferably from 0 to 40%, more preferably from 0 to 15% and most preferably from 0 to 5% by weight of the composition) At least one nonionic, amphoteric, zwitterionic or anionic surfactant 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 may range from 0 to 80%, preferably from 0 to 50%, all especially from 0 to 35% of the weight of the composition)

• if necessary, a pH regulating agent, in an amount to reach, optionally after dilution or dissolution of the composition, a pH of use ranging from 7.5 to 13; the pH-regulating agent can in particular be a buffer system comprising monoethanolamine and / or a beta-aminoalkanol and potentially but preferably alkaline materials "co-buffer" of the ammonia group, C2-C4 alkanolamines, hydroxides of alkalis, silicates, borates, carbonates, bicarbonates and mixtures thereof. Preferred cotampons are alkali hydroxides. From 0.5 to 98%, preferably from 25 to 95%, especially from 45 to 90% by weight of water

A cleaning or degreasing organic solvent, in an amount which may represent from 0 to 60%, preferably from 1 to 45%, more particularly 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 which is not very clean, in an amount which can represent from 0 to 25%, preferably from 1 to 20%, especially 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.

Advantageously, a formulation for cleaning kitchens, comprises:

From 0.001 to 1% by weight of the microgel

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,

From 0 to 1% by weight of at least one cationic surfactant with a disinfecting property (in particular a mixture of n-alkyl dimethylethylbenzyl ammonium chloride and n-alkyl dimethyl benzyl ammonium chloride), the total amount of surfactant (s) (s) representative of 1 to 50% by weight

From 0 to 2% by weight of a dicarboxylic acid as antiscaling agent

• from 0 to 5% of a bleaching agent

And from 70 to 98% by weight of water. The pH of such a formulation is preferably from 7.5 to 13, more preferably from 8 to 12.

Acid-like compositions having a pH of less than 5 are particularly useful for the removal of mineral-type soils; they are particularly well suited for cleaning toilet bowls. They can comprise from 0.001 to 5%, preferably from 0.01 to 2% of their weight of the microgel.

The acid compositions generally comprise, in addition to the microgel,

A mineral or organic acidic 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 nonionic, amphoteric, zwitterionic or anionic surfactant 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-alkyl benzyl dimethyl ammonium chloride, N-alkyl dimethyl ethylbenzyl ammonium chloride, N-didecydimethylammonium halide, and di-N-alkyl dimethyl ammonium chloride; (in an amount ranging from 0.01 to 2%, preferably from 0.1 to 1% by weight of the composition) • optionally a thickening agent (in an amount ranging from 0.1 to 3%, by weight of the composition)

Optionally a bleaching agent (in an amount ranging from 1 to 10%, by weight of the composition)

From 0.5 to 99%, preferably from 50 to 98% by weight of water, a solvent, such as glycol or an alcohol, (in an amount ranging from 0 to 10%, preferably from 1 to 5% by weight), 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.

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

From 0.05 to 5%, preferably from 0.01 to 2% by weight of the microgel

A quantity of cleaning acidic agent such that the final pH of the composition is from 0.5 to 4, preferably from 1 to 4; this amount is generally from 0.1 to about 40%, and preferably from 0.5 to about 15% by weight based on the weight of the composition; the acidic agent may in particular be a mineral acid such as phosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, chromic acid and mixtures thereof or an organic acid, especially acetic, hydroxyacetic or adipic acid, citric, formic, fumaric, gluconic, glutaric, glycolic, malic, maleic, lactic, malonic, oxalic, succinic and tartaric acid as well as mixtures thereof, acid salts such as sodium bisulfate and mixtures of those -this ; 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 surfactant

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, especially 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 implemented 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 microgel introduced will generally be such that, when using the cleaning composition, after dilution, the microgel concentration is between 0.001 g / l and 2 g / l, preferably 0.005 g / l and 0.5 g / l.

The cleaning composition of the panes according to the invention comprises: from 0.001 to 10%, preferably from 0.005 to 3% by weight of the microgel;

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. 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 remainder being constituted by water and usual additives (especially perfumes). The pH of the composition is advantageously between 6 and 1 1.

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 microgel. 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. Thus they may further comprise 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, whether or not associated with a bleach activator Up to 50% by weight of at least one filler, preferably sodium sulfate or sodium chloride

The pH is advantageously between 8 and 13.

The compositions for easy rinsing of the dishes in an automatic dishwasher according to the invention may advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5% by weight, of the microgel relative to the 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.

The invention also relates to a cleaning composition for the easy washing of dishes by hand. Preferred detergent formulations of this type comprise from 0.1 to 10 parts by weight of the microgel per 100 parts by weight of said composition and contain from 3 to

50, preferably from 10 to 40 parts by weight of at least one surfactant, preferably anionic, chosen in particular from sulphates of saturated C ₅ -C ₂₄ , preferably C ₈ -C ₁₆ , aliphatic alcohols, optionally condensed with about 0.5 to 30, preferably 0.5 to 8, most preferably 0.5 to 5 moles of ethylene oxide, in acid form or in the form of a salt, especially alkali (sodium), alkaline earthy

(calcium, magnesium) ...

