EP1594945B1 - Spül- und reinigungsmittel für harte oberflächen - Google Patents

Spül- und reinigungsmittel für harte oberflächen Download PDF

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Publication number
EP1594945B1
EP1594945B1 EP03799667.5A EP03799667A EP1594945B1 EP 1594945 B1 EP1594945 B1 EP 1594945B1 EP 03799667 A EP03799667 A EP 03799667A EP 1594945 B1 EP1594945 B1 EP 1594945B1
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EP
European Patent Office
Prior art keywords
weight
polybetaine
composition
active agent
agent
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EP03799667.5A
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English (en)
French (fr)
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EP1594945A1 (de
Inventor
Cédric Rés. de la Porte de Paris GEFFROY
Ian Harrison
Marie-Pierre Labeau
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Rhodia Chimie SAS
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Rhodia Chimie SAS
Rhone Poulenc Chimie SA
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Priority claimed from FR0302079A external-priority patent/FR2851573B1/fr
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    • 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
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the subject of the present invention is a cleaning or rinsing composition intended for the treatment of industrial, domestic or community hard surfaces, in particular of the ceramic, tiling, glass, metal, melamine, formica or plastic type, aimed at conferring on them, in particular, anti-deposition and / or non-sticking properties of the stains; it can also provide them with antistatic properties, gloss, anti-slip properties.
  • detergent formulations can effectively clean industrial, domestic or community hard surfaces. They generally consist of an aqueous solution of surfactants, especially nonionic and anionic surfactants, or nonionic and cationic surfactants, solvents, alcohol (s) to facilitate drying, and optionally sequestering agents and bases or acids to adjust the pH.
  • surfactants especially nonionic and anionic surfactants, or nonionic and cationic surfactants
  • solvents especially alcohol (s) to facilitate drying, and optionally sequestering agents and bases or acids to adjust the pH.
  • alcohol (s) to facilitate drying
  • sequestering agents and bases or acids to adjust the pH.
  • a frequent disadvantage of these detergent formulations is that the subsequent contact of the hard surface with water leads to the formation of traces during drying.
  • the treatment with these formulations is, for most of them, only purely curative and non-preventive.
  • industrial or household cleaners are effective for cleaning the soiled hard surface but do not prevent or limit its future fouling, or even to promote its subsequent
  • EP-A-1196527 , EP-A-1196528 and EP-A-1196523 by depositing on the surface, by means of a cleaning or rinsing formulation, a water-soluble amphoteric organic copolymer derived from a cationic monomer and an anionic or potentially anionic monomer, in an amount sufficient to render the surface hydrophilic (or improve its hydrophilicity, in order to obtain the lowest possible contact angle between the hard surface to be treated and a drop of water) but also to ensure the retention of water near the hard surface thus treated.
  • FR2813312 relates to a composition for the care of laundry comprising at least one nanolatex of a polymer insoluble in the conditions of use in aqueous or wet medium of said composition.
  • the copolymers described in this document are obtained by radical emulsion polymerization and comprise at least 70% by weight of hydrophobic monomeric units.
  • the Applicant has now found that the deposition on a hard surface, by means of a cleaning or rinsing formulation, of polybetaine zwitterions having one or more permanent positive charges and one or more permanent negative charges on the same monomer unit, the number positive charges being equal to the number of negative charges on the same monomer unit, allowed to confer on the surface thus treated persistent anti-deposition and / or anti-adhesion properties of particularly effective soiling; in addition, the presence of polybetaine zwitterions makes it possible to improve the cleaning capacity of said formulation.
  • 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 of products of rinsing, splashing fat, soaps ). This property of remanence can be observed beyond a dozen rinsing cycles, or even in some particular cases where the rinses are numerous (eg toilets), beyond 100 cycles of rinsing.
  • the presence of polybetaine zwitterions makes it possible 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 polybetaine zwitterion-containing formulation makes it possible to clean a larger number of soiled objects than a formulation that is free of it.
  • polybetaine zwitterions in hard surface treatment formulations makes the surface hydrophilic or improves its hydrophilicity.
  • the hydrophilic property of the surface also makes it possible to reduce the formation of condensation on the surface; this benefit can be exploited in cleaning formulas for windows and mirrors, especially in bathrooms.
