EP2340299A1 - Copolymer zur oberflächenverarbeitung oder modifizierung - Google Patents

Copolymer zur oberflächenverarbeitung oder modifizierung

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Publication number
EP2340299A1
EP2340299A1 EP09809323A EP09809323A EP2340299A1 EP 2340299 A1 EP2340299 A1 EP 2340299A1 EP 09809323 A EP09809323 A EP 09809323A EP 09809323 A EP09809323 A EP 09809323A EP 2340299 A1 EP2340299 A1 EP 2340299A1
Authority
EP
European Patent Office
Prior art keywords
units
composition
copolymer
composition according
chloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09809323A
Other languages
English (en)
French (fr)
Other versions
EP2340299B1 (de
Inventor
Katerina Karagianni
Wojciech Bzducha
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
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Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2340299A1 publication Critical patent/EP2340299A1/de
Application granted granted Critical
Publication of EP2340299B1 publication Critical patent/EP2340299B1/de
Active legal-status Critical Current
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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
    • 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
    • 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
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to a composition for the treatment and / or modification of surfaces, particularly hard surfaces or textile surfaces.
  • the composition comprises a synthetic copolymer comprising cationic units and nonionic units.
  • the subject of the present invention is in particular a cleaning or rinsing composition intended for the treatment of textile-type surfaces or of industrial, domestic or community hard surfaces, in particular of the ceramic, tile, glass, metal, melamine, formica or plastic type, aimed at to confer on them, in particular, improved drying properties, and / or anti-deposition and / or non-sticking properties of the stains; it can also provide them with antistatic properties, gloss, anti-slip properties.
  • the invention more particularly relates to a cleaning or rinsing composition for the treatment of a surface, a composition which is capable of imparting thereto improved drying properties and / or residual properties of hydrophilicity, anti-exposure and / or anti-adhesion of soiling, so as to avoid the subsequent presence of traces due in particular: - drying drops of water deposited on said surface (eg deposit of mineral salts).
  • 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.
  • water or an aqueous composition is applied to the object to be cleaned, it is optionally rinsed and then allowed to dry. This is the case for example when cleaning dishes by hand, or when cleaning dishes automatically using a dishwasher.
  • the drying phase may take a certain time and / or may leave traces of water-soluble or water-dispersible materials (for example traces of mineral matter contained in the water) and / or traces of dirt, generally oily, originating from the water. object to clean.
  • PVP poly (vinylpyrrolidone)
  • the PVP allows a fast drying, and perceptible: we can observe the composition leave gradually the surface, and observe a front of composition to move on the surface like the ebb of a wave. We often speak of progressive dewetting, it is a discharge of water by flow rather than by evaporation. This is appreciated by the consumer who perceives the effect of the composition, and / or who perceives an effective drying.
  • the drying obtained following the application of a composition comprising PVP is indeed rapid.
  • the evacuation by flow also makes it possible to limit the traces.
  • PVP is of limited application: it can not be formulated in certain compositions, especially in dishwashing compositions, or only with difficulty in very narrow formulation windows.
  • dishwashing compositions generally significantly charged with surfactants, it is indeed poorly dispersible, and / or of low stability in these compositions. In particular, it can undermine transparency compositions, while transparency is a quality sought by consumers.
  • the quality of the drying following the application of a dishwashing composition in particular remains to be improved.
  • the present invention fulfills at least one of the above-mentioned needs, by providing a composition for treating and / or modifying surfaces, comprising a copolymer comprising cationic units A and other units B, characterized in that:
  • the units A comprise at least one quaternary ammonium group or an inium group
  • the units B are units derived from a monomer of the following formula:
  • R 2 is a divalent alkyl group a CrC 4 , preferably C 2 -
  • copolymer of the invention is designated "copolymer of the invention”.
  • the copolymer of the invention may in particular provide the following advantages, in particular for example in a dishwashing composition:
  • the copolymer of the invention is preferably used or is present in said composition in an amount effective to provide said surfaces with improved drying, and / or anti-deposition and / or anti-adhesion properties of soils deposited on said surfaces.
  • the composition may in particular have a slow dewetting and / or rapid drying and / or without trace.
  • the invention also relates to the use of the copolymer in treatment compositions and / or surface modifications. It may in particular be used as an agent for promoting dewetting, for example progressive and / or noticeable dewetting and / or rapid drying and / or without trace.
  • the invention also relates to a method for treating and / or modifying the surfaces, by applying the copolymer of the invention to the surface, preferably in the composition of the invention, said composition being optionally diluted in water with prior.
  • the invention also relates to the surfaces thus treated and / or modified.
  • the unit derived from a monomer for the different units of the precursor units A, denotes a unit which can be obtained directly from said monomer by polymerization.
  • a unit derived from an ester of acrylic or methacrylic acid does not cover a unit of 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 of vinyl acetate, respectively, and then hydrolyzing.
  • a unit derived from acrylic or methacrylic acid for example covers a unit obtained by polymerizing a monomer (for example an acrylic or methacrylic acid ester), then reacting (for example by hydrolysis) the polymer obtained so as to obtain units of formula -CH 2 -CH (COOH) -, or -CH 2 -C (CH 3 ) (COOH) -.
  • a unit derived from a vinyl alcohol for example covers a unit obtained by polymerizing a monomer (for example a vinyl ester), then reacting (for example by hydrolysis) the polymer obtained so as to obtain units of formula -CH 2 -CH (OH) -.
  • Units derived from a monomer A may for example have been obtained by polymerization of monomers A pre seu cu r r s and then post-polymerization reaction to obtain units comprising the betaine group.
  • a units are not considered to be units derived from pre- cursor monomers not comprising a betaine group. In the present application, unless otherwise indicated, when we speak of molar mass, it will be the average molar mass in absolute mass, expressed in g / mol.
  • This can be determined by aqueous gel permeation chromatography (GPC), by light scattering (DDL or MALLS for an aqueous eluent), with an aqueous eluent or an organic eluent (for example formamide) according to the composition of the polymer.
  • GPC aqueous gel permeation chromatography
  • DDL or MALLS light scattering
  • MALLS for an aqueous eluent
  • an aqueous eluent or an organic eluent for example formamide
  • the copolymer of the invention comprises cationic units A and other units B.
  • the units A comprise at least one quaternary ammonium group or an inium group.
  • the units B are units derived from a vinyl-lactam.
  • the A units are typically derived from monomer A comprising ethylenic unsaturation. It is preferably a linear random copolymer. It is noted that the positive charge carried by a nitrogen atom is typically located in a group lateral to the macromolecular chain that constitutes the copolymer.
  • the macromolecular chain is typically a polyethylene chain (from the unsaturations of the monomers), with cationic groups and side lactam groups.
  • Cationic units are cationic units. They include cationic groups, including a quaternary ammonium group or an inium group. In the present application, the cationic groups do not cover cationic groups, of weak base type, which may become cationic by adding a proton such as primary amines, or secondary amines, or even as amide groups.