Preferentially, it is a foamy liquid detergent aqueous formulations for the hand-washed washing of dishes. Said formulations may further contain other additives, including other surfactants, such as: nonionic surfactants such as amine oxides, alkylglucamides, alkyl polyglucosides, oxyalkylenated derivatives of fatty alcohols, alkylamides, alkanolamides, amphoteric or zwitterionic surfactants. non-cationic bactericidal or disinfecting agents such as triclosan of synthetic cationic polymers

polymers for controlling the viscosity of the mixture and / or the stability of the foams formed on use

hydrotropic agents-moisturizing or humectant or skin-protecting agents for dyes, perfumes, preservatives, divalent salts (in particular magnesium salts). The pH of the composition is advantageously between 5 and 9.

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

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

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

nonionic surfactants (at the rate of 0 to 30%, preferably from 0.1 to 15% of the formulation),

amphoteric and / or zwitterionic surfactants (at the rate of 0 to 30%, preferably from 0.01 to 10% of the formulation)

cationic surfactants (at the rate of 0 to 30%, preferably from 0.05 to 15% of the formulation);

anionic surfactants (at the rate of 0 to 30%, preferably from 0.1 to 15% of the formulation); builders (1 to 99%, preferably 40 to 98% of the formulation); hydrotropic agents

- fillers, agents regulating the pH ...

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

The pH of the composition is advantageously between 8 and 13. The composition of the invention is also particularly suitable for easy cleaning of ceramic-type hard surfaces (tiles, bathtubs, washbasins, etc.), especially for bathrooms.

The cleaning formulation advantageously comprises from 0.02 to 5% by weight of the microgel relative to the total weight of said composition as well as at least one surfactant.

As surface-active agents, nonionic surfactants are preferred, in particular compounds produced by condensation of alkylene oxide groups 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 the 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, detersive enzymes, compatible bleaching agents, gel-forming control agents, freezing stabilizers, defrosting, bactericides, preservatives, solvents, fungicides, insect repellents, hydrotropic agents, perfumes and opacifiers or pearls. The pH of the composition is advantageously between 2 and 12.

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

The aqueous shower wall rinsing compositions comprise from 0.02% to 5% by weight, preferably 0.05 to 1% of the microgel.

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 US Pat. Nos. 5,536,452 and 5,587,022, the contents of which are incorporated by reference in the present description.

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

The pH of the composition is advantageously between 7 and 11. The composition according to the invention can also be used for the facilitated 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 microgel; 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 alkalinization agents or sequestering agents. The pH of the composition is advantageously between 7 and 12.

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

Advantageously, said compositions comprise:

from 0.02 to 5% by weight of the microgel; 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, in particular nonionic surfactants such as ethoxylated fatty alcohols and anionic surfactants such as lauryl benzene sulphonate; from 0 to 30% by weight of a solvent such as diisobutyl ester. The pH of such a composition is generally 8 to 14.

Another object of the invention is the use, in a composition, preferably comprising at least one surfactant, for the modification and / or treatment of hard surfaces, preferably for cleaning or rinsing in an aqueous medium or hydroalcoholic hard surfaces, microgel, for example as an agent to provide said surfaces antideposition properties and / or anti-adhesion soils may be deposited on said surfaces.

Another subject of the invention consists in a process for treating and / or modifying hard surfaces, for improving the properties of compositions optionally comprising at least one surfactant, preferably for cleaning or rinsing in aqueous or aqueous-alcoholic hard surfaces, by adding to said compositions the microgel.

Another subject of the invention consists of a process for treating and / or modifying hard surfaces, preferably to facilitate the cleaning or rinsing of hard surfaces, by bringing said surfaces into contact with a composition in an aqueous or aqueous-alcoholic medium, comprising the microgel and optionally at least one surfactant.

The microgel is preferably used or is present in said composition in an amount effective to provide said surfaces with anti-deposition and / or anti-adhesion properties soils may be deposited on said surfaces. The nature and amounts of the microgel present or used in said composition, as well as the other additives and different modes of application of said composition have already been mentioned above.

Other details or advantages of the invention may appear in the light of the following nonlimiting examples:

EXAMPLES

Example 1: Preparation of microqels

Three architectures of microgels have been synthesized:

1 / C-branch microgels _b ι _O c having branches of identical chemical nature, each comprising a neutral hydrophilic block polyacrylamide, and a hydrophilic block loaded poly (trimethyl ammonium ethyl methyl sulfate acrylate). These microgels were synthesized by the "core-first" method, which consists in synthesizing a cross-linked core with living character on which the branches are polymerized.

2 / C-branch microgels _M ικτo having branches of different chemical nature, comprising a neutral hydrophilic polyacrylamide branch, and a hydrophilic charged branch, poly (trimethyl ammonium ethyl methyl sulfate acrylate). These stars were synthesized by the method "arm-first", which consists of synthesizing the branches containing a living end on which is then polymerized a cross-linked core.