  • the rate of drying of the surface, immediately after its treatment by the application of the polymer but also after repeated and repeated contacts with an aqueous medium is significantly improved.
  • a first subject of the invention consists of a composition for cleaning or rinsing in aqueous or aqueous-alcoholic medium of the hard surfaces, comprising at least one surfactant and at least one polybetaine (B), with the weight ratio polybetaine (B) / agent (s) surfactant (s) being between 1/1 and 1/1000, and said polybéta ⁇ ne (B) being as defined in claim 1.
  • hard surfaces is to be taken broadly; these are non-textile surfaces, which can be household, community or industrial.
  • 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).
  • composition according to the invention can be in any form and can be used in many ways.
  • said polybetaine (B) is present in the composition subject of the invention in an amount effective to provide said surfaces with anti-deposition and / or anti-adhesion properties soils may be deposited on said surfaces .
  • composition which is the subject of the invention may contain, according to its application, from 0.001 to 10% of its weight of at least one polybetaine (B).
  • 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.
  • 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.
  • molar mass when we speak of molar mass, it will be the average molar mass, expressed in g / mol. This can be determined by aqueous gel permeation chromatography (GPC), by light scattering (DDL or MALLS), with an aqueous eluent or an organic eluent (for example dimethylacetamide, dimethylformamide, etc.) according to the polymer composition.
  • GPC gel permeation chromatography
  • DDL or MALLS light scattering
  • an aqueous eluent or an organic eluent for example dimethylacetamide, dimethylformamide, etc.
  • polybetaines are polymeric zwitterions carrying one or more positive charges and one or more negative charges on the same betaine monomer unit. On a single betaine monomer unit, the number of positive charge (s) is equal to the number of negative charge (s).
  • the polybetaine (B) has a permanent anionic charge and a permanent cationic charge at both pH strongly acidic and pH strongly basic; these fillers are permanent in a pH range of 1 to 14.
  • the permanent anionic charge can be provided by one or more anions sulfonate, phosphate, phosphonate, phosphinate, ethenolates ....
  • the cationic charge is provided by one or more onium or inium cations of the family of nitrogen (ammonium, pyrididium, imidazolinium cations), phosphorus (phosphonium, etc.) or sulfur (sulfonium, etc.).
  • the betaine functions of polybetaine (B) are carried by pendant groups.
  • the atom carrying the permanent cationic charge is preferentially connected to the anionic charge bearing anion by an optionally substituted hydrocarbon multivalent group, in particular an alkylene group, optionally substituted by one or more hydroxyl groups.
  • the betaine functions can be connected to the carbon atoms of the hydrocarbon chain (also called the backbone) of the polybetaine (B) via, in particular, a divalent or polyvalent hydrocarbon-based unit (for example alkylene or arylene) optionally interrupted by one or several heteroatoms, oxygen in particular, an ester unit, an amide unit, or by a valence bond.
  • a divalent or polyvalent hydrocarbon-based unit for example alkylene or arylene
  • oxygen in particular, an ester unit, an amide unit, or by a valence bond.
  • the hydrocarbon chain (or backbone) of polybetaine (B) is a polyalkylene chain (linear or branched) optionally interrupted by one or more heteroatoms of nitrogen and / or sulfur.
  • the polybetaine (B) according to the invention may be a homopolymer formed of similar betaine units, or a copolymer formed of betaine units, at least two of which are different.
  • Said polybetaine (B) may further contain at least one nonionic or nonionic unit at the pH of the composition or at the pH of use of the composition comprising polybetaine (B), and / or at least one anionic unit or potentially anionic at the pH of the composition or at the pH of use of the composition comprising polybetaine (B). These units may be hydrophilic or hydrophobic.
  • Non-ionic, non-ionogenic, anionic or potentially anionic units are limited in number to keep said polybetaine (B) its main characteristic of zwitterion.
  • Polybetaine (B) contains less than 50% of its weight or more precisely less than 70 mol% of nonionic, nonionic, anionic or potentially anionic units; very preferably polybetaine (B) may contain less than 50 mol%, and more particularly less than 30 mol% of nonionic, nonionic, anionic or potentially anionic units.
