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
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

• composition for household care comprising a cationic nanogel
• the present invention relates to compositions for household care comprising a cationic nanogel, especially for the treatment and / or modification of hard surfaces or textiles.
• the composition makes it possible in particular to hydrophilize hard surfaces, which are particularly useful in cleaning or rinsing operations.
• the household care compositions comprise various ingredients which, individually or in combination, confer on said compositions the properties of uses for the application for which they are intended, or modify certain properties.
• Cleaning compositions often include, for example, surfactants.
• Some compositions include polymers for example to give them particular rheological properties (for example to thicken) or to modify surface properties including deposition.
• WO 2007/071591 describes the implementation of nanogels for the treatment of hard surfaces.
• This document teaches, in Examples 3.1 and 3.2, that star copolymers having cationic peripheral branches make it possible to facilitate the cleaning of bathroom surfaces.
• These copolymers require multistage sequential polymerization processes, which make them expensive.
• star copolymers there is a need for simpler compounds to be prepared and / or for compounds having application advantages at least of the same order of magnitude, if not higher, and / or having in addition to other advantages.
• polymers providing a more durable treatment, for example providing a cleaning even after more time and / or submitting to water passages, for example during rinsing, splashing or cleaning in the absence of polymer.
• Example 6.1 that nanogels consisting of a neutral core C, without peripheral branches, provides good hydrophilization.
• polymers providing a more durable treatment, for example providing an easy cleaning even after more time and / or submission to passages to water for example during rinsing, splashing or cleaning in the absence of polymer.
• nanogels or microgels and processes for their preparation have been described in the literature.
• WO2004048429 discloses a process for preparing monofunctional and multifunctional monomer-based microgels where the reactivity of these two types of monomers is appropriately selected to produce discrete particles of average molecular weight of at least 10 5 .
• non-cationic nanogels especially based on (meth) acrylate are prepared.
• WO2004048428 discloses microgels characterized by certain rheological properties.
• non-cationic nanogels especially based on (meth) acrylate are prepared.
• WO0056792 discloses gels prepared from triethylenically unsaturated monomers.
• non-cationic nanogels based in particular on acrylamide are prepared.
• WO9831739 describes the preparation of nanogels by controlled radical polymerization using nitroxides.
• non-cationic nanogels based in particular on styrene monomers are prepared.
• composition for household care comprising a cationic nanogel, consisting of chemically crosslinked macromolecules having a core C comprising:
• crosslinking units R derived from a crosslinking monomer R comprising at least two polymerizable groups, and core units C derived from at least one monomer C comprising a single polymerizable group, comprising: - cationic or potentially cationic units C cat derived from at least one monomer C cat cationic or potentially cationic, and
• nanogel optionally neutral C N hydrophilic or hydrophobic units derived from at least one hydrophilic or hydrophobic neutral C N monomer, the nanogel being different from a star copolymer comprising macromolecular branches at the periphery of the core
• the average size of the macromolecules being preferably from 5 to 500 ⁇ m, preferably from 30 to 170 nm.
• the invention also relates to the use of cationic nanogel in household care compositions.
• the cationic nanogel may in particular be used as a foam stabilizing agent, preferably with the addition of soil, and / or as an anti-redeposition agent or as a hydrophilizing agent and / or as an anti-fouling agent.
• the invention also relates to the use of the compositions in the context of household care, for example in the context of treatment, preferably cleaning, hard surfaces or textile surfaces.
• the nanogels used for the invention are macromolecules. They are sometimes referred to as "the polymer (s)” or “the copolymer (s)” in the present application.
• the average size of the macromolecules is defined as the mean hydrodynamic diameter measured by light scattering (Dynamic Light Scattering).
• nanogel is understood to mean a macromolecular compound, copolymer, having a core.
• a core is a chemically crosslinked macromolecule comprising units derived from a monomer comprising a single polymerizable function and units comprising at least two polymerizable functions.
• the nanogel of the invention is different from a nanogel comprising at the periphery of the heart of the macromolecular branches, linked to the heart.
• the term heart is used as opposed to macromolecular branches at the periphery.
• Nanogels having a core and no branches on the periphery are macromolecular architectures known to those skilled in the art.
• star copolymer is sometimes also used to designate nanogels comprising the macromolecular branches at the periphery of the core.
• core C a nanogel comprising a polymer core chemically crosslinked, but not comprising macromolecular branches at the periphery of the heart. This is microscopic macromolecules with intra-chain crosslinking.
• Such cores C can be obtained by copolymerization of a 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 small amount surfactant (eg less than 10% by weight, preferably less than 5% by weight, or even less than 1% by weight or not at all).
• a surfactant eg less than 10% by weight, preferably less than 5% by weight, or even less than 1% by weight or not at all.
• they are distinguished from “nanolatex" polymers obtained by emulsion polymerization in the presence of high amounts of surfactants at thermodynamic equilibrium or near.
• 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) -.
• N R is the number of polymerizable functions (typically of ethylenically unsaturated functions) in a crosslinking monomer
• n R is the number of moles of monomer (s) crosslinking (s) R
• n ⁇ is the total number of moles of monomers (monomer (s) C + monomer (s) R)
• Nco n t r oi is the number of control groups in a control agent if such an agent is used in the polymerization
• hydrophobic for a monomer is used in its usual sense of "which has no affinity for water”; this means that the monomer can form a two-phase macroscopic solution in distilled water at 25 ° C, at a concentration greater than or equal to 1% by weight, or that it has been categorized as hydrophobic in the present application.
• hydrophilic for a monomer, 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 distilled water at 25 ° C at a concentration greater than or equal to 1% by weight, or that it has been categorized as hydrophilic in the present application.
• 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 nanogel 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 nanogel 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.