3 / Heart C microgels

In the examples given below, the polymerization reactions are carried out under light argon flushing in simple glass apparatus immersed in an oil bath preheated to 70 ^° C. As free radical generators, 4 is used. 4'-Azan-4-cyanopentanoic acid (ACP), or sodium persulfate (Na ₂ S ₂ O ₈ ). The crosslinking agent used in the following examples is N, N'-methylene- (bis) acrylamide (MBA). By way of example, the cationic monomer used below is trimethyl ammonium methyl methyl sulfate acrylate (ADAMQUAT), in all the syntheses below an 80 weight percent solution of ADAMQUAT in water is used. . The neutral hydrophilic monomer used below is acrylamide (AM), and for reasons of toxicity it is handled from aqueous solutions. The conversion of the first-generation polymer is evaluated by analyzing the (co) polymers in steric exclusion chromatography (SEC), or by gas chromatography (GC) of the residual monomers, or by high-performance liquid chromatography. performance (HPLC). The average molar masses in number M _n (g.mol ^-1 ) are expressed as polyethylene oxide equivalents. The molar mass distribution is evaluated by the polymolecularity index (l _p ) corresponding to the ratio of the mass-average molar mass and the number-average molar mass (l _p = MJM _n ). These examples show that the number-average molecular weight of the first-generation polymers resulting from the radical polymerization of the ethylenically unsaturated monomers is mainly determined by the initial molar ratio between the monomer and the control agent. UV detection at 290 nm in SEC chromatography provides information on the presence of the control agent fragment at the end of the polymer chains, characteristic of the controlled nature of the polymerization. Abbreviations: AA = acrylic acid ADAMQUAT = trimethyl acrylate ammonium ethyl methyl sulfate AM = acrylamide

MBA = N, N'-methylene- (bis) acrylamide

Xant = xanthate of type: EtOC (= S) SCH (CH ₃ ) COOCH ₃

ACP = 4,4'-azobis of 4-cyanopentanoic acid

Example 1 .1 - Preparation of a C / MBA Core C microel

In a two-necked flask surmounted by a condenser, 9.64 g (46.28 × 10 ^-3 mol) of EtOC (= S) SCH (CH ₃ ) COOCH ₃ xanthate are added to 50 g of ethanol. The reaction mixture is brought to 70 ^° C. At this temperature 1, 927 g (6.87 × 10 ³ mol) of ACP is added all at once. A mixture of 13.42 g (188.77 × 10 ^-3 mol) of AM, 4.28 g (27.78 × 10 ^-3 mol) of MBA, 100.54 g of deionized water and 57.39 g are then added. ethanol continuously over 3 hours. At the end of the continuous addition, the annealing is maintained for 2 hours before introducing, in one go, the last initiator fraction (PCA) 1, 445 g (5.158 × 10 ^-3 mol). The annealing is prolonged for another 5 hours.

EXAMPLE 1 Preparation of a Micro-Cell with Cationiangile Diblock C-branches _h inπ by "heart first" (heart AM / MBAHAMsk-ADAMQuatmk)

In a two-necked flask surmounted by a condenser, 20 g of the solution "C2" of Example 1.1 are heated to 70 ^° C. At this temperature, a mixture of 40.24 g (566.10 × 10 ^-3 mol ) of AM (ie 82.12 g of the 49% by weight solution in water), 0.230 g (0.822 × 10 ^-3 mol) of ACP and 38.88 g of deionized water is added over a period of 2.5 hours. . The annealing is maintained for an additional 2.5 hours before the addition of 0.1 15 g (0.41 × 10 ^-3 mol) of PCA The annealing is continued for 4 more hours. A certain quantity of the solution obtained is removed to keep only 50 g of the reaction medium in the bicol, to which is added, still at 70 ^° C., a mixture of 7.38 g (27.42 × 10 ³ mol) of ADAMQUAT (either 7.384 g of the 80% by weight solution in water), 0.108 g (0.385 × 10 ^-3 mol) of PCA and 18.84 g of deionized water over a period of 2 h. The annealing is maintained for a further 5h before adding 0.086 g (0.308x10 ³ mol) of ACP. The annealing is continued 4h more.

Example 1 .3 Preparation of a Microqel with Cationic Mikto Branches C-Branches MiKtn by "Arm First" Mikto AlvU-C-ADAMQuaU 03MBN052

Step A: Synthesis of P (AM) -5K: 03MBN48

In a two-necked flask surmounted by a condenser, 1.458 g (7.0 × 10 ³ mol) of the EtOC (= S) SCH (CH ₃ ) COOCH ₃ xanthate at 50.0 g (703.43 × 10 ^{-3) are added.} mol) of AM (ie 166.67 g of a solution of MA at 30% by weight in water), to a mixture comprising 31.35 g of ethanol and 8.71 g of deionized water. The reaction mixture is then heated to 70 ^° C. At this temperature, 0.392 g (1.40 × 10 ^-3 mol) of ACP in 2 ml of ethanol is added dropwise for 30 minutes, after 4 hours of annealing at 70 ^° C. 0.392 g (1.40 × 10 ^-3 mol) of PCA are added in one go. The annealing is then maintained for another 4 hours. Mn = 5630 g / mol; Mw / Mn = 1, 43

Step B Synthesis of P (ADAMQUAT) -5K: 03MBN06

In a two-necked flask surmounted by a condenser, 2.08 g (10.0 × 10 ³ mol) of EtOC (= S) SCH (CH ₃ ) COOCH ₃ xanthate at 50 g (185.65 × 10 ³ mol) were added. ADAMQUAT (ie 62.50 g of the 80% by weight solution in water), to a mixture comprising 24.73 g of ethanol and 86.43 g of deionized water. The reaction mixture is then heated to 70 ^° C. At this temperature, 0.456 g (2.00 × 10 ^-3 mol) of ammonium peroxodisulfate (Na ₂ S ₂ O ₈ ) is added all at once. 70 ^° C., 0.456 g (2.00 × 10 ^-3 mol) of ammonium peroxodisulfate (Na ₂ S ₂ O ₈ ) are added in one portion, the annealing is then maintained for a further 4 hours, Mn = 5459 g / mol; Mw / Mn = 1, 28