  • nonionic units those derived from ethylenically unsaturated nonionic monomers such as acrylamide, vinyl acetate (capable of forming, by hydrolysis, vinyl alcohol units), the C 1 -C 4 alkyl esters of acrylic acid and of methacrylic acid, the hydroxyalkyl esters of C 1 -C 4 acrylic acid and methacrylic acid, including acrylate and methacrylate ethylene glycol and propylene glycol, polyalkoxylated esters of acrylic acid and methacrylic acid, including polyethylene glycol and polypropylene glycol esters ....
  • nonionic monomers such as acrylamide, vinyl acetate (capable of forming, by hydrolysis, vinyl alcohol units), the C 1 -C 4 alkyl esters of acrylic acid and of methacrylic acid, the hydroxyalkyl esters of C 1 -C 4 acrylic acid and methacrylic acid, including acrylate and methacrylate ethylene glycol and propylene glycol, polyalkoxylated
  • the polybetaine (B) contains no monomeric units other than betaines carrying as much anionic charge (s) as permanent cationic charge (s) at a pH ranging from from 1 to 14. If other units are present, they are rather potentially anionic units, in an amount of less than 50 mol%, preferably less than 30 mol%.
  • Said polybetaine (B) according to the invention can also be obtained in known manner by chemical modification of a so-called precursor polymer polymer.
  • a polysulfobetaine can be obtained by chemical modification, using a sultone (propanesultone, butanesultone), a halogenoalkylsulfonate or any other sulfonated electrophilic compound, a polymer with pendant amine functions.
  • the polybetaine B is chosen from alkylsulfonates or hydroxyalkylsulfonates of dialkylammonium alkyl methacrylates or methacrylamides and sulphobetaines derived from a vinylpyridine. Even more preferably, it is alkylsulfonates or hydroxyalkylsulfonates of dialkylammonium methacrylamides.
  • the homopolymers or copolymers comprising betaine units chosen from those of formulas (-SPE-), (-SPP-), (-SHPE-) and (-SHPP-) have an average molar mass in absolute mass (M w ) ranging from 10,000 to 150,000 g / mol.
  • the cleaning or rinsing composition according to the invention also comprises at least one surfactant.
  • This may be nonionic, anionic, amphoteric, zwitterionic or cationic.
  • Nonionic surfactants is given in US Patent 4,287,080 and US Patent 4,470,923 .
  • Alkylene oxide condensates in particular ethylene oxide and optionally propylene condensates with alcohols, polyols, alkylphenols and acid esters, may be mentioned in particular.
  • fatty acids 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 ).
  • 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.
  • surfactants are compounds generally used as surfactants referred to in well-known textbooks.
  • 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 polybetaine (B) / agent (s) surfactant (s), is between 1/1 and .1 / 1000, preferably 1/2 and 1/200.
  • the cleaning or rinsing composition according to the invention may further comprise at least one other additive, especially chosen from the usual additives present in the cleaning or rinsing compositions for 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.
  • the 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 11.5) are particularly useful for the removal of greasy soils and are particularly suitable for kitchen cleaning .
  • polybetaine B
  • B polybetaine
  • 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.
  • 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 .
  • polybetaine B
  • B polybetaine
  • 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 polybetaine (B) introduced will generally be such that, when using the cleaning composition, after optional dilution, the concentration of polybetaine (B) is between 0.001 g / l and 2 g / l, preferably of 0.005 g / l and 0.5 g / l.
  • the pH of the composition is advantageously between 6 and 11.
  • 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 polybetaine (B).
  • Said detergent compositions for dishwashers also comprise at least one surfactant, preferably nonionic in an amount ranging from 0.2 to 10%, preferably from 0.5 to 5% by weight, of the said detergent composition, the remainder being by various additives and fillers, as already mentioned above.
  • the pH is advantageously between 8 and 13.
  • 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 polybetaine (B) relative to the weight. total of the composition.
  • compositions may also comprise from 0.1 to 20%, preferably from 0.2 to 15% by weight relative to the total weight of said composition of a surfactant, preferably a nonionic surfactant.