• the units or anionic groups are units or groups 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), regardless of the pH of the medium where the nanogel 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 nanogel 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 where the nanogel 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 three cycles of rinsing, even in some particular cases where the rinsings are numerous (case of toilets for example), beyond 6, 10 or 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 nanogel 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 nanogel can clean more soiled objects than a formulation that is free of it.
• the deposition on a hard surface of the nanogel 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 nanogel in the hard surface treatment formulations makes it possible to render the surface hydrophilic or to improve its hydrophilicity.
• the surface-freeze-drying property further reduces fogging of 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 are non-textile surfaces, which can be household, community or industrial. They may be of any material, including: ceramic (surfaces such as washbasin, bathtubs, wall or floor tiles, toilet bowls ”) 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 .%) synthetic resins (eg bodywork or interior surfaces of motorized vehicles (cars, trucks, buses, trains, airplanes ...) melamine or formica surfaces for office interiors, kitchens, Among) plastics (for example polyvinyl chloride, polyamide, for the interior of vehicles, including cars)
• 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).
• the nanogel of the invention (Heart C) comprises:
• crosslinking units R derived from a crosslinking monomer R comprising at least two polymerizable groups
• core units C derived from at least one monomer C comprising a single polymerizable group, comprising
• neutral C N hydrophilic or hydrophobic units derived from at least one hydrophilic or hydrophobic neutral C N monomer.
• the polymerizable groups of the monomers C and R are preferably ethylenically unsaturated groups, preferably alpha-ethylenically unsaturated groups.
• the monomers C are thus preferably monoethylenically unsaturated monomers, preferably mono-alpha-ethylenically unsaturated monomers.
• the monomers R are thus preferably multiethylenically unsaturated monomers, preferably di- or tri-ethylenically unsaturated, for example di-alpha-ethylenically unsaturated or tri-alpha-ethylenically unsaturated monomers.
• the C units and the C monomers comprise several different units or derive from several different monomers. It is not excluded that the C ca units and the C ca monomers comprise several different units or derive from several different monomers. It is noted that the C units or the C monomers can comprise both C ca units and C N OR units can derive from both C ca and C N monomers.
• the C units and the monomers C may further optionally include other types of units, or may optionally derive other monomers.
• the units C may in particular comprise, in addition, zwitterionic units C z , derived from zwitterionic monomers C z , and / or anionic or potentially anionic units C A derived from anionic or potentially anionic monomers C A.
• the nanogel is likely to be obtained by a method implementing a controlled radical polymerization process, as explained below.
• the nanogel is different from a star copolymer comprising a core C and at the periphery of the core of the macromolecular branches.
• the nanogel may have a control group or a residue of such a group at ends of the polymeric molecules.
• the nanogel 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. These last two forms can be assimilated to forms in dispersed environments.
• the nanogel may for example be included in an aqueous medium (comprising water), for example in an aqueous medium or the like.
• the form generally depends on the requirements related to the use of the nanogel. It can also be related to the nanogel preparation process.
• the nanogel may especially consist of crosslinked macromolecules of average size ranging from 5 to 500 nm, preferably from 30 to 170 nm. Sizes can be determined conventionally by light scattering or X-ray diffraction techniques in dispersed media.
• the nanogel, and its method of preparation is preferably such that it does not form a macroscopic macromolecular crosslinked network (inter-chain crosslinking). If it is in a dispersed medium, for example in an aqueous medium, the nanogel advantageously has a viscosity (Brookfield) of less than 20000 cP, preferably less than 10000 cP, at 25 ° C., at a shear of 100 s -1 or less , or preferably at a shear of 10 s -1 .
• Brookfield Brookfield
• nanogels having cationic or potentially cationic units C ca could have particularly small sizes, and that processes employing monomers C ca could make it possible to reduce the size of the nanogels substantially.
• the invention can make it possible to reduce the sizes in a simple manner.
• the nanogel (Heart C), comprises polymerized units. All the units mentioned below are possible, as well as their combinations. Certain combinations are the subject of particular embodiments.
• N, N (dialkylaminoalkyl) amides of ⁇ - ⁇ monoethylenically unsaturated 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
• ⁇ - ⁇ 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
• Vinylimidazolines amino-precursor monomers such as N-vinyl formamide, N-vinyl acetamide, which generate primary amine functions by simple acid or basic hydrolysis
• cationic monomers Cn 51 which may be derived cationic units C cat may be mentioned: - ammoniumacryloyl or acryloyloxy monomers as
• acryloyloxyethyltrimethylammonium salts such as acryloyloxyethyltrimethylammonium chloride; or acryloyloxyethyltrimethylammonium methylsulphate (ADAMQUAT Cl or ADAMQUAT MeS), methylmethylldiethylammonium methylethyl acrylate (ADAEQUAT MeS), benzyldimethylammonium ethyl acrylate chloride or methyl sulfate (ADAMQUAT BZ 80),
• DADMAC N-dimethyldiallylammonium chloride
• DIQUAT chloride Dimethylaminopropylmethacrylamide, N- (3-chloro-2-hydroxypropyl) trimethylammonium chloride (DIQUAT chloride), dimethylaminopropylmethacrylamide methylsulfate, N- (3-methylsulfate-2-hydroxypropyl) trimethylammonium (DIQUAT methylsulfate)
• X " is an anion, preferably chloride or methylsulfate - their mixtures or combinations.
• Hydroxyalkyl esters of ⁇ - ⁇ ethylenically unsaturated acids such as hydroxyethyl acrylate, hydroxypropyl acrylate and methacrylate, glycerol monomethacrylate, etc.
• ⁇ - ⁇ ethylenically unsaturated amides such as acrylamide, methacrylamide, N, N-dimethyl methacrylamide, N-methylolacrylamide, etc.
