EP2346974B1 - Zusammensetzung zur haushaltspflege mit kationischem nanogel - Google Patents

Zusammensetzung zur haushaltspflege mit kationischem nanogel Download PDF

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Publication number
EP2346974B1
EP2346974B1 EP09740106.1A EP09740106A EP2346974B1 EP 2346974 B1 EP2346974 B1 EP 2346974B1 EP 09740106 A EP09740106 A EP 09740106A EP 2346974 B1 EP2346974 B1 EP 2346974B1
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EP
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Prior art keywords
composition
les
nanogel
des
monomer
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EP09740106.1A
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English (en)
French (fr)
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EP2346974A1 (de
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Katerina Karagianni
Iñigo GONZALEZ
David James Wilson
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Rhodia Operations SAS
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Rhodia Operations SAS
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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
    • 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

  • 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.
  • 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 wherein 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 describes microgels characterized by certain rheological properties.
  • non-cationic nanogels especially based on (meth) acrylate are prepared.
  • WO0056792 describes 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.
  • 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 means 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.
  • 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.
  • the word "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 core. This is microscopic macromolecules with intra-chain crosslinking.
  • cores C may be obtained by copolymerization of a monomer C having a single polymerizable group and a crosslinking monomer R have at least two polymerizable groups (crosslinking monomer), in the absence of 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).
  • they are distinguished from “nanolatex" polymers obtained by emulsion polymerization in the presence of high amounts of surfactants at thermodynamic or near equilibrium.
  • 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 acrylic or methacrylic acid ester, 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) -.
  • hydrophobic for a monomer is used in the 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 anionic units or 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.
  • persistent antideposition properties and / or anti-adhesion means that the treated surface retains these properties over time, including after further contact with soiling (for example rainwater, water added rinsing water distribution network 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.
  • 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 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 hydrophilic property of the surface also makes it possible to reduce the formation of condensation on the surface; this benefit can be exploited in cleaning formulas for windows and mirrors, especially in bathrooms.
  • the rate of drying of the surface, immediately after its treatment by the application of the polymer but also after repeated and repeated contacts with an aqueous medium is significantly improved.
  • 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 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 cat units and the C cat 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 cat units and C N units or can derive from both C cat 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 process 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 consists in particular 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 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 C cat units may have particularly small sizes, and that processes using C cat monomers may make it possible to substantially reduce the size of the nanogels.
  • the invention can make it possible to reduce the sizes in a simple manner.
  • 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.
  • the cross-linking 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.
  • These monomers may also contain functional groups other than ethylenic unsaturations, for example hydroxyl, carboxyl, ester, amide, amino or substituted amino, mercapto, silane, epoxy or halogen functions.
  • the monomers belonging to these families are divinylbenzene and derivatives of divinylbenzene, vinyl methacrylate, methacrylic acid anhydride, allyl methacrylate, ethylene glycol dimethacrylate, phenylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, butanediol 1,3-dimethacrylate, butanediol 1,4-dimethacrylate, 1,6-dimethacrylate hexanediol, dodecanediol 1,12-dimethacrylate, glycerol 1,3-dimethacrylate, diurethane dimethacrylate, trimethylolpropane trimethacrylate.
  • vinyl acrylate epoxy bisphenol A diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol 600 diacrylate, ethylene glycol diacrylate, diacrylate diethylene glycol, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, aliphatic urethane diacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate ethoxylated, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, aliphatic urethane triacrylate, trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate.
  • vinyl ethers there may be mentioned vinyl crotonate, diethylene glycoldivinyl ether, butanediol-1,4-divinyl ether, 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 there may be mentioned N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, glyoxal bisacrylamide, diacrylamido acetic acid.
  • styrenic derivatives there may be mentioned divinylbenzene and 1,3-diisopropenylbenzene.
  • diene monomers there may be mentioned butadiene, chloroprene and isoprene.
  • N, N'-methylenebisacrylamide (MBA), divinylbenzene (DVB), ethylene glycol diacrylate, triallycyanurate (TAC) or trimethylolpropane triacrylate are preferred.
  • MSA N, N'-methylenebisacrylamide
  • DVB divinylbenzene
  • TAC triallycyanurate
  • trimethylolpropane triacrylate are preferred.
  • the nanogel comprises C N units, it may advantageously be Nphile C units derived from a hydrophilic neutral monomer C Nphile .