Step C: In a two-necked flask surmounted by a condenser, 8.929 g of the crude synthetic solution P (AM) -5K, 8.333 g of the crude solution P (ADAMQUAT) -5K and 32.74 g are mixed together. of deionized water. This mixture is heated at 70 ^° C. At this temperature, a mixture of 1. 340 g (18.848 × 10 ³ mol) of AM (ie 4.4657 g of a 30% by weight solution of AM in water). ), MBA (see table below for the amounts), and 0.050 g (0.179 x 10 ^-3 mol) of ACP in ethanol, (see Table 1 for quantities), is added over a period of 2 hours. The annealing is maintained for 2 more hours before the addition of 0.050 g (0.179x10 ³ mol) of ACP. The annealing is continued 5h more.

EXAMPLE 14 Preparation of a Mixture of 2 Linear Polymers of AMg ₁ Acrylamide and PolvadamQuaU 03MBN049

In a two-necked flask surmounted by a condenser, 8.929 g of the crude synthetic solution P (AM) -5K (Step A of Example 1) was mixed with 8.333 g of the solution P (ADAMQUAT). 5K crude synthetic (Step B of Example 1.4) and 32.74g of deionized water. This mixture is heated at 70 ^° C. At this temperature, a mixture of 1. 340 g (18.848 × 10 ³ mol) of AM (ie 4.4657 g of a 30% by weight solution of AM in water). ), MBA (see table below for amounts), and 0.050 g (0.179 x 10 ^"3 mol) in ethanol PCR (see table 1 for amounts) is added over a period of 2h The annealing is maintained for 2 more hours before the addition of 0.050 g (0.179 × 10 ³ mol) of PCA, the annealing is continued for another 5 hours.

Example 2: Evaluations

2.1 Adsorption on a model surface

- A composition is prepared comprising: - distilled water

50 ppm by weight of the microgel of Example 1 .2

- pH 6 (by addition of hydrochloric acid or NaOH)

- KCl 10 ³ m

The kinetic adsorption of the microgel of the composition on an oxidized silica slab (surface close to a glass or ceramic surface, available from Silicon Inc, under the description "100 mm Silicon Wafers, single side polished", is monitored by reflectometry. P-type, (100) orientation, thickness 500-550 microns, with 1000 (+/- 3%) Angstroms SiO2 applied, clean room processed and packaged "). We operate by comparison using a reference comprising distilled water and KCl 10 ^{~ 3} M, according to the method below:

The technique is based on the reflection of light: a polarized ray of a He-Ne laser (632.8 nm) enters a cell through a glass prism following the Brewster angle at the water / silicon interface (71). °) on a silicon wafer covered by a thin film of the adsorbent support to be studied. The ray is reflected and then separated into two components (perpendicular Is and parallel Ip) and then recovered by photodiodes. The quantity recorded during the adsorption is ΔS = S-So in volts. So is the value of S = 1p / 1s in the presence of only the solvent in the cell with the substrate. The measurement is made at the point called "stagnation". At this point, no flow exists to avoid a coupling between the mechanism of transport of the molecule and its organization on the surface. The flow of polymer solution to be studied is taken to the cell only by level difference; it must be laminar of the order of 2 ml / min. To calculate the adsorbed quantity r, it is necessary to determine, using an optical model, the sensitivity factor As. This factor depends on the wavelength of the laser, the angle of incidence, the thickness of the adsorbent and refractive indices of the solvent and the surface. We can then deduce the adsorbed quantity r in mg / m2 by the relation T = (1 / As) (ΔS / So). (As = O, 171 1 ^* dn / dc = 0, 171 1 ^* 0, 17 = 0.029).

Results:

- Fast adsorption is observed, with a plateau after 4 minutes at 0.9 mg / m ² of adsorbed microgel.

- The resistance of the adsorption to rinsing is tested: the adsorbed microgel is resistant to rinsing (rinsing with a solution comprising distilled water and KCl 10 ^'3 M).

2.2 Treatment / Modification of glass surface

Compositions comprising:

- distilled water

50 ppm by weight of the microgel of Example 1 .2 - pH 6

Comparative compositions are prepared comprising:

- water

50 or 200 ppm of a comparative copolymer: ampholytic random linear copolymer comprising units derived from acrylic acid and cationic units as described in document WO 01/05920. - pH 8

- Treatment / Surface Modifications Glass plates 10cm x 15cm are used. The plates are washed with 10% Decon 90 alkaline solution. Then rinse with tap water and then with distilled water. It is wiped with paper towels (precision wipers, KIMTECH, Kimberly-Clark) and the above compositions are sprayed. It is wiped again with absorbent paper and allowed to dry for about 30 minutes.

- The contact angle of a drop of distilled water is measured using a goniometer (Rame-hart Inc. NRL CA.GONIOMETER, Model No. 100-00-230), before and after treatment / modification above. We postpone the difference (initial - final) as well as the final value. An important value for the difference indicates a significant hydrophilization (the contact angle decreases). A low value for the end value indicates a significant hydrophilic character.

Example 3: Cleaning bathroom surfaces

The following compositions are prepared:

Mirapol Surf S 210, marketed by Rhodia (quantity expressed as weight of polymer active ingredient of the commercial product)

The surface modification is evaluated by means of the compositions by: a) application of a characteristic bathroom stain on ceramic tiles, b) application of the composition, cleaning and drying (evaluation of the appearance of the surface after cleaning) c) application of a new characteristic bathroom stain, d) new cleaning and drying (evaluation of the appearance of the surface after cleaning).