• 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 ⁇ -behenyl methacrylate), the RHODIA SI PO MERSE M-25 (polyoxyethylene ⁇ -tristyrylphenyl methacrylate) ...
• Vinyl alcohol ⁇ - ⁇ 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;
• Vinyllactams such as vinylpyrrolidones, or N-vinylcaprolactam, ⁇ - ⁇ -ethylenically unsaturated monomers of the ureido type and in particular 2-imidazolidinone ethyl methacrylamido (Sipomer WAM II from RHODIA)
• Nonethyleneglycolmethyletheracrylate or nonethyleneglycolmethylethermethacrylate • mixtures or combinations thereof.
• hydrophobic neutral monomers CiMnhnhR from which hydrophobic neutral units C Np hobe can 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, and the 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,
• diethylene glycol ethyl ether acrylate or diethylene glycol ethyl ether methacrylate • their mixtures or combinations.
• anionic or potentially anionic monomers CA from which anionic or potentially anionic units C A may be derived, mention may be made of: monomers having at least one carboxylic function, such as ⁇ - ⁇ ethylenically unsaturated carboxylic acids or anhydrides corresponding, such as acrylic, methacrylic, maleic acid, fumaric acid, itaconic acid, N-methacroyl alanine, 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.
• carboxylic function such as ⁇ - ⁇ ethylenically unsaturated carboxylic acids or anhydrides corresponding, such as acrylic, methacrylic, maleic acid, fumaric acid, itaconic acid, N-methacroyl alanine, N-acryloylglycine and their water-soluble salts
• Monomers having at least one sulphate or sulphonate function such as 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allyl sulphonic 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
• 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 crosslinking monomers R from which R crosslinking units may be derived may in particular be chosen from organic compounds comprising at least two ethylenic unsaturations and at most 10 unsaturations and known to be reactive by a radical route. Preferably, these monomers have two or three ethylenic unsaturations. Thus, mention may in particular be made of acrylic, methacrylic, acrylamido, methacrylamido, vinyl ester, vinyl ether, diene, styrenic and alpha-methyl derivatives. styrenic and allylic.
• 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, 1,4-butanediol imethacrylate, 1, 6 hexanediol dimethacrylate, dodecanediol 1,12-dimethacrylate, glycerol 1,
• 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.
• acrylamido derivatives mention may especially be made of N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, glyoxal bisacrylamide and diacrylamidoacetic 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 (MBA), divinylbenzene (DVB), ethylene glycol diacrylate, triallycyanurate (TAC) or trimethylolpropane triacrylate are preferred.
• These multiethylenically unsaturated monomers can be used alone or in mixtures.
• the nanogel comprises C N units
• it may advantageously be Cnphiie units derived from a hydrophilic neutral monomer C Np h ⁇ ie-mol ratio between Ccat units and C N units, preferably C Np h ⁇ ie, may in particular be between 1/99 and 99/1, preferably between 1/99 and 50/50, preferably between 1/99 and 40/60, preferably between 1/99 and 25/75, for example between 2 / 99 and 10/90.
• Nanogels whose composition in C units is as follows can in particular be prepared:
• APTAC / AM for example with an APTAC / AM mole ratio of 1/99 to 40/60, preferably 5/95 to 30/70.
• DIQUAT / AM for example with a molar ratio DIQUAT / AM of 1/99 to 10/90
• MAPTAC / AM for example with a MAPTAC / AM mole ratio of 1/99 to 10/90
• Particularly advantageous processes use a controlled (or "living") polymerization, using an agent or a control group (sometimes referred to as a transfer group), for example by a controlled radical polymerization process ( or “living”).
• a controlled radical polymerization process or "living”
• Such methods 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.
• copolymers obtained as above by controlled radical polymerization can undergo a purification reaction of their sulfur chain end, for example by hydrolysis, oxidation, reduction, pyrolysis or substitution type processes
• the method of the WO application 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)
• ATRP radical polymerization by atom transfer
• agents or control groups having a group -S-CS- (Xanthates, dithioesters, trithiocarbonates, dithiocabamates, dithiocarbazates, etc.) are particularly interesting.
• a practical process for the preparation of the nanogel is a preparation process comprising the following step a): step a) polymerization, preferably controlled radical polymerization, of a monomer mixture comprising: at least one multiethylenically unsaturated crosslinking R monomer, and at least one monoethylenically unsaturated C monomer, comprising:
• the process preferably not comprising a subsequent polymerization step which can lead to the formation of macromolecular branches at the periphery.
• the ratio between the units C and the units R can be identical.
• the nanogel is obtained by a method implementing a controlled radical polymerization process using control groups.
• the molar ratio between the number of control groups i.e., the amount of control agent multiplied by the number of control groups carried by an agent
• the number of control groups i.e., the amount of control agent multiplied by the number of control groups carried by an agent
• the number of control groups i.e., the amount of control agent multiplied by the number of control groups carried by an agent
• the number of control groups of polymerizable groups of the crosslinking monomer R i.e. half of the amount by mole of monomer multiplied by the number of unsaturated groups of the monomer
• the crosslinking monomer R i.e. half of the amount by mole of monomer multiplied by the number of unsaturated groups of the monomer
• 0.05 and 0.5 for example between 0 , 05 and less than 0.1 or between 0.1 and less than 0.2, or between 0.2 and less than 0.3, or
• the nanogel may in particular have a molar mass (typically a weight average molar mass, typically determined by GPC coupled gas phase chromatography technique MALS or by MALS coupled Steric Exclusion Chromatography technique) greater than or equal to 100,000 g / mol. preferably greater than or equal to 350000 g / mol, for example between 500000 and 3500000 g / mol, for example between 1000000 and 2000000 g / mol.