  • the cationic groups can in particular be groups of type:
  • quaternary ammonium (of formula -N + R 3 in which R, identical or different, is a group other than the hydrogen atom, for example a hydrocarbon-based group, optionally substituted, optionally interrupted by heteroatoms, for example a linear or branched C 1 -C 22 alkyl group, for example a methyl group), or
  • R identical or different, is a group different from the hydrogen atom, one of which is optionally part of a cycle connected to the double bond, said ring optionally being aromatic, at least one of the groups R possibly being, for example, an optionally substituted hydrocarbon-based group, optionally interrupted by heteroatoms, for example a linear or branched C 1 -C 22 alkyl group, for example a group methyl).
  • quaternary ammonium groups it may in particular be a trimethylammonium group.
  • inium groups it may especially be a pyridinium group, preferably an alkylpyridinium group, preferably a methylpyridinium group.
  • the cationic group may be associated with a counter ion (anion). It may especially be a chloride, bromide, iodide, methylsulfate or ethylsulfate ion. It is noted that the anionic or potentially anionic groups of part A may constitute all or part of the counter ions associated with the cationic group. It is mentioned that the cationic units are not zwitterionic units comprising both a cationic group and an anionic or potentially anionic group (they would then be of generally zero charge). In other words, the R groups mentioned above do not include an anionic substituent.
  • MATAC (3-methacrylamidopropyl) trimethylammonium chloride
  • ATAC (3-acrylamidopropyl) trimethylammonium chloride
  • ADAMQUAT acryloyloxyethyltrimethylammonium salts
  • DMAC N, N-dimethyldiallylammonium chloride
  • X " is an anion, preferably chloride or methylsulfate, - bromide, chloride or methylsulfate of 1-ethyl 2-vinylpyridinium, or 1-ethyl-4-vinylpyridinium,
  • the units A can in particular be obtained by copolymerization, of monomers comprising the monomers A, mixed with other monomers).
  • a precursor of monomers comprising precursor monomers of the A units (in admixture with other monomers), leading to precursor units of the A units, and then chemical modification of the precursor units to obtain the A units.
  • modifications are known. For example, they may be quaternized, for example with dimethyl sulfate or halogenoalkylammonium or quaternary haloalkylhydroxyalkylammonium.
  • Units B are units derived from a monomer of the following formula:
  • R 1 is a hydrogen atom.
  • R 1 is a hydrogen atom
  • X -O-
  • R 2 is a divalent C 2 alkyl. It is then the monomer hydroxyethylacrylate (HEA).
  • the copolymer of the invention may comprise units C t e r, optional, different units A and B above.
  • the units A and B can represent from 1% to 100%, preferably from 50 to 100%, preferably from 75 to 100% by mole of the units of the copolymer.
  • the copolymer comprises:
  • the molar ratio between the units A and the units B is between 1/99 and 25/75, preferably between 5/95 and 15/85.
  • the copolymer may in particular comprise, as C units at t r e:
  • nonionic, hydrophilic or hydrophobic C N units and / or
  • anionic or potentially anionic C A units and / or
  • cationic or potentially cationic C c units different from A units, and / or zwitterionic C z units.
  • the units C N may for example be chosen from units derived from a vinyl lactam, preferably vinylpyrrolidone. It is specified that it is preferably N-vinyl-pyrrolidone.
  • the copolymer may for example comprise:
  • the copolymer does not comprise more than 50%, preferably 35%, preferably 25% in total, of such units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 50%, preferably 35%, preferably 25% by moles in total of C N units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 25 mol% in total of C A units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 25 mol% in total of C c units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 25 mol% in total of C z units, preferably not at all.
  • the copolymer is substantially free (it comprises less than 1 mol%, preferably less than 0.5%, preferably not at all) of the following units:
  • R 6 is a hydrogen atom or a methyl group
  • - X 2 is a group of formula -CO-O-, -CO-NH- or -C 6 H 4 -CH 2 -
  • n is an integer or mean number greater than or equal to 1
  • R 7 is a hydrogen atom, an alkyl group or a tristyrylphenyl group, and / or
  • R 6 is a hydrogen atom or a methyl group
  • X 2 is a group of formula -CO-O-, -CO-NH- or -C 6 H 4 -CH 2 -
  • R 8 is a hydrocarbon group containing at least two carbon atoms, comprising at least two -OH groups, preferably two consecutive carbon atoms, and / or
  • the copolymer is substantially free of zwitterionic units
  • the copolymer is substantially free of anionic or potentially anionic units.
  • a units are derived from N, N-dimethyldiallylammonium chloride (DADMAC) and the B units are derived from hydroxylethylacrylate (HEA).
  • DMDMAC N, N-dimethyldiallylammonium chloride
  • HSA hydroxylethylacrylate
  • DMAC N, N-dimethyldiallylammonium chloride
  • the copolymer may be in any convenient form, for example in solid, dry or vectorized form, for example in the form of a solution or of an emulsion or a suspension, in particular in the form of a aqueous solution.
  • the vectorized form for example an aqueous solution, can in particular comprise from 5 to 50% by weight of the copolymer, for example from 10 to 30% by weight.
  • the aqueous solution can in particular be a solution obtained by a method of preparation in the aqueous phase, in particular a radical polymerization process.
  • the polymer of the invention may in particular have a molar mass ranging from 20,000 g / mol to 1,000,000 g / mol, preferably from 100,000 to 400,000 g / mol.
  • the copolymer of the invention may be prepared by any suitable method.
  • the process will generally comprise a radical polymerization (copolymerization) step, where monomers are brought together, and a source of free radicals.
  • polymerization copolymerization
  • the process comprises a step of copolymerization by bringing together:
  • A (or A pre seu cu r r), comprising an ethylenically unsaturated group and a cationic group, - vinyl-lactam, and
  • Radical polymerization processes are known to those skilled in the art.
  • the source of free radicals the amount of free radicals, the introduction phases of the various compounds (monomers, source of radicals, etc.), the polymerization temperature, and other parameters or operating conditions can be varied. known and appropriate way. Some details or indications are given below.
  • the processes can be batch type processes ("batch” in English), semi-batch type ("semi-batch” in English) or even continuous type.
  • a semi-continuous type process typically comprises a phase of gradual introduction of at least one monomer (comonomer), preferably of all the monomers (comonomers), into a reactor, without continuous output of the reaction product, the product of reaction, comprising the polymer, being recovered at once at the end of the reaction.
  • the polymerization may advantageously be carried out in aqueous solution.
  • free radicals can be generated spontaneously, for example by raising the temperature, with appropriate monomers such as styrene.
  • Free radicals can be generated by irradiation, especially by UV irradiation, preferably in the presence of appropriate UV-sensitive initiators. It is possible to use initiators (or "initiators") or initiator systems, of radical type or redox type.
  • the free radical source may be water soluble or not. It is preferable to use water-soluble or at least partially water-soluble initiators (for example water-soluble at least 50% by weight).