Good hydrophilization is observed (no traces of drops on drying) and a new cleaning improved or facilitated for the compositions of Examples 3.1, 3.2, 3.3 (in comparison with the composition of Example 3.4). The additives according to the invention make it possible in particular to obtain important effects with small quantities.

Example 4: Cleaning of toilet surfaces

The aqueous compositions below (amounts in% by weight) are prepared: The following compositions are prepared:

Mirapol Surf S 500, marketed by Rhodia (quantity expressed as weight of polymer active ingredient of the commercial product)

The surface modification is evaluated using the compositions by: a) Cleaning and drying of black ceramic tiles (cleaned with ethanol and de-ionized water and wiped with dry paper, and dried for hour), b) application of the composition to the black ceramic tiles (3 ml using a pipette covering the whole surface, without wiping and drying for one hour horizontally) c) application of a toilet stain (25 g of the stain below, using a film gun), and drying 12 hours horizontally d) rinsing, (using a flexible hose for 1 hour) minute at tap water at 1 L / 10 seconds, pipe diameter: 0.5 cm, 20 round trips) e) assessment of the appearance of the surface (image analysis, notation: plus ours is high, better it is) f) application of a new stain characteristic of toilets, and drying g) new rinsing h) evaluation of the appearance of the surface (analy image, notation). Composition of the stain:

In a plastic beaker, mix with an ultraturax:

The results are as follows:

Good hydrophilization (no traces of drops on drying) is observed and improved or facilitated cleaning for the compositions of Examples 4.1, 4.2, (in comparison with the composition of Example 4.3). This effect persists after at least 1 rinse. The additives according to the invention make it possible in particular to obtain important effects with small quantities.

Example 5: Cleaning of kitchen surfaces

The following compositions are prepared:

Mirapol Surf S 100, marketed by Rhodia (quantity expressed as weight of polymer active ingredient of the commercial product)

The surface modification is evaluated using the compositions by: a) application of the composition to ceramic tiles and drying b) application of a characteristic cooking stain, and drying c) rinsing d) visual evaluation of the appearance of the surface

Good hydrophilization (no traces of drops on drying) is observed and an improved or facilitated cleaning for the compositions of Examples 5.1, 5.2 (in comparison with the composition of Example 5.3). The additives according to the invention make it possible in particular to obtain important effects with small quantities.

Example 6: Surface Modification - Droplet Trail Test

The following compositions are prepared:

The present invention relates to a method comprising an acrylic resin and cationic units as described in WO 01/05920.

A drift test is carried out (a drop is poured on a vertical surface, and the width of the drag is observed at one point as a function of time), according to the following procedure: a) Treatment of the glass plate:

10cm x 15cm glass plates are used. The plates are washed with a solution of Decon 90, 10%. Then rinse with tap water and then with distilled water. It is wiped with absorbent paper (precision wipers, KIMTECH, Kimberly-Clark) and the composition to be studied is sprayed. It is wiped again with absorbent paper and allowed to dry for about 30 minutes. b) Drop course:

The plate is placed vertically. Drops of distilled water are placed successively on a line, on the upper part of the glass plate, using a pipette. Red and green light allows the visualization of the outline of the water film. By sliding, the drop leaves behind a film of water that spreads according to the wetting allowed by the substrate, and that empties because the film is vertical: the water flows. A camera records the flow of drops.

With the aid of image processing software, the width of the trail of the drop is followed at a given height, in time. This width gives an insight into the wettability of the surface: the larger the value, the more hydrophilic the surface.

The width of the drag (in pixels) as a function of time (average over several drops, in seconds) for the different compositions is shown in FIG. It is observed that the compositions according to the invention exhibit a hydrophilic and / or hydrophilic property. The additives according to the invention make it possible in particular to obtain important effects with small quantities.

Example 7: Cleaning the dishes (automatic dishwasher)

Dishwashers are washed in the dishwasher using a commercial product to which the polymer to be tested is added.

Two defects are visually assessed: - presence of spots on the glasses

- presence of a dull continuous film (deposit) on the glasses

Mirapol Surf S 410, marketed by Rhodia (quantity expressed as weight of polymer active ingredient of the commercial product)

The additives according to the invention make it possible in particular to obtain important effects with small quantities.

Examples 3, 4, 5 and 7 show in particular that the microgels according to the invention have a great modularity, the same microgel can provide interesting effects in several types of formulations and / or for several different applications of hard surface treatments.

Claims

A composition for treating and / or modifying hard surfaces, comprising a synthetic polymer, characterized in that the polymer is a microgel comprising:

a chemically crosslinked polymer core comprising C units derived from a core monomer C and crosslinking units R derived from a crosslinking monomer R, and

possibly macromolecular branches on the periphery of the heart.

2. Composition according to claim 1, characterized in that it comprises a surfactant.

3. Composition according to one of the preceding claims, characterized in that the microgel is obtainable by a method implementing a controlled radical polymerization process.

4. Composition according to one of the preceding claims, characterized in that the microgel comprises cationic or potentially cationic units or zwitterionic units.

5. Composition according to one of the preceding claims, characterized in that the core units C are:

cationic or potentially cationic units C _cat or zwitterionic units C ₂ - anionic or potentially anionic units C _A , or

neutral units C _N , hydrophilic or hydrophobic.