• a molar mass typically a weight average molar mass, typically determined by GPC coupled gas phase chromatography technique MALS or by MALS coupled Steric Exclusion Chromatography technique
• step a) may in particular be carried out by bringing into the presence: the monomers, a control agent, for example an agent comprising a group -S-CS-, and a source of free radicals.
• a control agent for example an agent comprising a group -S-CS-
• a source of free radicals Such typologies of polymerizations are known to those skilled in the art and have been the subject of numerous publications. In particular, reference is made to the list established above.
• step a) can be followed by an optional step b) of chemical modification of the macromolecular chains and / or deactivation of transfer groups carried by macromolecular chains, destruction or purification of by-products of the modification. chemical and / or deactivation.
• Chemical modification steps of the macromolecular chains are aimed at adding functional groups to the chains, removing groups from the macromolecular chains or substituting groups of macromolecular chains. These groups may in particular be carried by units derived from monomers or worn in macromolecular chain ends. Such processes are known to those skilled in the art. Examples include complete or partial hydrolysis steps, or complete or partial crosslinking steps.
• the polymerization step a) will generally be carried out in the presence of a control agent (or transfer agent) having a control group (or transfer group).
• the control group is preferably a group of formula -S-CS-. It is preferably a non-polymeric transfer agent comprising a control group of formula -S-CS-.
• Control groups of the formula -S-CS- and compounds comprising these groups, in particular control agents, are known to those skilled in the art and are described in the literature. In particular, reference is made to the list established above. They can in particular be selected according to their reactivity with respect to certain monomers, and / or according to their solubility in the reaction medium.
• the control group can in particular comprise a group of formula -S-CS-Z- where Z is an oxygen atom, a carbon atom, a sulfur atom, a phosphorus atom or a silicon atom, these atoms being where appropriate substituted so as to have an appropriate valence.
• Z is an oxygen atom, a carbon atom, a sulfur atom, a phosphorus atom or a silicon atom, these atoms being where appropriate substituted so as to have an appropriate valence.
• an agent of Xanthate type having a control group of formula -S-CS-O-.
• the polymerization step a) will generally be carried out in the presence of a source of free radicals.
• a source of free radicals for certain monomers, such as styrene, the free radicals for initiating the polymerization can be generated by a monoethylenically unsaturated monomer, at sufficiently high temperatures generally above 100 ° C. In this case, it is not , necessary to add a source of additional free radicals.
• the source of free radicals 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-butyl peroxybenzoate, t-butylperoxyoctoate, t-butylperoxynethodecanoate and 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 (isobutyronitrile), azobis (cyclohexane-carbonitrile), 2- (t-butylazo) -2-cyano opropa, 2,2'-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) - 2 ', 2-methyl-N-hydroxyethyl] -propionamide, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dichloride, 2,2'-azobis (N, N'-dimethyl- 2,2'-azobis (2-amidinopropane) dichloride, 2,2'-azobis (N, N '-dimethyleneisobutyramide), 2,2'-azobis (2-methyl-N- [1,1-bis] (2,2-hydroxyethyl
• 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 polymerization can be carried out by heating, in known manner, so as to initiate and / or maintain the polymerization process.
• the degree of polymerization, and the masses, can be controlled by controlling the polymerization time. In particular, it is possible to stop the polymerization by lowering the temperature.
• the polymerizations may be carried out in any appropriate physical form, for example by solution polymerization in an aqueous medium (comprising water), for example in water or in an aqueous-alcoholic medium (for example, hydro-ethanol) or in a solvent for example an alcohol (for example ethanol) or THF, or by emulsion polymerization, preferably in inverse emulsion, if necessary by controlling the temperature and / or the pH in order to make liquid and / or soluble species or insoluble.
• the polymerization is preferably carried out in solution, as opposed to dispersed phase polymerizations (emulsion, microemulsion, polymerization with precipitation of the polymer formed). It is preferred to keep the nanogel in solution after such polymerization. It is specified that the nanogels are preferably obtained directly after the polymerization and the possible deactivation, elimination or destruction of transfer groups, without a functionalization step after the polymerization.
• the respective and relative amounts of monomer (s) C, crosslinking monomer (s), and control agent may be varied so as to control the size of the macromolecules generated, and / or to control the non-formation of a macroscopic macromolecular network.
• Some indications are given below: at constant amounts of monomer (s) C and control agent, when the amount of monomer (s) R is increased, the molecular masses and the polydispersity index are increased, and macroscopic macromolecular networks can be formed.
• at constant amounts of monomer (s) C and monomer (s) R when the amount of control agent is reduced, the molecular weights are increased and the polydispersity index macroscopic macromolecular networks can be formed.
• the polymerization is performed in the presence of a control agent in an amount such that (N * n C ⁇ ntroi C ⁇ ntroi / ⁇ n) is from 0.05 to 10%, preferably from 0.1 to 10%, preferably from 0.2 to 5%.
• the polymerization is carried out in the presence of crosslinking monomers R in an amount such that (N R / 2) * (n R / n ⁇ ) is from 0.01 to 40 mol%, preferably from 0.1 to 40% by weight. in moles, preferably from 1 to 40 mol%, for example from 5 to 20%.
• the polymerization is preferably carried out in the presence of a control agent and R-crosslinking monomer (s) in amounts such that r ⁇ 0.05, especially in one or both of the ranges mentioned above. preferably r ⁇ 0.1, preferably r ⁇ 0.2, preferably r ⁇ 0.25, preferably r ⁇ 0.3.
• a control agent and R-crosslinking monomer s
• r ⁇ 0.05 especially in one or both of the ranges mentioned above.
• the higher r the further away from a potential zone of macroscopic unwanted macromolecular lattice formation. It is not excluded that the number r is greater than or equal to 0.5 or 1.