  • nonionic surfactants mention may be made of polyoxyethylenated C 6 -C 12 alkylphenol-type surfactants, polyoxyethylenated and / or polyoxypropylenated C 8 -C 22 aliphatic alcohols, ethylene oxide-oxide block copolymers, and the like. propylene, possibly polyoxyethylenated carboxylic amides ....
  • compositions may furthermore comprise from 0 to 10%, preferably from 0.5 to 5% by weight relative to the total weight of the composition of an organic acid sequestering calcium, preferably citric acid.
  • They may also comprise a copolymer auxiliary agent of acrylic acid and maleic anhydride or homopolymers of acrylic acid in a proportion of 0 to 15%, preferably 0.5 to 10% by weight relative to the weight total of said composition.
  • the pH is advantageously between 4 and 7.
  • the invention also relates to a cleaning composition for the easy washing of dishes by hand .
  • Preferred detergent formulations of this type comprise from 0.1 to 10 parts by weight of polybetaine (B) per 100 parts by weight of said composition and contain from 3 to 50, preferably from 10 to 40 parts by weight of, at least a surfactant, preferably anionic, chosen in particular from sulphates of saturated C 5 -C 24 , preferably C 8 -C 16 , aliphatic alcohols, optionally condensed with approximately 0.5 to 30, preferably 0.5 to 30, preferably 8, in particular 0.5 to 5 moles of ethylene oxide, in acid form or in the form of a salt, in particular alkaline (sodium), alkaline earth (calcium, magnesium) ...
  • a surfactant preferably anionic, chosen in particular from sulphates of saturated C 5 -C 24 , preferably C 8 -C 16 , aliphatic alcohols, optionally condensed with approximately 0.5 to 30, preferably 0.5 to 30, preferably 8, in particular 0.5 to 5 moles of ethylene oxide, in acid form or in the form of
  • it is a foamy liquid detergent aqueous formulations for the hand-washed washing of dishes.
  • the pH of the composition is advantageously between 5 and 9.
  • Another particular embodiment of the invention consists of an easy external cleaning composition , in particular of the bodywork, of motorized vehicles (cars, trucks, buses, trains, planes, etc.).
  • motorized vehicles cars, trucks, buses, trains, planes, etc.
  • it may be a cleaning composition itself or a rinse composition.
  • the 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.
  • composition of the invention is also particularly suitable for easy cleaning of ceramic- type hard surfaces (tiles, bathtubs, washbasins, etc.), especially for bathrooms .
  • the cleaning formulation advantageously comprises from 0.02 to 5% by weight of polybetaine (B) 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 of the 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. composition.
  • the pH of the composition is advantageously between 2 and 12.
  • composition according to the invention is also suitable for easy rinsing of the walls of the showers.
  • the aqueous shower wall rinsing compositions comprise from 0.02% to 5% by weight, preferably from 0.05% to 1% polybetaine (B).
  • 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.
  • 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).
  • Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan mono-oleates and polyethoxylated castor oil.
  • Specific examples of such surfactants are the condensation products of 20 moles of ethylene oxide and sorbitan mono-oleate (marketed by Rhodia Inc. under the name ALKAMULS PSMO-20® with a HLB of 15.0). and 30 or 40 moles of ethylene oxide and castor oil (marketed by RHODIA Inc. under the name ALKAMULS EL-620® (HLB 12.0) and EL-719® (HLB 13.6). ) respectively).
  • the degree of ethoxylation is preferably sufficient to obtain a surfactant having an HLB greater than 13.
  • the pH of the composition is advantageously between 7 and 11.
  • composition according to the invention can also be used for the easy cleaning of vitroceramic plates .
  • 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 .
  • the pH of such a composition is generally 8 to 14.
  • a second object of the invention is the use, in a composition comprising at least one surfactant for cleaning or rinsing in aqueous or aqueous-alcoholic medium of the hard surfaces, of at least one polybetaine (B) as defined in the claims as an agent for providing said surfaces with anti-deposition and / or anti-adhesion properties of soils that may deposit on said surfaces.