6. Composition according to one of the preceding claims, characterized in that the crosslinking units R are units derived from a diethylenically unsaturated monomer RcMunct-

7. Composition according to one of the preceding claims, characterized in that the microgel is a core C which does not comprise macromolecular branches at the periphery of the core, obtained by polymerization, preferably by controlled radical polymerization, of a monomer mixture comprising :

at least one core monomer C comprising a single polymerizable group, preferably a monoethylenically unsaturated monomer, and at least one crosslinking monomer R comprising at least two polymerizable groups, preferably a multiethylenically unsaturated monomer.

8. Composition according to claim according to claim 7, characterized in that the molar ratio between the core monomer C and the crosslinking monomer R is greater than or equal to 1.

9. Composition according to one of claims 7 or 8, characterized in that:

the core C is obtained by controlled radical polymerization using a "precursor" control or transfer agent,

the crosslinking monomer R is a diethylenically unsaturated monomer Rdifunct, and

in that the theoretical branching coefficient r is greater than or equal to 0.25.

10. Composition according to one of claims 1 to 6, characterized in that the microgel is a microgel C-Branches comprising the macromolecular branches at the periphery of the core, selected from the following microgels:

- C-branchesHomo, where each branch is of identical chemical nature, comprising at least 90% in moles of identical units, - C-branchSbioc, where each branch is of identical chemical nature, each comprising at least one block A comprising units A and at least one block B comprising units B, block B being different from block A,

- C-Branch _stat , where each branch is of identical chemical nature, each comprising less than 90 mol% of A units and less than 90 mol% of different B units of the A units, statistically or gradient distributed,

C-Branches _M ικτo, comprising at least one branch A comprising units A, and at least one branch B comprising units B different from units A, branch A and branch B being of different chemical natures.

1. Composition according to claim 10, characterized in that the microgel is obtainable by an "arm-first" or "heart-first" type process.

12. Composition according to one of claims 10 or 1 1, characterized in that the microgel is a microgel C-branches _b ι _O c where

block A is a hydrophilic intermediate block bound to the heart or at least partly comprised in the heart, block B is a block bound to block A, comprising cationic or potentially cationic units B _cat or zwitterionic units B _z .

13. Composition according to claim 12, characterized in that: the core C comprises neutral hydrophilic core units C _N p _hl ie,

the intermediate block A comprises hydrophilic neutral units A _Nphl | _e , and

the peripheral block B comprises cationic or potentially cationic units B _cat or zwitterionic units B _z .

14. Composition according to one of claims 10 or 1 1, characterized in that the microgel is a microcogel C-branches _b ι _O c where

the block A is an intermediate block linked to the core or at least partly comprised in the core, comprising cationic or potentially cationic units A _cat or zwitterionic units A ₂ , and block B is a hydrophilic peripheral block bound to the block AT.

15. Composition according to claim 14, characterized in that:

the core comprises neutral hydrophilic core units C _Np hιie,

the intermediate block A comprises cationic or potentially cationic units A _cat , and

the peripheral block B comprises neutral hydrophilic units B _Nphl | _e .

16. Composition according to one of claims 10 or 1 1, characterized in that the microgel is a microgel C-branches _M ικτo where: - the branches A are hydrophilic branches, and

branches B comprise cationic or potentially cationic units B _cat or zwitterionic units B _z .

17. Composition according to claim 16, characterized in that the core comprises hydrophilic neutral core C units C _Np hιie,

the branches A comprise neutral hydrophilic units A _Nphl ie, and

the branches B comprise cationic or potentially cationic units B _cat or zwitterionic units B ₂ .

18. Composition according to one of claims 10 or 1 1, characterized in that the microgel is a microgel C-branches _sta t where the branches comprise: anionic or potentially anionic units A _A and / or hydrophilic or hydrophobic neutral units A _n

cationic or potentially cationic units B _cat or zwitterionic units B _z .

19. Composition according to Claim 18, characterized in that:

the core comprises hydrophilic neutral core units C _N p _hl ie,

- branches include

anionic or potentially anionic units A _A , cationic units B _cat , and

potentially cationic units B _cat and / or hydrophilic neutral units

BNphile

20. Composition according to one of the preceding claims characterized in that: - the microgel comprises cationic or potentially cationic units A _cat and / or B _ca , and / or Ccat, and

the cationic or potentially cationic units A _cat or B _cat or C _cat are units derived from monomers chosen from the following monomers:

N, N-dimethylaminomethyl-acrylamide or methacrylamide, 2 (N, N-dimethylamino) ethyl-acrylamide or methacrylamide,

3 (N, N-dimethylamino) propyl-acrylamide or -methacrylamide,

4 (N, N-dimethylamino) butyl-acrylamide or -methacrylamide

2 (dimethylamino) ethyl acrylate (ADAM),

2 (dimethylamino) ethyl methacrylate (DMAM or MADAM), 3 (dimethylamino) propyl methacrylate, 2 (tert-butylamino) ethyl methacrylate,

2 (dipentylamino) ethyl methacrylate,

- 2 (diethylamino) ethyl methacrylate

vinylpyridines

- vinyl amine - vinylimidazolines

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),

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

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

21. Composition according to one of the preceding claims, characterized in that:

the microgel comprises neutral hydrophilic or hydrophobic units A _N and / or B _N and / or C _N , and

these units are hydrophilic neutral units A _Nphl ie and / or B _Nphl ie and / or C _Nphl ie derived from monomers chosen from the following monomers: hydroxyethyl acrylates and methacrylates, acrylamide, methacrylamide, - vinyl alcohol.

