Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent

Definitions

• 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 ...)
• 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.
• surfactants especially nonionic and anionic surfactants, or nonionic and cationic surfactants
• solvents especially alcohol (s) to facilitate drying, and optionally sequestering agents and bases or acids to adjust the pH.
• alcohol (s) to facilitate drying
• 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.
• the treatment with these formulations is, for most of them, only purely curative and non-preventive.
• 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
• compositions comprising synthetic polymers.
• 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.
• the microgel can contribute to:
• 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.
• 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.
• star copolymer is sometimes also used to designate microgels comprising the macromolecular branches at the periphery of the core.
• star copolymer and microgel overlap partially, the common part being compounds comprising a chemically crosslinked polymeric core comprising macromolecular branches at the periphery.
• the term “arm” is also used in place of "branches” and covers the same notion.
• Heart C a microel comprising a polymer core chemically crosslinked, but not comprising macromolecular branches on the periphery of the heart.
• 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).
• 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.
• C-branches a microgel comprising a chemically crosslinked polymer core and macromolecular branches a periphery of the heart.
• 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.
• the unit derived from a monomer denotes a unit that can be obtained directly from said monomer by polymerization.
• 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) -.
• the theoretical average molar mass M b ⁇ O c or M breche of a block or of a branch is calculated according to the following formula:
• M block or branch 1 ⁇ 2- JVL ⁇ 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.
• n dlfun ct is the number of moles of monomer moles of a crosslinking monomer R dlfUn ct diethylenically unsaturated.
• the measured molar mass of a microgel M star is a weight-average molar mass measured by static light scattering experiments, using Zimm curves.
• M star M w * n arm
• M w 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.
• 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.
• 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.
• 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.
• cationic or potentially cationic units 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.
• 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.
• 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.
• soiling eg rain water, water from the distribution network, added rinse water or not rinsing products, splashing oils, soaps .
• 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.
• 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.
• 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.
• 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.
• 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)
• - 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).
• microgels for the invention 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.
• 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
• 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.
• 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.
• 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
• C-branchSioc microgel star copolymer
• block A is hydrophilic and block B is hydrophobic, or block A is hydrophilic and block B is cationic or potentially cationic hydrophilic.
• 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.
• 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.
• Heart C includes:
• crosslinking units R which can be derived from the crosslinking monomer R.
• the units C and the monomers C comprise several different units or are derived from several different monomers.
• microgel C-Branches can be chosen from microgels. following:
• each branch is of identical chemical nature, comprising at least 90 mol% of identical units
• 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,
• 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 ⁇ o 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.
• 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 H ⁇ mo, C-branches sta , or C-branches microgels.
• branchesMiKTo by units A of block A, for microgels C-branches b
• O c in this case are at least partly included in the heart.
• 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 ⁇ o or A units for microgels C-branches b
• 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 ⁇ o 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.
• 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.
• 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.
• 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:
• 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:
• anionic or potentially anionic units A A or
• the B units can be:
• anionic or potentially anionic units B A or neutral B N units, hydrophilic or hydrophobic.
• the microgel is a C-branchSbbc microgel
• 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 .
• the core C comprises neutral hydrophilic core units C Nphl ie
• the intermediate block A comprises hydrophilic neutral units A Nphl ie
• the peripheral block B comprises cationic or potentially cationic units B cat or zwitterionic units B z .
• 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.
• 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 .
• the peripheral block B comprises neutral hydrophilic units B Nphl
• the microgel is a microgel C-branchesMiKTo where:
• the branches A are hydrophilic branches
• the branches B comprise cationic or potentially cationic units B ca , or zwitterionic units B z .
• the core comprises neutral hydrophilic core units C Np h ⁇ ie,
• 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 .
• 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
• the heart comprises neutral hydrophilic core units C Np h ⁇ ie, the branches comprise
• 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:
• N, N (dialkylaminoalkyl) amides of monoethylenically unsaturated ⁇ - ⁇ carboxylic acids such as N, N-dimethylaminomethyl
• methacrylamide ⁇ - ⁇ 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
• Amine precursor monomers such as N-vinyl formamide, N-vinyl acetamide, which generate primary amine functions by simple acid or basic hydrolysis.
• 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
• ADAMQUAT methacryloyloxyethyltrimethylammonium chloride or methylsulfate
• ADAMQUAT acryloyloxyethyltrimethylammonium salts
• ADAMQUAT Cl acryloyloxyethyltrimethylammonium methylsulfate
• ADAEQUAT MeS methyldiethylammonium methyl ethyl acrylate
• DADMAC N-dimethyldiallylammonium chloride
• 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
• X ' is an anion, preferably chloride or methylsulfate.