  • the molar ratio between the C cat units and the C N units, preferably C Nphile units may in particular be between 1/99 and 99/1, preferably between 1/99 and 50/50, preferably between 1/99 and 99/50. and 40/60, preferably between 1/99 and 25/75, for example between 2/99 and 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.
  • agents or control groups having a group -S-CS- (Xanthates, dithioesters, trithiocarbonates, dithiocabamates, dithiocarbazates, etc.) are particularly interesting.
  • 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 that is to say the quantity of control agent multiplied by the number of control groups carried by an agent
  • half the number of groups polymerizable monomers R that is to say half of the amount by mole of monomer multiplied by the number of unsaturated groups of the monomer
  • the molar ratio between the number of control groups that is to say the quantity of control agent multiplied by the number of control groups carried by an agent
  • half the number of groups polymerizable monomers R that is to say half of the amount by mole of monomer multiplied by the number of unsaturated groups of the monomer
  • the molar ratio between the number of control groups that is to say the quantity of control agent multiplied by the number of control groups carried by an agent
  • half the number of groups polymerizable monomers R that is to say half of the amount by mole of monomer multiplied by the number of unsaturated groups of
  • 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) 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, 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 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.
  • 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 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.
  • 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 polymerization is carried out in the presence of a control agent in an amount such that (N Control® n Control / n T ) is from 0.05 to 10%, preferably from 0.1 to 10%, preferably from 0 to 10% by weight. , 2 to 5%.
  • the polymerization is preferably carried out in the presence of crosslinking monomers R in an amount such that (N R / 2) * (n R / n T ) 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 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 if 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.
  • 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 antideposition and / or anti-adhesion of dirt likely to be deposited on said surfaces.
  • 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 such quantity that, after possible rinsing and drying, the amount of polybetaine (B) deposited on the surface is from 0.0001 to 10 mg / m 2 preferably from 0.001 to 5 mg / m 2 of treated surface.
  • 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 preferred zwitterionic surfactants are alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyldimethylsulphobetaines or alkylamidopropyldimethylsulfobetaines, such as Mirataine JCHA or H2CHA, and Mirataine CBS sold by Rhodia, or those of the same type marketed by Sherex Company under the name "Varion CADG Betaine". "and” Varion CAS Sulfobetaine ", the condensation products of fatty acids and protein hydrolysates.
  • Other zwitterionic surfactants are also described in US Patent 4,287,080 , and in US-A-4,557,853 .
  • surfactants are compounds generally used as surfactants referred to in well-known "Surface Active Agents” manuals, Volume I by Schwartz and Perry and “Surface Active Agents and Detergents", Volume II by Schwartz, Perry. and Berch.
  • the surfactants may represent from 0.005 to 60%, especially from 0.5 to 40% by weight of the composition of the invention, depending on the nature of the surfactant (s) and the destination. of the cleaning composition.
  • 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.
  • 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.
  • Said alkaline compositions may be in the form of a ready-to-use formula or of a dry or concentrated formula to be diluted in water in particular, before use; they can be diluted 1 to 10,000 times, preferably 1 to 1000 times before use.
  • Said acid compositions are preferably in the form of a ready-to-use formula.
  • composition according to the invention can be used for the easy cleaning treatment of glass surfaces, in particular windows.
  • This treatment can be performed by the various known techniques.
  • 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.
  • compositions for easy rinsing of the automatic dishwashing machine 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.
  • 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.
  • 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.
  • 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 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).
  • Certain surfactants which can be used in this type of application are described in the patents US5,536,452 and 5587022 whose contents are incorporated by reference in the present description.
  • Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan mono-oleates and polyethoxylated castor oil.
  • surfactants are the condensation products of 20 moles of ethylene oxide and sorbitan mono-oleate (marketed by Rhodia Inc. under the name ALKAMULS PSMO-20® with a HLB of 15.0). and 30 or 40 moles of ethylene oxide and castor oil (marketed by RHODIA Inc. under the name ALKAMULS EL-620® (HLB 12.0) and EL-719® (HLB 13.6). ) respectively).
  • the degree of ethoxylation is preferably sufficient to obtain a surfactant having an HLB greater than 13.
  • the pH of the composition is advantageously between 7 and 11.
  • 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 antideposition and / or antiadhesive hydrophilic properties of soils capable of being deposited on said surfaces.
  • 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.
  • a linear copolymer is prepared having 95 mol% Acrylamide and 5 mol% MAPTAC, with an average molecular weight of 400 kg / mol.
  • compositions are prepared (per 1000 g of composition):
  • the foam index and the persistence of the foam are tested according to the protocol detailed below.