22. Composition according to one of claims 1 to 12, 14, 16, or 18 to 21, characterized in that:

the microgel comprises anionic or potentially anionic units A _A and / or C _A , and

these units are units derived from monomers chosen from the following monomers:

acrylic acid, methacrylic acid, maleic acid or anhydride, and their water-soluble salts - 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulphonic acid, acrylate or sulfoethyl methacrylate, sulfopropyl acrylate or methacrylate and their water-soluble salts.

23. Composition according to one of the preceding claims, characterized in that

the microgel comprises:

cationic or potentially cationic units A _cat and / or B _cat and / or C _ca t,

neutral hydrophilic units A _Nphl ie and / or B _Nphl ι _e and / or C _Nphl ι _e , and

the weight ratio between the cationic or potentially cationic units and the hydrophilic neutral units is greater than or equal to 1.

24. Composition according to one of claims 10 to 23, characterized in that: the ratio by weight between the units B and the units A is greater than or equal to 1.

25. Composition according to one of claims 2 to 24, characterized in that the surfactant is selected from anionic surfactants, amphoteric surfactants, cationic surfactants, neutral surfactants, and mixtures or combinations thereof.

26. Composition according to any one of the preceding claims, characterized in that the microgel represents from 0.001 to 10% of the weight of the composition.

27. Composition according to one of claims 2 to 26, characterized in that the surfactant or surfactants represent from 0.005 to 60%, preferably from 0.5 to 40% of the weight of the composition.

28. Composition according to any one of the preceding claims, characterized in that it further comprises at least one additive chosen from chelating agents, sequestering or antiscaling agents, mineral builders, agents bleaching agents, fillers, bleaching catalysts, pH-modifying agents, polymers capable of controlling the viscosity of the mixture and / or the stability of foams, hydrotropic agents, moisturizing or humectant agents, biocides or disinfectants, solvents with cleaning or degreasing activity, industrial cleaners, water-soluble organic solvents with little cleaning, co-solvents, anti-foaming agents, abrasives, enzymes, perfumes, dyes, corrosion inhibitors for metals.

29. Composition according to any one of the preceding claims, for cleaning or rinsing hard surfaces made of ceramic, glass, metal, synthetic resin or plastic material.

30. Composition according to any one of the preceding claims, for household use, for cleaning or rinsing bathrooms, kitchens, linoleum floors, tiles or cement, toilet bowls, windows or mirrors, dishes by hand or machine.

31 Composition according to any one of the preceding claims, for industrial or community use, for cleaning or rinsing reactors, blades steel, sinks, vats, dishes, outer or inner surfaces of buildings, windows of buildings or buildings, bottles.

32. Composition according to any one of the preceding claims, characterized in that it has a pH of at least 7.5 and comprises from 0.001 to

5%, preferably from 0.005 to 2% by weight of the microgel.

33. A composition according to claim 32, characterized in that it further comprises at least one additive chosen from sequestering or antiscaling agents, cationic biocides or disinfectants, surfactants, pH-regulating agents, water, cleaning or degreasing organic solvents, co-solvents, water-soluble organic solvents with low cleaning properties, bleaching agents and perfumes.

34. Composition according to one of claims 31 or 32, characterized in that it is intended for cleaning kitchens, and in that it comprises:

From 0.001 to 1% by weight of the microgel

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,

From 0 to 1% by weight of at least one cationic surfactant with 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) ( s) representative of 1 to 50% by weight

From 0 to 2% by weight of a dicarboxylic acid as antiscaling agent

From 0 to 5% of a bleaching agent and from 70 to 98% by weight of water. and in that it has a pH of preferably 7.5 to 13, preferably 8 to 12.

35. Composition according to any one of claims 1 to 31, characterized in that it has a pH of less than 5 and in that it comprises an inorganic or organic acid agent and from 0.001 to 5%, preferably from 0 to , 01 to 2% of its weight of the microgel.

36. Composition according to claim 35, characterized in that it further comprises at least one additive chosen from nonionic, amphoteric, zwitterionic or anionic surfactants or mixtures thereof, cationic biocides or disinfectants, thickening agents, bleaching agents, water, solvents, perfumes, abrasives.

37. A composition according to claim 35 or 36, characterized in that it is intended for the cleaning of toilet bowls, in that it comprises: "from 0.05 to 5%, preferably from 0.01 to 2% , by weight of the microgel

From 0.1 to about 40%, and preferably from 0.5 to about 15%, by weight of at least one acidic cleaning agent

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 disinfecting property, preferably a mixture of n-alkyl dimethyl ethylbenzyl ammonium chloride and n-alkyl dimethyl benzyl ammonium chloride

Optionally from 0.1 to 3% by weight of at least one thickening agent, preferably a gum, especially a xanthan gum or a succinoglycan

Optionally from 1 to 10% by weight of at least one bleaching agent

• possibly a preservative, a dye, a perfume or an abrasive

And from 50 to 95% by weight of water. and in that it has a pH of 0.5 to 4, preferably 1 to 4.