• hydrophilic neutral monomers A h ⁇ iP Np and / or B NPHL ie and / or C Np h ⁇ ie which may be derived neutral hydrophilic units A NPHL ie and / or B NPHL ie and / or C Np h ⁇ ie there may be mentioned: we can mention:
• Hydroxyalkyl esters of ⁇ - ⁇ ethylenically unsaturated acids such as hydroxyethyl acrylate, hydroxypropyl acrylate and methacrylate, glycerol monomethacrylate, etc.
• ⁇ - ⁇ ethylenically unsaturated amides such as acrylamide, methacrylamide and N, N dimethyl methacrylamide, N-methylolacrylamide ...
• Ethylenically unsaturated ⁇ - ⁇ monomers bearing a water-soluble polyoxyalkylene segment of the polyethylene oxide type such as polyethylene oxide ⁇ -methacrylates (BISOMER S20W, S10W, ... from LAPORTE) or ⁇ , ⁇ -dimethacrylates, SIPOMER RHODIA BEM (polyoxyethylene caset-behenyl methacrylate), the
• 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 ⁇ - ⁇ 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
• ⁇ -olefins such as ethylene ... conjugated dienes, such as butadiene, isoprene, chloroprene,
• part B may be a silicone, for example a polydimethylsiloxane chain or a copolymer comprising dimethylsiloxy units,
• Diethyleneglycolethyletheracrylate or diethyleneglycolethylethermethacrylate Diethyleneglycolethyletheracrylate or diethyleneglycolethylethermethacrylate.
• 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 ⁇ - ⁇ 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.
• 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,
• SPE sulphopropyl dimethyl ammonium ethyl methacrylate
• the crosslinker R monomers from which R cross-linking units may be derived 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.
• 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.
• vinyl ethers there may be mentioned vinyl crotonate, diethylene glycoldivinyl ether, butanediol-1,4-divinyl ether, and triethylene glycol divinyl ether.
• 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.
• N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, glyoxal bisacrylamide, diacrylamido acetic acid there may be mentioned N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, glyoxal bisacrylamide, diacrylamido acetic acid.
• styrenic derivatives there may be mentioned divinylbenzene and 1,3-diisopropenylbenzene.
• diene monomers there may be mentioned butadiene, chloroprene and isoprene.
• N, N'-methylenebisacrylamide, divinylbenzene, ethylene glycol diacrylate, or trimethylolpropane triacrylate are preferred.
• multiethylenically unsaturated monomers can be used alone or in mixtures. Furthermore, they are polymerized preferably in the presence of core monomers, preferably monoethylenically unsaturated.
• the microgel comprises: cationic or potentially cationic units A ca and / or b ca and / or c ca t
• the weight ratio between the cationic or potentially cationic units and the hydrophilic neutral units is greater than or equal to 1.
• 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.
• 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.
• 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.
• 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.
• living or controlled polymerization processes reference may especially be made to:
• ATRP radical polymerization by atom transfer
• the controlled or living radical polymerizations carrying out transfer agents or groups (or control agents) having a group -S-CS- 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
• a core C chemically crosslinked polymer
• step b) growth of macromolecular branches microgels C-branches b ⁇ O c or C-brancheSstat or C-branches H ⁇ mo from monoethylenically unsaturated monomers A and / or B, by polymerization, controlled radical Preferably, to obtain the branches related to the heart.
• 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.
• the microgel is a microgel C-branches b
• O c macormolé vide the chain is a block copolymer, preferably comprising a group of control or transfer at the end of block A.
• crosslinking monomer R preferably multiethylenically unsaturated
• core monomer C preferably monoethylenically unsaturated
• step a ' 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
• 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:
• 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.
• the mole fraction is between 0.01 and 1.
• the first steps of the processes are carried out in the presence of a source of free radicals.
• a source of free radicals 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
• alkali metal bisulfite such as sodium metabisulphite
• alkali metal persulfates in combination with an arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.
• an arylphosphinic acid such as benzene phosphonic acid and the like
• 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.
• a solvent for example an alcohol or THF
• latex emulsion in water
• 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.
• 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.
• 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 can be universal or can be more specific, such as a composition for cleaning or rinsing
• 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.
• 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.
• 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.