  • the foam index and the persistence of foam, for a composition tested are determined using the following roller device, according to the protocol below.
  • 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.
  • Foam height Hight of foam + liquid composition - liquid composition height .
  • 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 an initial temperature controlled 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 6 th waiting period of 3 minutes. For the sake of precision, each measurement is repeated at least twice, the foam index is the average.
  • 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.
  • the soiling used in the example is a synthetic sebum simulating greasy soils such as those from human skin, mixed with a clay (bentonite) simulating particulate soils (dust, ).
  • the ratio by weight between synthetic sebum and clay is 12/4.
  • composition for 950g of synthetic sebum Synthetic sebum Ingredient boy Wut % Palmitic acid 100 10.5 Stearic acid 50 5.3 Sebacic acid 50 5.3 Oleic acid 100 10.5 Linoleic acid 50 5.3 Paraffin wax (40-50 ° C) 100 10.5 Coconut oil (copprah) 100 10.5 squalene 50 5.3 Mineral oil 200 21.1 Soya oil 50 5.3 Colza oil 100 10.5
  • Preparation The ingredients are placed in a Pyrex® beaker and heated at 80 ° C for 15 minutes, with magnetic stirring on a hot plate.
  • the formed liquid is transparent and weakly colored. On cooling, it forms a white and opaque waxy paste that can be stored for several weeks in the freezer.
  • the final soil is prepared by melting 12 sebum, at 80 ° C with mechanical stirring, and adding 4g of clay.
  • the dirt becomes opaque and slightly viscous and is agitated during the entire operation.
  • a fresh mix sample is prepared for each new experiment, the soil never being stored for more than one hour.
  • the washing solution tested, used for washing, is a Brazilian brand ACE laundry, to which the polymer to be tested is added. 0.025 g of active polymer is used per 5 g of lye.
  • the removal percentage is reported lower as the value related to redeposition (the higher it is, the lower the repositioning).
  • Example 2.1c 2.2c 2.3 Formulation 1 2 1 Polymer tested Control - None 0.05 g
  • Example 1.3 Quantity of polymer (foam tests) 0 0.05 g (50 ppm) 0.05 g (50 ppm) Quantity of polymer (redeposition) 0 0.025g for 5g of laundry 0.025g for 5g of laundry Foam index (FHU) 70 72 70 Persistence of the foam (FHU after three implementations of addition of soil) 28 41 50 redeposit 92 86 94
  • Example 3.1 c 3.2c 3.3c 3.4 Vector Distilled water Distilled water Distilled water Distilled water Distilled water Surfactant: Synperonic A7, Uniquema 0.5% 0.5% 0.5% 0.5% Polymer tested Control - No polymer 200 ppm - Example 1.1 c 250 ppm-commercial polymer * 07JWN305 200ppm-Example 1.4 pH (by adding, if appropriate, citric acid or citrate) 4 4 4 4 4 * 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.
  • the kinetics adsorption of the nanogel of the composition is monitored by reflectometry on an oxide silica slab (surface close to a glass or ceramic surface, available from Silicon Inc, under the description "100 mm Silicon Wafers, single side polished, P -type, (100) orientation, thickness 500-550 microns, with 1000 (+/- 3%) Angstroms SiO2 applied, clean room processed and packaged ").
  • the procedure is carried out by comparison using a reference comprising distilled water and KCl 10 -3 M, according to the method below:
  • a polarized ray of a He-Ne laser (632.8 nm) enters a cell through a glass prism following the Brewster angle at the water / silicon interface (71). °) on a silicon wafer covered by a thin film of the adsorbent support to be studied.
  • the ray is reflected and then separated into two components (perpendicular Is and parallel Ip) and then recovered by photodiodes.
  • Rinse adsorption resistance was tested with a solution comprising distilled water and KCI 10 -3 M).
  • Example 4.1C Polymer tested
  • Example 1.3 Adsorbed amount (plateau after 4 minutes) 0.9 1.08 Resistance to rinsing resists resists

Claims (18)

  1. Zusammensetzung zur Haushaltspflege, die ein kationisches Nanogel umfasst, das aus chemisch vernetzten Makromolekülen besteht, mit einem C-Kern, umfassend:
    - vernetzende R-Einheiten als Derivat eines vernetzenden Monomers R mit mindestens zwei polymerisierbaren Gruppen, und
    - C-Herz-Einheiten als Derivat mindestens eines Monomers C mit einer einzigen polymerisierbaren Gruppe, umfassend:
    - kationische oder potentiell kationische Ccat-Einheiten als Derivat mindestens eines kationischen oder potentiell kationischen Monomers Ccat, und
    - eventuell hydrophile oder hydrophobe neutrale CN-Einheiten als Derivat mindestens eines hydrophilen oder hydrophoben neutralen Monomers CN,
    - wobei das Nanogel von einem Stern-Copolymer unterschiedlich ist, das makromolekulare Zweige an der Peripherie des Kerns umfasst,
    - wobei die durchschnittliche Größe der Makromoleküle 5 bis 500 nm, vorzugsweise 30 bis 170 nm, beträgt.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass das Nanogel herstellbar ist, durch die Umsetzung eines kontrollierten Radikalpolymerisation Verfahrens.