38. Composition according to any one of claims 1 to 31, characterized in that it is intended for cleaning windows, in that it comprises:

From 0.001 to 10%, preferably from 0.005 to 3% by weight of the microgel

From 0.005 to 20%, preferably from 0.5 to 10% by weight, of at least one nonionic and / or anionic surfactant

From 0 to 10%, preferably from 0.5 to 5% by weight, of at least one amphoteric surfactant

• some water

0 to 30%, preferably 0.5 to 15% by weight of at least one solvent, preferably an alcohol and in that it has a pH of 6 to 1 1.

39. Composition according to any one of claims 1 to 31, characterized in that it is intended for washing dishes in automatic dishwashers, in that it comprises: • from 0.01 to 5%, advantageously from 0.1 to 3% by weight of the microgel

From 0.2 to 10%, advantageously from 0.5 to 5% by weight of at least one surfactant, preferably nonionic, and optionally

Up to 90% by weight of at least one 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, 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 and in that it has a pH of 8 to 13.

40. Composition according to any one of claims 1 to 31, characterized in that it is intended for rinsing dishes in automatic dishwasher, in that it comprises:

From 0.02 to 10%, preferably from 0.1 to 5% by weight of the microgel

From 0.1 to 20%, advantageously from 0.2 to 15% by weight of at least one surfactant, preferably nonionic surfactant;

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

From 0 to 15%, advantageously from 0.5 to 10% by weight of at least one auxiliary detergency agent, preferably a copolymer of acrylic acid and of maleic anhydride, and homopolymers of acrylic acid and in this case it has a pH of 4 to 7.

41. Composition according to any one of claims 1 to 31, characterized in that it is intended for washing dishes by hand, in that it comprises:

From 0.1 to 10% by weight of the microgel

From 3 to 50%, advantageously from 10 to 40% by weight of at least one surfactant, preferably anionic and optionally

At least one nonionic surfactant At least one bactericidal agent or non-cationic disinfectant, triclosan preferably

At least one synthetic cationic polymeric agent

At least one polymer capable of controlling the viscosity of the mixture and / or the stability of the foams

At least one hydrotropic agent

At least one moisturizing or humectant agent or a skin protection agent and in that it has a pH of 5 to 9.

42. Composition according to any one of claims 1 to 31, characterized in that it is intended for the external washing of motorized vehicles, in that it comprises:

From 0.005 to 10% by weight of the microgel

From 0 to 30%, preferably from 0.1 to 15% by weight, of at least one nonionic surfactant;

From 0 to 30%, preferably from 0.1 to 15% by weight, of at least one anionic surfactant;

From 0 to 30%, preferably from 0.01 to 10% by weight, of at least one amphoteric and / or zwitterionic surfactant; From 0 to 30%, preferably from 0.05 to 15% by weight, of at least one cationic surfactant; the minimum amount of surfactant being at least 0.5% by weight;

From 0 to 99%, preferably from 40 to 98% by weight of at least one builder; Optionally a hydrotropic agent, fillers, pH-regulating agents and in that it has a pH of 8 to 13.

43. Composition according to any one of claims 1 to 31, characterized in that it is intended for cleaning ceramic surfaces, including bathrooms, in that it comprises:

From 0.02 to 5% by weight of the microgel

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

From 0 to 30%, preferably from 0 to 20% by weight, of at least one anionic surfactant; the total amount of surfactant is from 0.5 to 50%, preferably from 1 to 30%, more preferably from 2 to 20% by weight;

From 0 to 25%, preferably from 0.1 to 25% by weight of at least one builder; From 0 to 2%, preferably from 0.005 to 2%, most preferably from 0.5 to 2% by weight of a foam regulating agent and having a pH of 2 to 12.

44. Composition according to any one of claims 1 to 31, characterized in that it is intended for rinsing shower walls, in that it comprises:

From 0.02 to 5%, preferably from 0.05 to 1% by weight of the microgel

From 0.5 to 5% by weight of at least one nonionic surfactant, preferably a polyethoxylated fatty acid ester;

• water • possibly at least one lower alcohol

Optionally from 0.01 to 5% by weight of at least one metal chelating agent and in that it has a pH of 7 to 1 1.

45. Composition according to any one of claims 1 to 31, characterized in that it is intended for the cleaning of glass-ceramic plates, in that it comprises:

From 0.01 to 5% by weight of the microgel

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

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

From 1 to 10% by weight of at least one nonionic surfactant

From 0 to 7% by weight of at least one solvent, butyldiglycol preferably

• possibly alkanizing agents or sequestering agents and in that it has a pH of 7 to 12.

46. Composition according to any one of claims 1) to 31, characterized in that it is intended for the cleaning of reactors, in that it comprises:

From 0.02 to 5% by weight of the microgel

From 1 to 50% by weight of at least one alkaline salt, preferably a phosphate, carbonate, sodium or potassium silicate From 1 to 30% by weight of a mixture of surfactants, preferably nonionic and anionic surfactants, especially ethoxylated fatty alcohols and lauryl benzene sulphonate;

From 0 to 30% by weight of at least one solvent, diisobutyl ester preferably and in that it has a pH of 8 to 14.

47. Use of a microgel as defined in one of the claims for the treatment and / or modification of hard surfaces.

48. Use according to claim 47, for

- hydrophilization of hard surfaces

- facilitate the cleaning of hard surfaces, and / or

- facilitate the subsequent cleaning of hard surfaces.

49. Use according to one of claims 47 or 48, to provide antideposition properties and / or anti-adhesion of dirt likely to be deposited on said surfaces.