• the household care composition may include treatment, preferably cleaning, hard surfaces or textile surfaces.
• Household care operations include care in the sphere of the private home, and in the public institutional or industrial sphere, for example in offices, hotels, restaurants, schools, where appropriate by service companies.
• Textile surface treatments include laundry operations on finished textile articles.
• the composition is a laundry composition, in a machine or by hand, advantageously by hand or in a semi-automatic machine, the nanogel being used as:
• the composition is a hard surface cleaning composition, the nanogel being used as a hydrophilizing agent and / or as an antifouling agent.
• the invention also relates to a method of implementing household care, comprising a step of contacting a household surface, preferably a textile surface or a hard surface household, with the composition where appropriate after prior dilution.
• 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 surface of the surface to be treated with hydrophilic, antideposition and / or antiadhesion properties. It can be for example:
• a cleaning or rinsing composition for household use may be universal or may be more specific, such as a composition for cleaning or rinsing a bathroom; said composition prevents, in particular, the deposition of the soap salts around the baths and on the washbasins, and / or prevents the growth and / or deposition of limestone crystals on these surfaces, and / or facilitates the direct or subsequent cleaning of soap stains (soap scum in English) and / or delays the appearance of subsequent soap scum tasks. 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.
• 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 thus does not escape the hands of the user; it has also been found a "squeaky clean" effect, namely that the surface "crunch” under the effect of a rub with the finger.
• 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, such as a composition for the cleaning of reactors, steel blades, sinks, vats, dishes on the outer or inner surfaces of glass buildings and buildings - bottles
• 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 it is, especially by spraying, - directly on the surfaces to be cleaned or rinsed, or on a sponge or other support (cellulose article for example, woven or non-woven) before to be applied on the surface to be treated
• composition • a liquid absorbed on an absorbent support in a woven or nonwoven article including (wipe) • a solid, especially tablet, optionally trapped in a water-soluble bag, said composition may represent all or part of the tablet.
• the nanogel is present in the composition subject of the invention in an amount effective to modify and / or treat the surface.
• it may be an effective amount to supply said surfaces of hydrophilic properties and / or anti-deposition and / or anti-adhesion of dirt likely to be deposited on said surfaces.
• Said composition subject of the invention may contain, according to its application, from 0.001 to 10% of its weight of the nanogel.
• 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.
• composition preferably cleaning or rinsing according to the invention, may further comprise at least one surfactant.
• This may be nonionic, anionic, amphoteric, zwitterionic or cationic. It may also be a mixture or combination of surfactants.
• the alkyl ester sulphonates of formula R-CH (SO 3 M) -COOR ' where R represents a C 8-20 alkyl radical, preferably C 0 - Ci 6 , R 'is an alkyl radical in dC 6 , preferably in C 1 -C 3 and M is an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium). .) or derivative of an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ).
• the alkylamide sulphates of formula RCONHR'OSO 3 M O ⁇ R represents a C 2 -C 22 alkyl radical, preferably C 6 -C 20 radical, R 'a C 2 -C 3 alkyl radical, M representing an atom of hydrogen or a cation of the same definition as above, as well as their
• 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 ).
• 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 ).
• alcohols polyols, alkylphenols, fatty acid esters, fatty acid amides and fatty amines
• amine oxides
• alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms, such as Miranol C2M Conc NP marketed by RHODIA, the amphoteric derivatives of the alkylpolyamines such as AM PHIONIC XL® marketed by RHO DIA, AM P HOLAC 7T / X® and AMPHOLAC 7C / X® marketed by BEROL NOBEL.
• zwitterionic surfactants include those described in U.S. 5,108,660,
• Preferred zwitterionic surfactants are alkyldimethyl betaines, alkylamidopropyldimethylbetaines, alkyldimethylsulfobetaines or alkylamidopropyldimethylsulfobetaines, such as Mirataine JCHA or H2CHA, and Mirataine CBS marketed 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 may together with the nitrogen atom N form at least one aromatic or heterocyclic ring
• R 4 represents a C 8 -C 22 alkyl or alkenyl group. preferably C-12-C22. an aryl or benzyl group, and X is a solubilizing anion such as halide (eg chloride, bromide, iodide), sulfate or alkylsulfate (methylsulfate), carboxylate (acetate, propionate, benzoate), alkyl or arylsulfonate.
• halide eg chloride, bromide, iodide
• sulfate or alkylsulfate methylsulfate
• carboxylate acetate, propionate, benzoate
• alkyl or arylsulfonate e.g chloride, bromide, iodide
• Other 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 'and R' are C8-C22 alkyl or alkenyl. preferably in
• - X ' is an anion such as halide (e.g. chloride, bromide, iodide), sulfate or alkylsulfate (methylsulfate), carboxylate (acetate, propionate, benzoate), alkyl or arylsulfonate.
• halide e.g. chloride, bromide, iodide
• sulfate or alkylsulfate methylsulfate
• carboxylate acetate, propionate, benzoate
• alkyl or arylsulfonate alkyl or arylsulfonate.
• dialkyldimethylammonium chlorides such as ditallow dimethylammonium chloride or methylsulphate, etc.
• alkylbenzyldimethylammonium chlorides alkylbenzyldimethylammonium chlorides.
• C 1 -C -alkylimidazolium salts such as C 1 -C 25 alkyl klyimidazolinium methyl sulphates
• Substituted polyamine salts such as N-tallow-N, N ', N', triethanol-1,3-propylenediamine dichloride or dimethylsulphate, 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%, in particular from 0.5 to
• the weight ratio nanogel / surfactant (s) is between 1/1 and 1/1000, advantageously 1/2 and 1/200.