  • the following initiators may especially be used: hydrogen peroxides, such as tertiary butylhydroxyperoxide, cumene hydroperoxide, tert-butyl peroxyacetate, t-butyl peroxybenzoate or t-butylperoxyoctoate; t-butylperoxyneodecanoate, t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate,
  • hydrogen peroxides such as tertiary butylhydroxyperoxide, cumene hydroperoxide, tert-butyl peroxyacetate, t-butyl peroxybenzoate or t-butylperoxyoctoate
  • t-butylperoxyneodecanoate
  • azo compounds such as: 2-2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1,1 ' -azobis (cyclohexanecarbonyl), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) -2- and 2,2-azobis (2-methyl-N-hydroxyethyl) propionamide, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dichloride, dichloride 2,2'-azobis (2-amidinopropane), 2,2'-azobis (N, N'-dimethyleneisobutyramide), 2,2'-azobis (2-methyl-N- [1,1-bis ( hydroxymethyl) -2-hydoxyethyldipropionamide), 2,2'-azobis (2-methyl-N- [1,1-
  • redox systems comprising combinations such as: mixtures of hydrogen peroxide, alkyl, peresters, percarbonates and the like and of any of the iron salts, titanous salts, zinc formaldehyde sulfoxylate or formaldehyde sulfoxylate sodium, and reducing sugars,
  • 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 polymerization temperature may especially be between 25 ° C and 95 ° C.
  • the temperature may depend on the source of free radicals. If it is not a source of the UV initiator type, it will be preferable to operate between 50 ° C. and 95 ° C., more preferably between 60 ° C. and 80 ° C. In general, the higher the temperature, the easier the polymerization is initiated (it is favored), the lower the molecular weights of the copolymers obtained.
  • composition of the invention may be in various forms. It can in particular be in a liquid form. It may then comprise a liquid application vector, for example water, an alcohol or a hydro-alcoholic mixture.
  • a liquid application vector for example water, an alcohol or a hydro-alcoholic mixture.
  • the composition of the invention most often comprises at least one surfactant.
  • the surface is a textile, the treatment preferably being a cleaning or rinsing of the laundry.
  • the treatment is typically a treatment applied to a finished textile article, where the fibers are assembled.
  • the treatment is typically not a treatment implemented during the manufacture of the textile article. This is typically a treatment step (cleaning, rinsing, and / or softening) after a first use (at least) by the consumer.
  • the laundry may include articles made of cotton or cotton and / or wool. It may alternatively or additionally comprise articles made of synthetic fibers, in particular polyester, polyamide or acrylic.
  • compositions may especially be compositions for washing and / or rinsing and / or softening articles made of textile fibers, for the stain removal of pre-washing textile fibers ("prespotting"), for drying fiber articles. textiles in tumble dryers or to facilitate the ironing of textile fiber articles.
  • pre-washing textile fibers for drying fiber articles.
  • the form of the composition and the conditions of use (or treatment) can be multiple. Said composition may occur
  • composition of the invention can be:
  • a liquid rinse and / or softening formulation capable of forming directly by dilution a rinsing bath and / or softening;
  • drying additive a solid material, in particular a textile, comprising the copolymer, intended to be brought into contact with the wet articles in a tumble dryer (said solid material is hereinafter referred to as "drying additive");
  • an aqueous ironing formulation a washing additive ("prespotter") intended to be deposited on the dry articles prior to a washing operation using a detergent formulation containing or not containing the copolymer (said additive is hereinafter referred to as "additive washing ").
  • the composition of the invention is particularly well suited to the care of articles (linen) in particular cotton-based, in particular containing at least 35% cotton. It is particularly adapted to the care of colored articles.
  • the amount of copolymer of the invention present in the treatment composition of textile articles according to the invention can range from 0.05 to 10% by dry weight of said composition in dry.
  • the composition may contain at least one surfactant and / or detergent and / or rinsing and / or softening additive for textile fiber articles.
  • the nature of these constituents is a function of the desired use of said composition.
  • a detergent formulation for washing textile fiber articles, it generally comprises:
  • an oxidizing agent or system optionally an oxidizing agent or system, and a series of specific additives.
  • the textile treatment formulation may include, in particular, surfactants in an amount corresponding to about 1 to 40% by weight of the detergent formulation.
  • the surface is a hard surface, the treatment being preferably a hard surface cleaning.
  • Hard surfaces and their treatments and / or modifications include in the present invention the dishes and its cleaning and / or rinsing.
  • the treatment can be a dishwashing, automatic or by hand.
  • the treatment may be cleaning transparent walls such as glass panes or plastic, preferably vertical or inclined.
  • the composition according to the invention is particularly likely to provide the hard surfaces to be treated antideposition and / or antiadhesive properties of stains and / or improved drying properties. It can be for example: - A cleaning or rinsing composition for household use; it can be universal or can be more specific, such as a composition for cleaning or rinsing bathroom; said composition prevents in particular the deposition of soap salts around the baths and on the washbasins, prevents the growth and / or deposition of limestone crystals on these surfaces, and delays the appearance of subsequent soap stains.
  • said composition makes it possible to improve the cleaning of the worktops when they are soiled by unsaturated fatty soils that may crosslink over time; the greasy stains leave the water without rubbing. floors (linoleum, tiles or cement); said composition makes it possible to improve the removal of dust, soils of clay-limestone types (earth, sand, mud, etc.); the tasks on the floor can be cleaned effortlessly by simply sweeping, without brushing; in addition, said composition provides anti-slip properties.
  • said composition prevents the adhesion of traces of excrement on the surface; the only flow of flush is enough to remove these traces; the use of a brush is useless, windows or mirrors; said composition makes it possible to prevent the deposit of particulate mineral or organic dirt on the surface, and / or to improve drying, in particular for vertical or inclined panes or mirrors. dishes, by hand or with the help of an automatic machine; said composition makes it possible to observe improved drying of the exterior of vehicles.
  • 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 • a gelled liquid or not, to dilute in water (possibly added another solvent) before being applied on the surface to be treated
  • a liquid absorbed on an absorbent support in a woven or non-woven article in particular (wipe)
  • composition may represent all or part of the tablet.
  • the copolymer of the invention is present in the composition subject of the invention in an amount effective to modify and / or treat the surface. It may for example be an amount effective to provide said surfaces with anti-deposition and / or anti-adhesion properties soils may deposit on said surfaces, and / or to provide improved drying.
  • composition subject of the invention may contain, according to its application, from 0.001 to 10% of its weight of the copolymer of the invention.
  • the pH of the composition or the pH of use of the composition according to the invention may vary, depending on the applications and the surfaces to be treated, from 1 to 14, or even from 0.5 to 14.
  • the extreme pH are conventional in industrial or community cleaning type applications. In the field of household applications, the pH range from 1 to 13 depending on the applications.
  • Said composition may be used for cleaning or rinsing hard surfaces, in 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 according to the invention when used in the context of a treatment of a textile surface, such as laundry to be cleaned, is particularly likely to protect the colors of the textile and / or prevent the transfer colors from one article to another, especially in a detergent bath.
  • the copolymer of the invention can be used as a color protection agent for the laundry and / or as a color transfer prevention agent.
  • the cleaning or rinsing composition according to the invention preferably further comprises at least one surfactant.