  • B polybetaine
  • a third subject of the invention consists of a process for improving the properties of compositions comprising at least one surfactant for cleaning or rinsing in aqueous or aqueous-alcoholic medium of the hard surfaces, by adding to said compositions at least one polybetaine (B ) as defined in the claims.
  • a fourth subject of the invention consists of a process for facilitating the cleaning or rinsing of hard surfaces, by bringing said surfaces into contact with a composition in an aqueous or aqueous-alcoholic medium, comprising at least one surfactant and at least one polybetaine (B), said polybetaine (B) as defined in the claims.
  • the polybetaine (B) is used or is present in said composition in an amount effective to provide said surfaces with anti-deposition and / or anti-adhesion properties soils may be deposited on said surfaces.
  • the molar masses mentioned are absolute mass average molar masses, measured by GPC aqueous gel permeation chromatography by MALLS light scattering, according to the following conditions: Eluent : Millipore water 18 M ⁇ , NO 3 NH 4 1M, N 3 Na 1/10 000 Debit : 1 ml / min Olume injected : 100 .mu.l Calibration : Nil, the mass is established by MALLS Columns : 2 columns GPC (SB806MHQ Shodex OH Pack 30cm, 5 ⁇ m) Detectors : Refractometer : RI Waters 410 DDL : Wyatt laser scattering light scattering MALLS, 633nm laser
  • the betaine polymers B1 to B8 tested are respectively used in the form of a solution at a concentration of 200 mg / l in a water / ethanol mixture containing 5% by volume of ethanol (in order to facilitate the drying of the deposited solution. on the surface to be treated); the solution is brought to pH 3 by adding hydrochloric acid
  • the operative protocol is the following
  • the plate is visually analyzed by a set of 20 testers.
  • the test described above is also carried out by replacing the polymers B1 to B8 by the copolymers C1 to C7.
  • betaine polymers B1 to B8 and C1 to C7 facilitate the removal of dirt.
  • the SPE / AMA molar ratio of the copolymers C1 to C7 has little impact in this test.
  • the betaine polymers B1, B5, B7, C1, C2, C4 and C6 tested are used in the form of solutions at a concentration of 200 mg / l in a water / ethanol mixture containing 5% by volume of ethanol (in order to facilitate the drying of the solution deposited on the surface to be treated); the solutions are brought to pH 3 by adding hydrochloric acid.
  • the operative protocol is the following
  • the treated plate is subjected to 200 rinsing cycles using 200 x 1 liter of water
  • the plate is visually analyzed by a set of 20 testers.
  • the betaine polymers especially the polymers B1, B7, C1 and C2, unlike a simple zwitterionic surfactant, remain on the surface for at least 200 rinsing cycles; the polymers of the invention are substantive of the surface.
  • the polymers do not leave at the same time as the dirt; without being linked to any mechanism, it is assumed that the anti-sticking mechanism of soiling is not "sacrificial".
  • Example 1 Compatibility of Polymer B1 and Copolymer C1 with Conventional Detergents.
  • the transmittance of the 24 solutions is measured using a photometer.
  • the transmittance of the 24 solutions is identical and comparable to that of a water solution at pH 3.
  • Polymers B1 and C1 are therefore compatible with all types of surfactants commonly used in detergency; they can therefore be formulated in any type of commercial formulation, without the risk of causing phase separation or instability over time.
  • a detergent composition containing the polymer B1 or C1 according to the invention facilitates the removal of toilet-type stains on ceramics.
  • the polymer B1 or C1 is particularly effective in the presence of nonionic or cationic surfactant at pH 3.
  • Example 2 Formulations for easy cleaning of windows
  • Formulation components A comp. (in weight) B (by weight) C (by weight) D (by weight) Isopropylic alcohol 7 7 7 7 alkylpolyglucoside 0 0.3 0 0.3 Sodium dodecylbenzene sulphonate 0.4 0 0.4 0 Ammonium hydroxide 0.3 0.3 0.3 0.3 0.3 Monomethyl ether of dipropylene glycol 3 3 3 3 3 Polymer B2 0 0 0.05 0.05 Water Qs 100 qs 100 qs 100 Qs 100 PH of the formula 7 7 7 7 7 Immediate aspect 5 5 5 5 Appearance after 1 week 4 4 5 5 2 weeks 3 4 5 5 4 weeks 2 3 5 5 6 weeks 1 3 5 4 8 weeks 1 2 4 4 4
  • Each formulation was sprayed onto the respective glass at a rate of 5 ml per m 2 of surface, and then is directly wiped with a commercial cellulose cloth.