• 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 type organic phosphonates and water-soluble aminophosphonates such as ethane 1-hydroxy-1,1-diphosphonates, aminotri (methylene diphosphonate) vinyldiphosphonates salts of the oligomers or polymers of vinylphosphonic acid or vinyldiphosphonic acid salts of random oligomers or copolymers of vinylphosphonic acid or vinyldiphosphonic acid and acrylic acid and / or maleic anhydride and / or vinylsulfonic acid and / or acrylamidomethylpropanesulfonic acid salts of polycarboxylic acids phosphonated polyacrylates terminated (s) phosphonate (s) salts of cotelomers of vinylphosphonic acid or vinyldiphosphonic acid and of acrylic acid such as those of the range BRIQUEST® or MIRAPOL A300 or 400 of RHODIA (at a rate of 0 to 10%, preferably from 0 to 5% of the total weight of cleaning composition);
• Polycarboxylic acids or their water-soluble salts and the water-soluble salts of carboxylic polymers or copolymers such as polyacrylic acid polycarboxylate ethers or hydroxypolycarboxylates or their salts (nitriloacetic acid, N, N-dicarboxymethyl-2-aminopentane dioic acid, ethylenediamine acid) tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetates, nitrilotriacetates, N- (2-hydroxyethyl) nitrilodiacetates), salts of C 5 -C 2 O alkyl succinic polyacetal carboxylic esters salts of polyaspartic or polyglutamic acids - citric acid, adipic acid, acid gluconic or tartaric acid or their salts Copolymers of acrylic acid and maleic anhydride or homopolymers of acrylic acid, such as Rhodoline DP
• 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; it may be amorphous silicates or lamellar silicates sold under the references NaSKS-5, NaSKS-7, NaSKS-1 and NaSKS-6 by Clariant;
• polymers used to control the viscosity of the mixture and / or the stability of the foams formed during 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)
• hydrotropic agents such as short C 2 -C 8 alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol, sodium xylene sulphonate, sodium naptalene sulphonate (at the rate of 0 to 10 g per 100 g of said cleaning composition)
• moisturizing agents or humectants for the skin such as glycerol, urea or skin-protecting agents, such as proteins or protein hydrolysates, vegetable oils such as soybean oil, cationic polymers such as cationic derivatives of the skin, guar (Jaguar C13S®, Jaguar C162®, HICARE 1000® sold by the company Rhodia, (at a rate of 0 to 40% of the total weight of said cleaning composition) * biocides or disinfectants as cationic biocides, for example
• Quaternary monoammonium salts such as - chlorides coco-alkyl dimethyl benzyl, C-
• amino heterocyclic monoquaternary salts such as laurylpyridinium chloride, cetylpyridinium, C-
• triphenyl phosphonium alkyl fatty salts such as myristyl triphenyl phosphonium bromide
• Polymer biocides such as those derived from the reaction of epichlorohydrin and dimethylamine or diethylamine - epichlorohydrin and imidazole from 1, 3-dichoro-2-propanol and dimethylamine 1, 3-dichloro-2-propanol and 1,3-bis-dimethylamino-2-propanol of ethylene dichloride and 1,3-bis-dimethylamino-2-propanol of bis (2-chloroethyl) ether and N , N'-bis (dimethylaminopropyl) urea or thiourea - the biguanidine polymer hydrochlorides, such as VANTOCIL IB
• Amphoteric biocides such as N- (N'-C8-C- ⁇ -alkyl-3-aminopropyl) -glycine derivatives of N- (N '- (N "-C8-C-) alkyl-2-aminoethyl) 2-aminoethyl) 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 such as parachlorometaxylenol, dichlorometaxylenol, 4-chloro-m-cresol, resorcinol monoacetate, mono- or polyalkyl or aryl phenols, cresols or resorcinols, such as o-phenylphenol, p-tert-butyl-phenol, 6-n-amyl-m-cresol, alkyl and / or aryl chloro or bromophenols, such as o-benzyl- p-chlorophenol halogenated diphenyl ethers such as 2 ', 4,4'-trichloro-2-hydroxy-diphenyl ether
• solvents before a good cleaning or degreasing activity 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 general formula, R 1 0 (R 20 where R1 is an alkyl group having from 3 to 8 carbons and each R2 is either ethylene or propylene and m is a number ranging from 1 to 3; mention may be made of monopropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, monopropylene glycol monobutyl ether, diethylene glycol monohexyl ether, monoethylene glycol monohexyl ether, monoethylene glycol monobutyl ether and mixtures thereof.
• octyl benzene alkylbenzenes olefins having a boiling point of at least
• 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.
• solvents such as pine oil, orange terpenes, benzyl alcohol, n-hexanol, phatlic esters of alcohols having 1 to 4 carbon atoms, butoxy propanol, butyl carbitol and the like.
• (2-n-butoxy-1-methylethoxy) propan-2-ol also called butoxy propoxy propanol or dipropylene glycol monobutyl ether, diglycol hexyl (Hexyl Carbitol), butyl triglycol, diols such as 2,2,4-trimethyl- 1,3-pentanediol, and mixtures thereof (at 0 to 30% of the total weight of said cleaning composition)
• non-cleaning, water-soluble organic solvents 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, especially greater than 11.7, since they help reduce the formation of films and traces on hard surfaces ( they can be used at a rate of 0.05 to 5% of the weight of the cleaning composition); solvent systems comprising monoethanolamide and / or beta-aminoalkanols are described in US 5,108,660. defoamers, such as soaps.
• Soaps are alkaline salts of fatty acids, including sodium, potassium, ammonium and higher alkanol ammonium salts of fatty acids containing from about 8 to 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms. carbon atoms; mention may especially be made of sodium and potassium mono-, di- and triethanolamine salts or mixtures of fatty acids derived from coconut oil and ground walnut oil.