  • This can 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
  • alkanolamine (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ”) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...) - alkylphosphates, alkylated or alkylaryl esters phosphates such as RHODAFAC RA600, RHODAFAC PA15 or RHODAFAC PA23 marketed by RHODIA; the cation may be an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative of an alkanolamine (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
  • Antarox B12DF Antarox FM33, Antarox FM63, Rhodia Antarox V74, Plurafac LF 400, Plurafac LF 220 from BASF, Rhodasurf ID 060, Rhodasurf ID 070, Rhodasurf LA 42 from Rhodia, Synperonic A5, A7, A9 from ICI amine oxides such as dodecyl di (2-hydroxyethyl) amine oxide phosphine oxides, such as tetradecyl dimethyl phosphine oxide
  • 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 the alkylpolyamines such as AM PHIONIC XL® marketed by RHO DIA, AM P HOLAC 7T / X® and AMPHOLAC 7C / X® marketed by BEROL NOBEL.
  • the zwitterionic surfactants include those described in US 5,108,660,
  • the preferred zwitterionic surfactants are alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyldimethylsulfobetaines or alkylamidopropyldimethylsulfobetaines, such as Mirataine JCHA or H2C HA, 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 1, R 3, R 3 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 with one or more hydroxyl function (s); (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 C12-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 alkyl or arylsulfonate.
  • cationic surfactants can also be mentioned, such as: • quaternary ammonium salts of formula
  • R 'and R' which are similar or different, represent H or an alkyl group containing less than 4 carbon atoms, preferably 1 or 2 carbon atoms, optionally substituted by one or more hydroxyl function (s), or may together with the nitrogen atom N form a heterocyclic ring
  • R 'and R' are C8-C22 alkyl or alkenyl. preferably in
  • - 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.
  • halide for example chloride, bromide, iodide
  • sulphate or alkyl sulphate methyl sulphate
  • carboxylate acetate, propionate, benzoate
  • alkyl or aryl sulphonate alkyl or aryl sulphonate.
  • dialkyldimethylammonium chlorides such as ditallow dimethylammonium chloride or methylsulphate, etc.
  • alkylbenzyldimethylammonium chlorides alkylbenzyldimethylammonium chlorides.
  • C -C1 alkylalkidazolium salts such as C1-C25 alkyl imidazolinium 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 copolymer / 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 in particular of the organic phosphonate type 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 salts of co-oligomers or random copolymers of vinylphosphonic acid or vinyldiphosphonic acid and acrylic acid and / or maleic anhydride and / or vinylsulfonic acid and / or racrylamidomethylpropane sulfonic acid salts of phosphonated polycarboxylic acids - phosphonate-terminated polyacrylates of cotelomers of vinylphosphonic acid or vinyldiphosphonic acid and of acrylic acid, such as those from the RHODIA range of BRIQUEST® or MIRAPOL A300 or 400 (at 0 to 10%, preferably from 0 to 5% of the total weight of cleaning composition); * sequester
  • Polycarboxylic acids or their hydrosoluble salts and water-soluble salts of carboxylic polymers or copolymers such as polyacetic acid polycarboxylate ethers or hydroxypolycarboxylates 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 2 0 alkyl succinic acid salts - polyacetal carboxylic esters salts of polyaspartic or polyglutamic acids citric acid, adipic acid , gluconic acid or tartaric acid or their salts
  • Copolymers of acrylic acid and maleic anhydride or homopolymers of acrylic acid such as Rhodoline DP 226 from Rhodia and Sokalan CP5 from BASF (from 0 to 10%, of the total weight of said composition cleaning) ;
  • RHODIAPHOS HD7 marketed by RHODIA, (from 0 to 70% of the total weight of cleaning composition); • alkaline pyrophosphates Alkali metal silicates, with SiO 2 / M 2 O ratio ranging from 1 to 4, preferably from 1.5 to 3.5, especially from 1.7 to 2.8; it may be amorphous silicates or lamellar silicates sold under the references NaSKS-5, NaSKS-7, NaSKS-1 and NaSKS-6 by Clariant; Alkali or alkaline earth borates, carbonates, bicarbonates, sesquicarbonates (in an amount of up to about 50% of the total weight of said cleaning composition);
  • 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
  • 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
  • transition-metal-containing bleach catalysts particularly iron, manganese and cobalt complexes, such as those of the type [F e "(MeN 4 py) (MeCN)] (ClO4) 2 ,
  • alkalizing additives alkali metal phosphates, carbonates, perborates, alkali metal hydroxides
  • acidifying additives which may be cleansers, such as mineral acids (phosphoric acid, polyphosphoric acid, sulphamic acid, hydrochloric acid, hydrofluoric acid, sulfuric, nitric, chromic), carboxylic or polycarboxylic acids (acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid, lactic acid, malonic acid, oxalic acid, succinic acid and tartaric acid) or salts thereof acids such as sodium bisulfate, alkali metal bicarbonates and sesquicarbonates.
  • polymers used to control the viscosity of the mixture and / or the stability of 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)
  • 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 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 of coconut alkyl benzyl dimethyl ammonium, C-12-C14 alkyl benzyl dimethyl ammonium chloride, coco-alkyl dichlorobenzyl dimethyl ammonium chloride, tetradecyl benzyl dimethyl ammonium, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromides myristyl trimethylammonium, cetyl trimethylammonium * salts of monoquaternary heterocyclic amines such as laurylpyridinium, cetylpyridinium, C-12-C14 alkyl benzylimidazolium chlorides
  • triphenyl phosphonium alkyl fatty salts such as myristyl triphenyl phosphonium bromide
  • 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 (triclosan), 2,2'-dihydroxy-5,5'-dibromo-diphenyl ether. chlorophenesine (p-chlorophenyl
  • 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 0 (R 20) m H where R 1 is an alkyl group having from 3 to 8 carbons and each R 2 is either ethylene or propylene and m is a number ranging from 1 to 3; mention may be made of monopropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, monopropylene glycol monobutyl ether, diethylene glycol monohexyl ether, monoethylene glycol monohexyl ether, monoethylene glycol monobutyl ether and mixtures thereof. diols having from 6 to 16 carbon atoms in their molecular structure; diols are particularly interesting
  • the diols containing from 8 to 12 carbon atoms are preferred, most preferably 2,2,4-trimethyl-1,3-pentanediol.
  • other solvents such as pine oil, orange terpenes, benzyl alcohol, n-hexanol, phatlic esters of alcohols having 1 to 4 carbon atoms, butoxy propanol, butyl carbitol and the like.
  • (2-n-butoxy-1-methylethoxy) propan-2-ol also called butoxy propoxy propanol or dipropylene glycol monobutyl ether, diglycol hexyl (Hexyl Carbitol), butyl triglycol, diols such as 2,2,4-trimethyl- 1,3-pentanediol, and mixtures thereof (at 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); cosolvents such as monoethanolamide and / or beta-aminoalkanols, which are particularly useful in compositions with pH greater than 1 1, especially greater than 11.7, since they help to reduce the formation of films and traces on hard surfaces (they can be implemented 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 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 copolymer of the invention.