• 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.
• 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 can be universal or more specific, like a composition for cleaning - reactors, steel blades, sinks, vats, dishes
• 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 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.
• 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.
• anionic surfactants there may be mentioned by way of example:
• 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
• M is an alkaline (sodium, potassium, lithium), substituted or unsubstituted ammonium methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine, etc.).
• 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;
• 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 (
• 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,
• 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 ).
• 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 ).
• 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.
• 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.
• 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
• 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.
• halide for example chloride, bromide, iodide
• alkyl sulphate methyl sulphate
• carboxylate acetate, propionate, benzoate
• alkyl or aryl sulphonate alkyl or aryl sulphonate.
• cationic surfactants such as:
• 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
• R 3 '4' - R and R represent a C8-C22 alkyl or alkenyl group, preferably
• 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.
• 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.
• 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.
• 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);
• RHODIAPHOS HD7 marketed by Rhodia, (from 0 to 70% of the total weight of cleaning composition);
• 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. ;
• 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)
• transition metal-containing bleach catalysts especially iron, manganese and cobalt complexes, such as those of the type [Mn ⁇ v 2 (OD) 3 (Me 3 TACN) 2 ] (PFe) 2 , [Fe "(MeN 4 py) (MeCN) (CIO 4 ) 2 ,
• alkalizing additives alkali metal phosphates, carbonates, perborates, alkali metal hydroxides
• 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.
• mineral acids phosphoric acid, polyphosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, chromic acid
• carboxylic acids or polycarboxylic acetic, hydroxyacetic,
• 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
• 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-
• 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
• 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)
• 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
• 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
• 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 monohexyl ether, monoethylene glycol, mono
• 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)
• water-soluble organic solvents with low cleaning properties such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and mixtures thereof (from 0 to
• 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
• 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
• 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)
• 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
• 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.
• a formulation for cleaning kitchens comprises:
• non-cationic surfactant preferably amphoteric or nonionic
• 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
• 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)
• 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)
• a bleaching agent in an amount ranging from 1 to 10%, by weight of the composition
• compositions 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.
• a solvent such as glycol or an alcohol
• Said acid compositions are preferably in the form of a ready-to-use formula.
• a formulation for cleaning the toilet bowls comprises:
• microgel 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
• 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
• 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)
• a bleaching agent in an amount ranging from 1 to 10%, the weight of the composition
• 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.
• 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;
• 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 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.
• At least one cleaning auxiliary agent 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.
• 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.
• 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.
• 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.
• 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
• 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
• 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
• 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
• 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.).
• motorized vehicles cars, trucks, buses, trains, planes, etc.
• 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
• 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.
• 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).
• HLB hydrophilic / hydrophobic balance
• 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.
• amphoteric, cationic or zwitterionic detergents 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:
• 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 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.
• 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.
• the formulations for the cleaning of vitroceramic plates of the invention comprise:
• microgel 0.01 to 5% by weight of the microgel; 0.1 to 1% by weight of a thickener such as xanthan gum;
• an abrasive agent such as calcium carbonate or silica
• a solvent such as butyldiglycol
• the pH of the composition is advantageously between 7 and 12.
• composition according to the invention can also be used in the field of industrial cleaning, in particular for easy cleaning of reactors.
• compositions comprise:
• microgel 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.
• 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.
• microgels b ⁇ 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.
• the polymerization reactions are carried out under light argon flushing in simple glass apparatus immersed in an oil bath preheated to 70 ° C.
• free radical generators 4 is used.
• the crosslinking agent used in the following examples is N, N'-methylene- (bis) acrylamide (MBA).
• 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).
• SEC steric exclusion chromatography
• GC gas chromatography
• HPLC high-performance liquid chromatography. performance
• the average molar masses in number M n (g.mol -1 ) are expressed as polyethylene oxide equivalents.
• MBA N, N'-methylene- (bis) acrylamide
• ACP 4,4'-azobis of 4-cyanopentanoic acid
• 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 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
• 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.
• composition comprising: - distilled water
• 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 adsorbed microgel is resistant to rinsing (rinsing with a solution comprising distilled water and KCl 10 '3 M).
• compositions comprising:
• Comparative compositions are prepared comprising:
• 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.
• compositions are prepared:
• 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).
• 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 Composition of the stain:
• 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
• 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:
• 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.
• 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.
• 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.
• Dishwashers are washed in the dishwasher using a commercial product to which the polymer to be tested is added.
• 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.

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