• the amount of soap may be at least 0.005% by weight, preferably from 0.5% to 2% by weight relative to the total weight of the composition.
• Additional examples of foam control materials are organic solvents, hydrophobic silica, silicone oil and hydrocarbons.
• abrasives such as silica, calcium carbonate
• 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 of 8.5 to
• the alkaline compositions generally comprise, in addition to the nanogel, at least one additive chosen from
• a sequestering or antiscaling agent in an amount ranging from 0 to 40%, preferably from 1 to 40%, more preferably from 2 to 30% and most preferably from 5 to 20% by weight of the composition
• a biocide or disinfectant cationic, especially quaternary ammonium 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 to 60%, preferably 0 to 40%, more preferably 0 to 15% and most preferably 0 to 5% 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%, especially from 2 to 15% by weight of said composition, a co-solvent such as monoethanolamine and / or beta-aminoalkanols, in an amount which can represent from 0 to 10%, preferably from 0.05 to 10%, more particularly from 0.05 to 5% by weight of said composition
• a water-soluble organic solvent with little cleaning in a quantity 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 1000.000 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 benzylammonium 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 nanogel.
• the acidic compositions generally comprise, in addition to the nanogel,
• 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 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:
• 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 nanogel introduced will generally be such that, when using the cleaning composition, after dilution, the nanogel 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 nanogel; 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 consisting of water and usual additives (perfumes in particular).
• the pH of the composition is advantageously between 6 and 11.
• the composition of the invention is also interesting for the easy cleaning of the dishes in automatic machine.
• the composition may be either a detergent (cleaning) formula used in the wash cycle or a rinse formula.
• the dishwashing detergent compositions in automatic dishwashers according to the invention preferably comprise from 0.01 to 5%, preferably 0.1 to 3% by weight of the nanogel.
• 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.
• 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
• AMPS methyl propane sulfonic acid
• the pH is advantageously between 8 and 13.
• compositions for easy rinsing of automatic dishwashing dishes according to the invention may advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5% by weight of the nanogel 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 nanogel 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 aliphatic saturated alcohols C 5 -C 40, preferably C 1 -C 4, optionally condensed with about 0.5 to 30, preferably 0.5 at 8, in particular 0.5 to 5 moles of ethylene oxide, in acid form or in the form of a salt, in particular alkaline (sodium), alkaline earth metal
• surfactant preferably anionic, chosen in particular from sulphates of aliphatic saturated alcohols C 5 -C 40, preferably C 1 -C 4, optionally condensed with about 0.5 to 30, preferably 0.5 at 8, in particular 0.5 to 5 moles of ethylene oxide, in acid form or in the form of a salt, in particular al
• 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 fatty alcohol derivatives, alkylamides, alkanolamides, amphoteric or zwitterionic surfactants.
• nonionic surfactants such as amine oxides, alkylglucamides, alkyl polyglucosides, oxyalkylenated fatty alcohol derivatives, alkylamides, alkanolamides, amphoteric or zwitterionic surfactants.
• non-cationic bactericidal or disinfecting agents such as triclosan of the synthetic cationic polymers polymers to control the viscosity of the mixture and / or the stability of the foams formed with the use of hydrotropic agents; moisturizing or humectant or protective agents for the skin of the skin; dyes, perfumes, preservatives, divalent salts (in particular magnesium) ...
• the pH of the composition is advantageously between 5 and 9.
• Another particular embodiment of the invention consists of an easy external cleaning composition, in particular of the bodywork, of motorized vehicles (cars, trucks, buses, trains, planes, etc.).
• 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 nanogel relative to the total weight of said composition, as well as: nonionic surfactants (from 0 to 30%, preferably from 0.1 to 15% of the formulation), amphoteric and / or zwitterionic surfactants (from 0 to 30%, preferably from 0.01 to 10% of the formulation) of the cationic surfactants (from 0 to 30%, preferably from 0.05 to 15% of the formulation); anionic surfactants (from 0 to 30%, preferably from 0.1 to 15% of the formulation); builders (1 to 99%, preferably 40 to 98% of the formulation); hydrotropic agents fillers, pH regulating agents ...
• the minimum amount of surfactant present in the composition type is preferably at least 0.5% of the formulation.
• the pH of the composition is advantageously between 8 and 13.
• the composition of the invention is also particularly suitable for the easy cleaning of ceramic-type hard surfaces (tiles, bathtubs, washbasins, etc.), especially for bathrooms. It can especially facilitate the cleaning of soaps (soap scum in English).
• the cleaning formulation advantageously comprises from 0.02 to 5% by weight of the nanogel 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).
• 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.
• Said cleaning composition may also comprise 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) - an agent for regulating 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 total weight of the composition) pH regulating agents, dyes, optical brighteners, soil-suspending agents, detersive enzymes, compatible bleaching agents, gel-forming control agents, stabilizers, freezing-thawing, 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, advantageously 0.05 to 1% of the nanogel.
• 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).
• 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 1 1.
• the composition according to the invention can also be used for easy cleaning of vitroceramic plates.
• formulations for the cleaning of vitroceramic plates of the invention comprise:
• nanogel 0.01 to 5% by weight of the nanogel; 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
• a nonionic surfactant 1 to 10% by weight of a nonionic surfactant; and optionally alkalinizing agents or sequestering agents.
• the pH of the composition is advantageously between 7 and 12.
• the composition according to the invention can also be used in the field of industrial cleaning, in particular for easy cleaning of reactors.
• said compositions comprise: from 0.02 to 5% by weight of the nanogel; from 1 to 50% by weight of alkaline salts (phosphates, carbonates, sodium or potassium silicates); from 1 to 30% by weight of a mixture of surfactants, especially nonionic surfactants such as ethoxylated fatty alcohols and anionic surfactants such as lauryl benzene sulfonate; from 0 to 30% by weight of a solvent such as diisobutyl ester.