  • the alkaline compositions generally comprise, in addition to the copolymer, at least one additive selected from
  • a sequestering or antiscaling agent (in an amount ranging from 0 to 40%, preferably from 1 to 40%, more preferably from 2 to 30% and most preferably from 5 to 20% by weight of the composition)
  • a cationic biocide or disinfectant especially of the quaternary ammonium type, such as N-alkylbenzyl dimethyl ammonium chlorides, N-alkyl dimethyl ethylbenzyl ammonium chloride, N-didecydimethylammonium halide and di-N-alkyl dimethyl ammonium chloride ( in an amount ranging from 0 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 surfactant, amphoteric, zwitterionic, or anionic or their mixture; when a cationic surfactant is present, said composition preferably further comprises an amphoteric and / or nonionic surfactant (the total amount of surfactants can range from 0 to 80%, preferably from 0 to 50%, all especially from 0 to 35% of the weight of the composition)
  • a pH regulating agent in an amount to reach, optionally after dilution or dissolution of the composition, a pH of use ranging from 7.5 to 13;
  • the pH-regulating agent can in particular be a buffer system comprising monoethanolamine and / or a beta-aminoalkanol and potentially but preferably alkaline materials "co-buffer" of the ammonia group, C2-C4 alkanolamines, alkali hydroxides, silicates, borates, carbonates, bicarbonates and mixtures thereof.
  • Preferred cotampons are alkali hydroxides.
  • an organic solvent which is a cleanser or degreaser, in an amount which can represent from 0 to 60%, preferably from 1 to 45%, especially 2 to 15% of the weight of said composition
  • a co-solvent such as monoethanolamine and / or beta-aminoalkanols, in an amount which may 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 10,000 times, preferably 1 to 1000 times before use.
  • a formulation for cleaning kitchens comprises: from 0.001 to 1% by weight of the copolymer of the invention
  • 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 may comprise from 0.001 to 5%, preferably from 0.01 to 2%, of their weight of the copolymer of the invention.
  • compositions generally comprise, in addition to the copolymer of the invention,
  • 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
  • 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)
  • 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 be in particular a mineral acid such as the acid phosphoric, sulfamic, hydrochloric, hydrofluoric, sulfuric, nitric, chromic and mixtures thereof or an organic acid, especially acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid lactic, malonic, oxalic, succinic and tartaric acid as well as mixtures thereof, acid salts such as sodium bisulfate and mixtures thereof; the preferred amount depends on the type of acid cleaner used: for example with sulfamic acid, it is between 0.2 and 10%, with hydrochloric acid between 1 and 15%
  • 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
  • the composition according to the invention can be implemented for the easy cleaning treatment of glass surfaces, in particular windows.
  • This treatment can be performed by the various known techniques.
  • techniques for cleaning windows by spraying a jet of water using devices of the Karcher® type can be mentioned.
  • the amount of copolymer of the invention introduced will generally be such that, when using the cleaning composition, after optional dilution, the copolymer concentration of the invention is between 0.001 g / l and 2 g / l, preferably 0.005 g / l and 0.5 g / l.
  • 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 copolymer of the invention; from 0.005 to 20%, preferably from 0.5 to 10% by weight, of at least one nonionic surfactant (for example an amine oxide or an alkyl polyglucoside) and / or anionic surfactant; and the remainder being water and / or various additives customary in the field.
  • 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 (especially perfumes).
  • the pH of the composition is advantageously between 6 and 1 1.
  • the composition of the invention is also interesting for the easy cleaning of the dishes in automatic machine.
  • the composition may be either a detergent (cleaning) formula used in the wash cycle or a rinse formula.
  • the dishwashing detergent compositions in automatic dishwashers according to the invention preferably comprise from 0.01 to 5%, preferably 0.1 to 3% by weight of the copolymer of the invention.
  • Said dishwashing detergent compositions also comprise at least one surfactant, preferably nonionic in an amount ranging from 0.2 to
  • At least one bleaching agent preferably perborate or percarbonate, associated or not with a bleach activator
  • At least one filler preferably sodium sulfate or sodium chloride
  • the pH is advantageously between 8 and 13.
  • compositions for easy rinsing of automatic dishwashing dishes may advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5% by weight of the copolymer of the invention relative to total weight of the composition.
  • Said compositions may also comprise from 0.1 to 20%, preferably from 0.2 to 15% by weight relative to the total weight of said composition of a surfactant, preferably a nonionic surfactant.
  • 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.
  • 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 copolymer of the invention, relative to the total weight of said composition, as well as: nonionic surfactants (from 0 to 30%, preferably from 0.1 to 15% of the formulation), amphoteric and / or zwitterionic surfactants (at a level of from 0 to 30%, preferably from 0.01 to 10% of the formulation) of the cationic surfactants (at the rate of 0 to 30%, preferably 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 (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.
  • the cleaning formulation advantageously comprises from 0.02 to 5% by weight of the copolymer of the invention, relative to the total weight of said composition and at least one surfactant.
  • 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 rinsing compositions of the shower walls comprise from 0.02% to 5% by weight, advantageously from 0.05% to 1% of the copolymer of the invention.
  • the other main active components of the aqueous shower rinse compositions of the present invention are at least one surfactant present in an amount ranging from 0.5 to 5% by weight and optionally a chelating agent of metals as mentioned above, present in an amount of from 0.01 to 5% by weight.
  • the aqueous shower rinse compositions advantageously contain water with optionally at least one lower alcohol in the majority 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).
  • 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® (H LB 1 3 , 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 the facilitated cleaning of vitroceramic plates.
  • formulations for the cleaning of vitroceramic plates of the invention comprise:
  • the copolymer of the invention 0.01 to 5% by weight of the copolymer of the invention; 0.1 to 1% by weight of a thickener such as xanthan gum; - 10 to 60% by weight of an abrasive agent such as calcium carbonate or silica; 0 to 7% by weight of a solvent such as butyldiglycol; 1 to 10% by weight of a nonionic surfactant; and optionally alkalinizing agents or sequestering agents.
  • 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: from 0.02 to 5% by weight of the copolymer of the invention; from 1 to 50% by weight of alkali metal salts (phosphates, carbonates, sodium or potassium silicates); from 1 to 30% by weight of a mixture of surfactants, especially nonionic surfactants such as ethoxylated fatty alcohols and anionic surfactants such as lauryl benzene sulfonate; from 0 to 30% by weight of a solvent such as diisobutyl ester.
  • the pH of such a composition is generally 8 to 14.
  • composition of the invention may especially be a dishwashing composition, automatic or by hand. Such compositions are known.
  • compositions may in particular comprise at least one surfactant.
  • Compositions for automatic dishwashing generally additionally include a builder agent ("builder").
  • the dishwashing detergent composition may comprise in particular from 0.01% to 5%, preferably from 0.05 to 3%, preferably from 0.2% to 1.5%, by weight, of the copolymer of the invention.
  • the dishwashing detergent composition may be in any form, especially in aqueous or non-aqueous liquid form, preferably concentrated in solid form or in gel form.
  • the dishwashing composition may be susceptible to foaming in an aqueous medium. It preferably comprises at least one surfactant.
  • Surfactants which can be used have been mentioned above.
  • the surfactant may especially be chosen from anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants or mixtures thereof.