  3. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die vernetzenden R-Einheiten Einheiten sind, die Derivate eines diethylenisch ungesättigten oder triethylenisch ungesättigten Monomers sind.
  4. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Nanogel durch Polymerisation, vorzugsweise durch kontrollierte Radikalpolymerisation, eines Monomergemischs hergestellt wird, umfassend:
    - mindestens ein vernetzendes Monomer R, das mindestens zwei polymerisierbare Gruppen, vorzugsweise ein multiethylenisch ungesättigtes Monomer, umfasst, und
    - mindestens ein Monomer C, das eine einzige polymerisierbare Gruppe, vorzugsweise ein monoethylenisch ungesättigtes Monomer, umfasst, umfassend:
    - mindestens kationisches oder potentiell kationisches Monomer Ccat, und
    - eventuell ein hydrophiles oder hydrophobes neutrales Monomer CN.
  5. Zusammensetzung nach Anspruch 4, dadurch gekennzeichnet, dass das molare Verhältnis zwischen dem/n Monomer(en) C und dem vernetzenden Monomer R größer oder gleich 1, vorzugsweise zwischen 80/20 und 99/1 inklusive, vorzugsweise zwischen 90/10 und 95/5 inklusive, ist.
  6. Zusammensetzung nach einem der Ansprüche 4 oder 5, dadurch gekennzeichnet, dass:
    - das Nanogel hergestellt ist, durch die Umsetzung eines kontrollierten Radikalpolymerisation Verfahrens, das Kontrollgruppen verwendet,
    - das molare Verhältnis zwischen der Anzahl der Kontrollgruppen und der Hälfte der Anzahl der polymerisierbaren Gruppen des vernetzenden Monomers R zwischen 0,05 und 0,5 inklusive ist.
  7. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Nanogel hydrophile neutrale CNphile-Einheiten als Derivat eines hydrophilen neutralen Monomers CNphile umfasst.
  8. Zusammensetzung nach Anspruch 7, dadurch gekennzeichnet, dass das Verhältnis in Mol zwischen den Ccat-Einheiten und den CNphile-Einheiten zwischen 1/99 und 50/50 inklusive ist.
  9. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die kationischen oder potentiell kationischen Ccat-Einheiten Derivateinheiten von Monomeren Ccat sind, die aus den folgenden Monomeren ausgewählt sind:
    - dem N,N-Dimethylaminomethyl-acrylamid oder -methacrylamid,
    - dem 2(N,N-Dimethylamino)ethyl-acrylamid oder -methacrylamid,
    - dem 3(N,N-Dimethylamino)propyl-acrylamid oder -methacrylamid,
    - dem 4(N,N-Dimethylamino)butyl-acrylamid oder -methacrylamid,
    - dem 2(Dimethylamino)ethylacrylat (ADAM),
    - dem 2(Dimethylamino)ethylmethacrylat (DMAM oder MADAM),
    - dem 3(Dimethylamino)propylmethacrylat, dem 2(Tertiobutylamino)ethylmethacrylat,
    - dem 2(Dipentylamino)ethylmwthacrylat,
    - dem 2(Diethylamino)ethylmethacrylat,
    - den Vinylpyridinen,
    - dem Vinylamin,
    - den Vinylimidazolinen,
    - dem Trimethylammoniumpropylmethacrylatchlorid,
    - dem Trimethylammoniumethylacrylamid- oder -methacrylamidchlorid oder -bromid,
    - dem Trimethylammoniumbutylacrylamid- oder -methacrylamidmethylsulfat,
    - dem Trimethylammoniumpropylmethacrylamidmethylsulfat (MAPTA MeS),
    - dem (3-Methacrylamidpropyl)trimethylammoniumchlorid (MAPTAC),
    - dem (3-Acrylamidpropyl)trimethylammoniumchlorid (APTAC),
    - dem Methacryloyloxyethyltrimethylammoniumchlorid oder -methylsulfat,
    - den Acryloyloxyethyltrimethylammoniumsalzen (ADAMQUAT),
    - dem 1-Ethyl 2-vinylpyridinium-, 1-Ethyl 4-vinylpyridiniumbromid, -chlorid oder -methylsulfat,
    - dem N,N-Dimethyldiallylammoniumchlorid (DADMAC),
    - dem Dimethylaminopropylmethacrylamide,N-(3-chloro-2-hydroxypropyl) trimethylammoniumchlorid (DIQUAT),
    - dem Monomer der Formel
    Figure imgb0011
     wobei X- ein Anion, vorzugsweise Chlorid oder Methylsulfat, ist.