• the pH of such a composition is generally 8 to 14.
• 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, nanogel, for example as an agent for providing said surfaces with anti-deposition and / or anti-adhesion properties soils may deposit 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 nanogel to said compositions.
• 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 nanogel and optionally at least one surfactant.
• the nanogel is preferably used or is present in said composition in an amount effective to provide said surfaces with hydrophilic properties anti-deposition and / or anti-adhesion soils may be deposited on said surfaces.
• the nature and amounts of the nanogel 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.
• compositions of the invention may be foaming compositions. This may include dishwashing compositions by hand or in cases of hand washing or semi-automatic, vehicle cleaning compositions.
• the nanogel can stabilize the foam, especially with the addition of soiling.
• it can be used as detergent as an anti-redeposition agent.
• MBA N, N 'methylenebisacryamide (crosslinking monomer)
• MAPTAC (3-methacrylamidopropyl) trimethylammonium chloride
• APTAC (3-acrylamidopropyl) trimethylammonium chloride
• a linear copolymer is prepared having 95 mol% Acrylamide and 5 mol% MAPTAC, with an average molecular weight of 400 kg / mol.
• Example 1.3 Preparation of a cationic nanogel based on AM, MAPTAC and MBA - AM / MAPTAC / MBA
• V50 are added. From this moment, 1.83 g (0.013 mol) of MBA, 19.6 g (0.28 mol) of Am and 3.23 g (0.015 mol) of MAPTAC are added for 4 hours. During this time, at 0 ° + 2 hours, 0.042 (1.54 ⁇ 10 -4 mol) of V 50 are added respectively, at the end of the addition, the reaction is continued for a further 2 hours.
• compositions are prepared (per 1000 g of composition):
• Rhodasurf L7 / 90 nonionic surfactant
• LABS linear alkyl benzene sulfonate, anionic surfactant
• Rhodasurf L7 / 90 nonionic surfactant
• the foam index and the persistence of the foam are tested according to the protocol detailed below.
• the effect of redeposition of dirt on the fabric is tested using the protocol detailed below.
• Foam Index and Foam Persistence Tests Foam index and foam persistence for a test composition are determined using the following roller apparatus, according to the following protocol.
• the device has six parallel Plexiglas® cylinders attached to a rotating frame. Each cylinder has an inside diameter of 9cm, and a useful height of 29cm. Each cylinder has a graduated scale for measuring the height of foam.
• the cylinders are fixed on a rotating frame, each occupying a position equivalent to the others. Moved by an electric motor, the frame is rotated on itself, driving the cylinders in a rotation along an axis perpendicular to their length intersecting said cylinders in the middle of their length in the plane of the frame.
• the composition in a cylinder flows into the cylinder and strikes its ends (bottom and top) during rotation, thereby generating turbulence resulting in foam formation.
• Each cylinder is closed by a removable cover, pierced with a hole of 8mm in diameter allowing the addition of additives (dirt ). This hole is closed with a rubber stopper when the rolls are rotated.
• the Foam Height Unit (FHU) is defined as follows: 10 FHU corresponds to a foam height of 25 mm.
• the rotation speed is 20 rpm.
• the cylinders are rotated in sets of 10 rotations (each lasting 30 seconds), followed by 3 minutes of rest between each run, to allow the measurement of foam height (performed at the end of the three minutes) and the possible addition of dirt.
• Each cylinder contains 500ml of composition to be tested.
• the composition to be tested has a controlled initial temperature at 20 ° C.
• test composition 500 ml of test composition are poured into a cylinder, avoiding the formation of foam.
• the frame carrying the cylinders is then rotated in six series of 10 rotations (total of 60 rotations), each series being followed by 3 minutes of waiting.
• the foam height is raised in the cylinder after 3 minutes.
• the foam index is defined as the foam height, given in FHU, after the
• the rotation / hold / measure / soil addition implementation is repeated until the foam height reaches a value of less than 10 FHU.
• the foam height can be plotted or reported according to the number of rotations (soiling is only added after 60 rotations). The foam height (persistence of foam) when adding dirt is of particular interest. A slight decrease in the foam indicates stabilization of the foam in the presence of soiling.
• Soiling composition The soil used in the example is a synthetic sebum simulating greasy soils, for example those originating from human skin, mixed with a clay (bentonite) simulating particulate soils (dust, etc.).
• the ratio by weight between synthetic sebum and clay is 12/4.
• composition for 950g of synthetic sebum Composition for 950g of synthetic sebum:
• the laundry tested, used for washes, is a Brazilian brand laundry
• ACE to which the polymer to be tested is added.
• active polymer 0.025 g of active polymer is used per 5 g of lye.
• a percentage of soil removal is calculated as follows:
• the software makes it possible to calculate the Delta E '(theoretical maximum detergency) as follows:
• 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 according to the following protocol.
• the first operation is to prepare the tile. Simply clean it with ethanol with a kimwipe. Half of the surface is treated with the test composition (comprising one polymer) and the other half with the control composition. For this we add 5 drops of product that is spread with a kimwipe. The tile dries for 1 minute then is rinsed with a flow rate of 4.5L / min for 5 seconds on each side. The tile dries again vertically.
• the soil is prepared from a solution of 13% by weight soap in water and a 35% by weight solution in ethanol of MgCl 2 , 6H 2 O. The soap solution is heated to to make it liquid.
• composition of the invention allows an effective and durable treatment, resistant to rinsing.
• Example 4 Adsorption on a surface A composition comprising:
• the procedure is carried out by comparison using a reference comprising distilled water and KCl 10 " 3 M, according to the method below:
• compositions comprising:

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