  • the amount of surfactant, expressed in seconds, may represent from 0.1 to 99
  • the dishwashing composition is a soap bar type solid
  • the amount of surfactant, expressed as dry can be up to 99%, preferably up to 95% of the total composition mass; this amount usually represents at least 50% of the total composition mass.
  • the soap bar solids may further contain water and / or a water-compatible solvent in an amount of up to 20% of the mass of said solid.
  • total composition mass is meant the mass of the whole composition including, in addition to the copolymer of the invention and optionally the surfactant (S), the other possible constituents (water, solvents, other additives).
  • Hand dishwashing compositions may further include foam modifying additives, including foam improvers, density, and / or whiteness, agents which increase the shelf life of the foam. foam and / or increasing the amount of foam. In some cases we speak of foam toners ("foam enhancers" or "foam boosters" in English).
  • AA aliphatic alcohols
  • AA aliphatic alcohols
  • It can also be (co) polymers, for example described in WO 00/71651, WO 00/71591, WO 02/026844, US 6656900, EP1 180061, WO 99/27058, WO 99/27054, WO 99/27053, WO 99/27057, WO 00/71660, WO 00/71659, WO 00/71241, WO 00/71652, WO 00/71658.
  • the dishwashing composition further comprises water and / or at least one water-compatible solvent.
  • Water-compatible solvent is understood to mean any solvent which, when mixed with water, forms, at ambient temperature, a single, transparent phase.
  • the water and / or the solvent can represent up to 99.5% of the total mass of said composition; the minimum amount of water and / or solvent compatible with water is usually 1%.
  • said solvent can represent up to 80% of the weight of said mixture.
  • Said solvent is preferably chosen from C 2 -C 8 aliphatic mono or polyalcohols, and their ethers. Examples of solvents that may be mentioned include ethanol, propanol, isopropanol, butanol, 2-butoxyethanol, diethylene glycol, 1-butoxyethanol-2-propanol and diethylene monobutyl ether.
  • Said dishwashing composition may further comprise at least one polymer for controlling the viscosity and / or the stability of the foams, such as polyacrylic acids or their water-soluble salts having a molecular weight of from 1000 to 5,000,000 g / mol, the ethylene oxide-oxide block copolymers propylene of molecular weight by weight up to 30,000 g / mol, polyethylene glycols having a molecular weight of at least 400 g / mol, the biopolymers having a molecular weight of at least 10,000 g / mol; when present, said polymer may represent from 0.01 to 10% of the dry mass of the concentrated liquid composition.
  • polyacrylic acids or their water-soluble salts having a molecular weight of from 1000 to 5,000,000 g / mol
  • polyethylene glycols having a molecular weight of at least 400 g /
  • concentrated composition any composition that can be diluted during use.
  • polymers capable of controlling the viscosity and / or the stability of the foams mention may be made of polyacrylic acids or their salts, such as CARBOPOL from B. F.
  • CARBOPOL 941 CARBOPOL 801, CARBOPOL 907, CARBOPOL 910, CARBOPOL 934, CARBOPOL 940 • Ethylene oxide-propylene oxide block copolymers, such as
  • Rhodia ANTAROX in particular ANTAROX F-88 "biopolymers such as guar, arabic, xanthan, rheozan, welan, carragenans, cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropyl- guar)
  • bleaching agents builders, hydrotropic agents, moisturizers, fragrances, biocides, preservatives and other usual additives, depending on the destination of the composition.
  • hydrotropic agents such as short C 2 -C 8 alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol,
  • moisturizing or humectant agents for the skin such as glycerol, urea or skin-protecting agents, such as proteins or protein hydrolysates, cationic polymers such as cationic guar derivatives (Jaguar C13S®, Jaguar C162®, HICARE 1000® marketed by RHODIA.
  • compositions can be diluted at the time of their use, they can be diluted 10 to 50 000 times their volume according to their destination.
  • Their concentration of surfactant, after dilution, can generally reach from 0.0001 to 10%, preferably from 0.001 to 5%, especially from
  • the dishwashing composition can be used in the usual manner.
  • a manual dishwashing process it is possible, for example, to operate according to a process comprising the following steps: Step a) optionally dilute the composition in water
  • Step b) bringing the dishwashing object to be cleaned into contact with the possibly diluted composition, where appropriate using an application means, Step c) generally scrub the dishes using a means of rubbing, Step d) possibly rinse the dishes Step e) dry.
  • Dishwashing processes may vary by individual.
  • Step a) may correspond to the constitution of a dishwashing bath.
  • the dilution ratio can typically be 100 to 2000. This is sometimes referred to as a "full sink" process.
  • the copolymer concentration of the invention may especially be from 0.00025% to 0.01%, preferably from 0.0001 to 0.005%.
  • the dilution ratio can be adapted for this purpose. In particular it can be prescribed by any means of communication related to the product, for example on the label, in an advertisement, via a consumer service, a website.
  • the copolymer concentration of the invention can in particular be from 1 to 100.
  • Step b) may in particular be performed by quenching the dishware object in a dishwashing bath.
  • the composition is applied directly to the dishware object, for example by pressure on a flexible or semi-flexible container comprising the composition or with the aid of a pump, or by simple gravity.
  • the composition is applied to an application means such as a sponge, a pad, a brush or the fingers of the person operating the dishes, possibly protected by gloves, and the means of application is put in contact of the dishware object.
  • an application means such as a sponge, a pad, a brush or the fingers of the person operating the dishes, possibly protected by gloves, and the means of application is put in contact of the dishware object.
  • the direct application type process may be preferred and provide a more significant drying improvement.
  • it can be prescribed by any means of communication related to the product, for example on the label, in an advertisement, via a consumer service, a website.
  • the friction step c) can be carried out in a conventional manner by circular movements and / or reciprocating movements of the friction means on the dishware object.
  • the friction means may be for example a sponge, a pad, a brush or the fingers of the person operating the dishes, possibly protected by gloves. It can also act on the means of application of step b). It is possible to operate the contacting while rubbing, step b) and step c) are then merged.
  • Step d) is generally recommended. It can be operated in a conventional manner, for example by quenching in clean water (the dishware is then removed), or by passing under a jet of water.
  • Step e) can be operated in a conventional manner. During this step, simply let the dishes dry, if necessary on a drainer or a cloth or other device promoting the evacuation and / or absorption of water.
  • the letter C indicates that it is a comparative example.
  • Example 1.1 C Preparation of a 90 mol% / 10 mol% PV / DADMAC Copolymer
  • a refrigerant and a temperature control by a cryothermostat 233 g of water are added. Under nitrogen sweep, the temperature of the reaction medium is brought to 75 ° C.
  • 76 mg of 2,2'-azobis (2-methylpropionamidine) dichloride are added, followed simultaneously by 38.5 g of 65% DADMAC in water over 3 hours and 310 g of 50% n-vinylpyrrolidone in water.
  • Example 1.2 Preparation of a 90 mol% / 10 mol% - 08DBT034 HEA / DADMAC copolymer
  • a refrigerant and a temperature control by a cryothermostat are added 390g of water. Under nitrogen sweep, the temperature of the reaction medium is brought to 75 ° C.