  10. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die eventuell neutralen CN-Einheiten hydrophile neutrale CNphile-Einheiten von Monomeren CNphilie sind, die aus den folgenden Monomeren ausgewählt sind:
    - den Hydroxyethylacrylaten und -methylacrylaten,
    - dem Acrylamid,
    - dem Methacrylamid,
    - dem Vinylalkohol,
    - dem Vinylpyrrolidon,
    - dem Vinylcaprolactam.
  11. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Nanogel eine molare Masse von mindestens 350000 g/mol aufweist.
  12. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass es sich um eine Zusammensetzung für die Behandlung, vorzugsweise für die Reinigung, von harten Flächen oder textilen Flächen handelt.
  13. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass sie mindestens ein Tensid umfasst.
  14. Verwendung des kationischen Nanogel nach einem der Ansprüche 1 bis 9 in einer Zusammensetzung zur Haushaltspflege.
  15. Verwendung nach Anspruch 14, dadurch gekennzeichnet, dass die Zusammensetzung zur Haushaltspflege eine Zusammensetzung für die Behandlung, vorzugsweise für die Reinigung, von harten Flächen oder textilen Flächen ist.
  16. Verwendung nach einem der Ansprüche 14 oder 15, dadurch gekennzeichnet, dass die Zusammensetzung eine Zusammensetzung für das Waschen von Wäsche mit der Hand oder in der halbautomatischen Maschine ist, wobei das Nanogel verwendet wird als:
    - Schaumstabilisator, vorzugsweise als Zusatz bei Verschmutzungen, und/oder
    - Mittel gegen Wiederablagerung.
  17. Verwendung nach einem der Ansprüche 14 oder 15, dadurch gekennzeichnet, dass die Zusammensetzung eine Zusammensetzung für die Reinigung von harten Flächen ist, wobei das Nanogel als Hydrophilisierungs- und/oder Anti-Verschmutzungs-Mittel verwendet wird.
  18. Methode der Umsetzung von Haushaltspflegen, die einen Schritt des Inkontaktversetzens einer Haushaltsfläche, vorzugsweise einer textilen oder einer harten Haushaltsfläche, mit einer Zusammensetzung nach einem der Ansprüche 1 bis 13, ggf. nach einer vorherigen Verdünnung, umfasst.
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2917415B1 (fr) * 2007-06-14 2012-10-12 Rhodia Recherches Et Tech Microgel polymerique comprenant des unites cationiques
ES2365315B1 (es) * 2010-03-18 2013-01-24 Universidad Del Pais Vasco Nanogeles catiónicos para aplicaciones biotecnológicas.
US8563498B2 (en) * 2010-04-01 2013-10-22 The Procter & Gamble Company Fabric care compositions comprising copolymers
WO2011123730A1 (en) 2010-04-01 2011-10-06 The Procter & Gamble Company Process for coating cationic polymers on microcapsules
FR2965564B1 (fr) 2010-09-30 2012-10-26 Rhodia Operations Preparation de polymeres hydrophiles de haute masse par polymerisation radicalaire controlee
WO2013030169A1 (en) 2011-08-31 2013-03-07 Akzo Nobel Chemicals International B.V. Laundry detergent compositions comprising soil release agent
WO2015139234A1 (en) * 2014-03-19 2015-09-24 The Procter & Gamble Company Liquid detergent composition
US20170096513A1 (en) * 2014-03-19 2017-04-06 Rhodia Operations New copolymers useful in liquid detergent compositions
US20160145547A1 (en) * 2014-11-25 2016-05-26 Milliken & Company Film-Encased Cleaning Composition
EP3034595B1 (de) * 2014-12-15 2018-12-05 S.P.C.M. Sa Kationische Polymerverdickungsmittel
CN105820806B (zh) * 2016-04-25 2019-01-08 中国石油集团渤海钻探工程有限公司 一种改性羧甲基胍胶稠化剂及其制备方法

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50127991A (de) 1974-03-29 1975-10-08
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
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
DE69617209T2 (de) 1995-02-02 2002-07-25 Procter & Gamble Verfahren zur entfernung von teeflecken in geschirrspülern mit zusammensetzungen enthaltend kobalt (iii)- katalysator
EP0807159B1 (de) 1995-02-02 2000-05-24 The Procter & Gamble Company Maschinengeschirrspülmittel zusammensetzungen mit kobalt chelatkatalysatoren
ES1030318Y (es) 1995-03-01 1996-02-01 Esteban German Monfort Dispositivo calefactor para motocicletas.