  • 0.10 g of initiator V-50 (2,2'-azobis (2-methylpropionamidine) dichloride) solubilized in 0.57 g of water are added.
  • a monomer mixture (41.3 g of 65% DADMAC in water with 173.1 g of 2-hydroxyethylacrylate) is added continuously over 3 hours.
  • V-50 initiator in 39.2 g of water is added over 4 hours. At the end of addition of initiator, the reaction mixture is maintained at 75 ° C. for 1 hour. Subsequently, 0.50 g of solubilized V-50 initiator in 2.80 g of water is added in one go, then the reaction mixture is maintained at 75 ° C. for 1 hour. 0.50 g of solubilized V-50 initiator in 2.80 g of water are then added in one go, and the reaction mixture is then maintained at 75 ° C. for 90 minutes. The reaction medium is then cooled to room temperature.
  • a refrigerant and a temperature control by a cryothermostat are added 509 g of water. Under nitrogen sweep, the temperature of the reaction medium is brought to 75 ° C. At 75 ° C., 0.13 g of initiator V-50 (2,2'-azobis (2-methylpropionamidine) dichloride) solubilized in 0.73 g of water are added.
  • a monomer mixture (54.0 g of 65% DADMAC in water, 48.1 g of 50% n-vinylpyrrolidone in water and 200.9 g of 2-hydroxyethylacrylate - this reaction mixture has a pH ⁇ 7 adjusted with 1.5g of 10% NaOH in water) is added continuously over 3h.
  • 1.04 g of V-50 initiator solubilized in 51.0 g of water is added over 4 hours.
  • the reaction mixture is maintained at 75 ° C. for 1 hour.
  • 0.65 g of V-50 initiator solubilized in 3.70 g of water are then added all at once, and the reaction mixture is then maintained at 75 ° C. for 1 hour.
  • V-50 initiator solubilized in 39.2 g of water is added over 4 hours. At the end of addition of initiator, the reaction mixture is maintained at 75 ° C. for 1 hour. Subsequently, 0.50 g of solubilized V-50 initiator in 2.80 g of water is added in one go, then the reaction mixture is maintained at 75 ° C. for 1 hour. Subsequently, 0.50 g of solubilized V-50 initiator in 2.80 g of water is added in one go, then the reaction mixture is maintained at 75 ° C. for 1 hour. 0.50 g of solubilized V-50 initiator in 2.80 g of water are then added in one go, and the reaction mixture is then maintained at 75 ° C. for 90 minutes. The reaction medium is then cooled to room temperature.
  • Example 2 Use of the copolymer in a dishwashing liquid by hand and evaluation of the drying speed
  • Evaluation Protocol Objective To estimate the drying quality of a kitchen glass that comes out of a basin of rinse water.
  • a kitchen glass is washed by hand using the formulation to be evaluated, rinsed and soaked in a basin of water, at 40 ° C. In order to facilitate the visualization of traces of persistent water after total drying of the glass, this dipping is carried out in water with very high hardness. For convenience, we use Contrex® brand commercial mineral water.
  • the glass loaded with water, at the outlet of the basin, is placed on a support placed on a scale.
  • the mass of the glass is recorded while the water is flowing to obtain the mass of water remaining on the glass as a function of time, and therefore the drying profile of said glass.
  • a metal support rod (2) whose upper end is slightly beveled, is placed on the scale (4).
  • a large funnel (3) turned over, covers the scale without touching the tray. The stem passes through the tube of the funnel.
  • the kitchen glass (1) will be placed upside down on the end of the support rod. The only point of contact is on the bottom of the glass, inside. The end being beveled, the glass leans so as to facilitate the flow of water at one point. Water flows on the funnel.
  • the scale measures the mass loss of the glass. The acquisition of the measurements is done automatically (connection of the scale on a computer by an RS232 port), by a Microsoft® Excel routine. In general, one reading per second is carried out for a period of about 200 seconds.
  • Figure 4 shows a diagram of the device.
  • the edges of the glass should not touch the funnel so as not to distort the weighing.
  • Test Formulations A quantity of a copolymer of Example 1 (copolymer and quantity specified in Table 1) is added to 100 g of a commercial formulation specified in Table 1.
  • FIGS. 1 to 3 are photographs of the glasses after drying. In the absence of copolymer (FIG. 1), a dull glass with traces of drying is observed. With the comparative copolymer of Example 1.1 C, the transparency of the glass is greatly improved, but there are, however, some traces of dried drops. With the comparative copolymer of Example 1, the transparency of the glass is greatly improved and no trace of dried drops remains.
EP09809323.0A 2008-08-26 2009-08-21 Copolymer zur oberflächenverarbeitung oder modifizierung Active EP2340299B1 (de)

Applications Claiming Priority (2)

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FR0804708A FR2935390B1 (fr) 2008-08-26 2008-08-26 Copolymere pour le traitement ou la modification de surfaces
PCT/EP2009/060825 WO2010023163A1 (fr) 2008-08-26 2009-08-21 Copolymere pour le traitement ou la modification de surfaces

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017510694A (ja) * 2014-03-19 2017-04-13 ザ プロクター アンド ギャンブル カンパニー 液体洗剤組成物
WO2015139221A1 (en) * 2014-03-19 2015-09-24 Rhodia Operations New copolymers useful in liquid detergent compositions
WO2015143997A1 (en) * 2014-03-26 2015-10-01 The Procter & Gamble Company Cleaning compositions containing cationic polymers, and methods of making and using same
WO2015143644A1 (en) * 2014-03-26 2015-10-01 The Procter & Gamble Company Cleaning compositions containing cationic polymers, and methods of making and using same
US9956153B2 (en) 2014-08-01 2018-05-01 Ecolab Usa Inc. Antimicrobial foaming compositions containing cationic active ingredients
US11052431B2 (en) * 2017-03-27 2021-07-06 Clear Solutions USA, LLC Compositions and methods for GRAS compliant cleaners for ethanol production equipment
WO2020007925A1 (en) * 2018-07-05 2020-01-09 Chemetall Gmbh Method for treating metallic surfaces with an acidic aqueous composition to improve corrosion resistance

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287280A (en) * 1979-06-27 1981-09-01 Xerox Corporation Release agent applicators and method of applying release agent emulsions upon fusers in electrostatic copiers
GR74545B (de) * 1980-11-28 1984-06-29 Procter & Gamble
US4557853A (en) * 1984-08-24 1985-12-10 The Procter & Gamble Company Skin cleansing compositions containing alkaline earth metal carbonates as skin feel agents
US4728455A (en) * 1986-03-07 1988-03-01 Lever Brothers Company Detergent bleach compositions, bleaching agents and bleach activators
US5108660A (en) * 1990-01-29 1992-04-28 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbyl amidoalkylenesulfobetaine
GB9003741D0 (en) * 1990-02-19 1990-04-18 Unilever Plc Bleach activation
EP0488868B1 (de) 1990-11-30 1996-02-21 Rhone-Poulenc Chimie Gerüststoff auf Basis von Alkalimetallsilikaten für Reinigungsmittelzusammensetzungen
US5308532A (en) * 1992-03-10 1994-05-03 Rohm And Haas Company Aminoacryloyl-containing terpolymers
FR2688798B1 (fr) 1992-03-20 1994-10-14 Rhobb Poulenc Chimie Agent "builder" a base de silicate et d'un produit mineral.
US5280117A (en) * 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst
US5536452A (en) * 1993-12-07 1996-07-16 Black; Robert H. Aqueous shower rinsing composition and a method for keeping showers clean
EP0807160B1 (de) 1995-02-02 2001-11-21 The Procter & Gamble Company Verfahren zur entfernung von teeflecken in geschirrspülern mit zusammensetzungen enthaltend kobalt (iii)- katalysator
WO1996023860A1 (en) 1995-02-02 1996-08-08 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt chelated catalysts
WO1996023859A1 (en) 1995-02-02 1996-08-08 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt catalysts
US5559261A (en) * 1995-07-27 1996-09-24 The Procter & Gamble Company Method for manufacturing cobalt catalysts
CA2248476A1 (en) 1997-10-01 1999-04-01 Unilever Plc Bleach activation
EP1032632A1 (de) 1997-11-21 2000-09-06 The Procter & Gamble Company Schaumstabile flüssige geschirrspülmittel
CN1284120A (zh) 1997-11-21 2001-02-14 宝洁公司 含有聚合泡沫增效剂的洗涤剂组合物及其用途
CN1284121A (zh) 1997-11-21 2001-02-14 宝洁公司 包含聚合型泡沫增效剂的液体洗涤剂组合物
AR017416A1 (es) 1997-11-21 2001-09-05 Procter & Gamble Composicion detergente adecuada para ser usada en el lavado de vajilla y estabilizador de espuma proteinaceo
BR0012289A (pt) 1999-05-26 2002-03-26 Procter & Gamble Composições detergente compreendendo realçadores poliméricos do volume de espumas e da duração das espumas e métodos de lavagem com as mesmas
JP4763137B2 (ja) 1999-05-26 2011-08-31 ローディア インコーポレイティド ポリマー、組成物及びフォーム、洗濯洗剤、シャワーリンス及び凝固剤のための使用法
WO2000071658A1 (en) 1999-05-26 2000-11-30 The Procter & Gamble Company Detergent compostitions comprising polymeric suds enhancers which have improved mildness and skin feel
MXPA01012191A (es) 1999-05-26 2003-06-30 Procter & Gamble Composiciones y metodos para el uso de mejoradores de espuma de jabon poolimericos.
JP2003500496A (ja) 1999-05-26 2003-01-07 ローディア インコーポレイティド ブロックポリマー、その組成物、並びに発泡体、洗濯用洗剤、シャワーリンス剤および凝固剤用の使用方法
EP1180130A1 (de) 1999-05-26 2002-02-20 The Procter & Gamble Company Flüssige waschmittelzusammensetzungen enthaltend polymere schaumbilder
WO2000071660A1 (en) 1999-05-26 2000-11-30 The Procter & Gamble Company Liquid detergent compositions comprising block polymeric suds enhancers
EP1180061B1 (de) 1999-05-26 2006-12-27 The Procter & Gamble Company Verwendungsverfahren von zwitterionischen polymeren schaumbildern
FR2796392B1 (fr) 1999-07-15 2003-09-19 Rhodia Chimie Sa Composition nettoyante comprenant un polymere hydrosoluble ou hydrodispersable
FR2796390B1 (fr) 1999-07-15 2001-10-26 Rhodia Chimie Sa Utilisation d'un polymere amphotere pour traiter une surface dure
US6924260B2 (en) * 1999-07-15 2005-08-02 Rhodia Chimie Method of reducing and preventing soil redeposition in an automatic dishwashing machine
FR2796391B1 (fr) 1999-07-15 2003-09-19 Rhodia Chimie Sa Composition nettoyante pour surfaces dures
BR0108014B1 (pt) * 2000-02-02 2011-04-05 composição para a lavagem e/ou enxágüe em lavagem de roupa e processo de liberação de sujeira de um artigo para lavagem de roupa.
JP2003003197A (ja) 2001-01-05 2003-01-08 Procter & Gamble Co:The アミンオキシドモノマー単位含有高分子石鹸泡増進剤を使用する組成物および方法
WO2003006595A1 (fr) * 2001-07-11 2003-01-23 Rhodia Chimie Procede de nettoyage d'une surface a l'aide d'une composition aqueuse contenant un polymere en dispersion
JP4786868B2 (ja) * 2001-11-02 2011-10-05 ザ プロクター アンド ギャンブル カンパニー 陽イオン性ポリマー及び水不溶性固体物質を含有する組成物
US6675093B1 (en) * 2001-12-21 2004-01-06 Garmin Ltd. Systems, functional data, and methods for generating a route
FR2839977B1 (fr) * 2002-05-27 2005-08-12 Rhodia Chimie Sa Utilisation, dans une composition lavante et rincante de la vaisselle en machine, d'un copolymere amphotere comme agent anti-redeposition des salissures
DE10257279A1 (de) * 2002-12-07 2004-06-24 Clariant Gmbh Flüssige Bleichmittelkomponenten enthaltend amphiphile Polymere
US20070060488A9 (en) * 2004-01-07 2007-03-15 Henri Samain Detergent cosmetic compositions comprising at least one polymer chosen from cationic and amphoteric polymers, at least one detergent surfactant, and at least one drawing polymer, and process of use
US20060025318A1 (en) * 2004-04-22 2006-02-02 Mireille Maubru Composition for washing and conditioning keratin materials, comprising a carboxyalkyl starch, and process for the use thereof
FR2875811B1 (fr) 2004-09-29 2008-08-22 Rhodia Chimie Sa Utilisation d'un alcool gras aliphatique dans les compositions moussantes detergentes pour l'entretien de surfaces dures ou textiles
KR101284386B1 (ko) * 2005-08-04 2013-07-09 미쓰비시 가가꾸 가부시키가이샤 공중합체 및 이것을 이용한 세정제 조성물
DE102005041349A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
US7867969B2 (en) * 2005-10-28 2011-01-11 L'oreal S.A. Composition for washing keratin materials comprising a magnesium salt anionic surfactant
KR20090051084A (ko) * 2006-08-11 2009-05-20 바스프 에스이 모발 화장품 제품에서의 아민-보유 아크릴레이트 및 ｎ-비닐 이미다졸륨 염으로부터의 양이온성 공중합체의 용도
EP1967545A1 (de) * 2007-03-09 2008-09-10 Rohm and Haas France SAS Kationisches Polymer-Latex
FR2917968B1 (fr) * 2007-06-29 2010-02-26 Oreal Compositions cosmetiques detergentes comprenant quatre tensioactifs, un polymere cationique et un agent benefique et utilisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010023163A1 *

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WO2010023163A1 (fr) 2010-03-04
FR2935390A1 (fr) 2010-03-05
EP2340299B1 (de) 2016-03-30
US8658586B2 (en) 2014-02-25
FR2935390B1 (fr) 2012-07-06

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