US5763548A (en) 1995-03-31 1998-06-09 Carnegie-Mellon University (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization
US5559261A (en) 1995-07-27 1996-09-24 The Procter & Gamble Company Method for manufacturing cobalt catalysts
DE69709110T2 (de) 1996-07-10 2002-04-25 Du Pont Polymerisation mit "living" kennzeichen
AUPO460797A0 (en) * 1997-01-15 1997-02-06 University Of Melbourne, The Polymerisation process
FR2764892B1 (fr) 1997-06-23 2000-03-03 Rhodia Chimie Sa Procede de synthese de polymeres a blocs
JP2001510208A (ja) 1997-07-15 2001-07-31 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド ニトロソ化合物又はニトロン化合物から誘導されたアルコキシアミン化合物を含む重合可能な組成物
CA2248476A1 (en) 1997-10-01 1999-04-01 Unilever Plc Bleach activation
KR100589073B1 (ko) 1997-12-18 2006-06-13 이 아이 듀폰 디 네모아 앤드 캄파니 리빙 특성의 중합 방법 및 이 방법으로 제조된 중합체
BR9916338B1 (pt) 1998-12-18 2009-01-13 processo para a preparaÇço de produto de reaÇço, processo para a preparaÇço de produto de um polÍmero, produto de reaÇço, polÍmero, mistura aquosa, e, uso de uma mistura aquosa.
JP4500450B2 (ja) 1998-12-23 2010-07-14 ビーエーエスエフ コーティングス アクチェンゲゼルシャフト 被覆組成物
AUPP939299A0 (en) 1999-03-23 1999-04-15 University Of Melbourne, The Polymer gels and methods for their preparation
FR2794463B1 (fr) 1999-06-04 2005-02-25 Rhodia Chimie Sa Procede de synthese de polymeres par polymerisation radicalaire controlee a l'aide de xanthates halogenes
FR2812293B1 (fr) 2000-07-28 2002-12-27 Rhodia Chimie Sa Procede de synthese de polymeres a blocs par polymerisation radicalaire controlee
US6569969B2 (en) 2000-09-28 2003-05-27 Symyx Technologies, Inc. Control agents for living-type free radical polymerization, methods of polymerizing and polymers with same
DE10141006A1 (de) * 2001-08-21 2003-03-06 Basf Ag Verwendung von amphoteren Polymeren als schmutzablösungsfördernder Zusatz von Mitteln für die Behandlung von Oberflächen
BR0311580B1 (pt) * 2002-06-04 2014-12-30 Ciba Sc Holding Ag Formulação aquosa contendo um polímero catiônico e composição de amaciante de tecido.
AU2002953359A0 (en) 2002-11-27 2003-01-09 The University Of Melbourne Microgel composition
AU2002953369A0 (en) 2002-11-27 2003-01-09 The University Of Melbourne Free radical polymerisation process for microgel preparation
ES2268490T3 (es) * 2002-11-29 2007-03-16 Ciba Specialty Chemicals Holding Inc. Composiciones acuosas que comprenden homo- y/o copolimeros.
EP1698688B1 (de) * 2005-03-04 2010-04-07 Rohm and Haas Company Waschmittel und deren Verwendung
FR2894971B1 (fr) * 2005-12-20 2008-05-16 Rhodia Recherches & Tech Composition pour le traitement et/ou la modification de surfaces dures, comprenant un polymere synthetique
EP2039338A1 (de) 2007-09-20 2009-03-25 Rhodia Opérations Hoch schäumende Zusammensetzung
US8828152B2 (en) * 2008-07-31 2014-09-09 Ppg Industries Ohio, Inc. Passivated metal core substrate and process for preparing the same

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WO2010046342A1 (fr) 2010-04-29
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