  • An observer panel notes on a scale of 1 to 5 the cleanliness of the windows (possible traces, gloss, carbon residues).
  • a score of 1 corresponds to a very dirty glass, 5 corresponds to the initial appearance, just after cleaning.
  • Example 3 Cleaning formulations for linoleum floors
  • formulations tested are shown in the following table: components formulations A (by weight) B (by weight) Alkyl ether sulfate (2EO) 7 7 Polyglucoside alkyl 3 3 Glycol ether 1 1 Citrate 1 1 Polymer B7 0 1 Water qs 100 Qs 100 Drying time 180 seconds 120 seconds
  • Formulations A and B are diluted before use, at the rate of 10 g of formulation in 1 liter of water. One half of the soil is treated with Formulation A and the other is treated with Formulation B additive.
  • the floor is in linoleum.
  • the user notes how fast the soil becomes dry by passing his hand over it.
  • Example A is given for comparison.
  • the drying rate results of formulas A and B show that the polymer provides in the formula a marked improvement in the drying speed for the consumer.
  • the drying time is reduced by about 30%.
  • the user also notes that the polymer B7 provides gloss properties during drying.
  • the part of the soil treated with the formulation B is significantly less slippery than the portion treated with the formulation A, thus giving the treated surface anti-slip properties.
  • an open container containing a mixture of egg, oil, cream, cheese and ketchup is simultaneously introduced into the dishwasher.
  • the dishwasher is kept closed for 3 hours.
  • the performance of the detergent composition is measured in terms of anti-redeposition of dirt on the glass surface (giving rise to a deposit / white haze), as well as the hydrophilicity of the surfaces thus treated.
  • composition of the formulations A, B, D and E is given in the table of Example 4 above
  • the dishes are prewashed with the "normal" program at 55 ° C.
  • the dishes P B and P E are washed (1 dish per dishwasher) for 3 consecutive cycles, using the formulation E (without polybetaine)
  • the batches are prewashed with the "normal" program at 55 ° C.
  • the 4 batches of prewashed plates are stained with a model stain containing egg, beef meat, vegetable fat and proteins. It is allowed to dry for 1 hour at 60.degree.
  • the batches L A and L D are washed (1 batch per dishwasher) for 3 consecutive cycles, using the formulation D (without polybetaine).
  • the polymers B1 and C3 thus improve the ability of the formulations to prevent the adhesion of dirt in automatic dishwashers.
  • Example 6 Anti-redeposition of phosphates and calcium carbonate on articles washed in the dishwasher.
  • the polymer B1 or the copolymer C3 is introduced into an automatic dishwashing formulation containing or not containing sodium tripolyphosphate.
  • the filming is forced (formation of a white veil by depositing calcium mineral salts on the surface) by the addition of 2 grams of orthophosphate (NaHPO4) at the beginning of each cycle in the dishwasher.
  • This type of polymer is recommended for use in 2-in-1 (washing and rinsing) or even 3-in-1 (softening, washing and rinsing) type dishwashing compositions.
  • the polymer of the invention advantageously makes it possible to substitute the amount of nonionic surfactant with a polymer providing the treated utensils with gloss properties (especially on glasses).
  • Example 8 Dishwashing formulation by hand
  • a Pyrex® P B type glass dish with the formulation B (comprising the betaine polymer B2) is diluted in a second sink and diluted 1000 times in water.
  • the dish P A is allowed to soak for 1 hour in a first sink filled with formulation A (without polybetaine) diluted a thousand times in water.
  • the dish P B was allowed to soak for 1 hour in a second sink filled with formulation A (without polybetaine) diluted a thousand times in water.
  • Lot C The first batch of 30 plates (called “Lot C”) is washed with formulation C (without polybetaine) in 2 liters of tap water; we count the number plates of Lot C that can be cleaned, the quantity counted is 15 plates.
  • Lot D The second batch of 30 plates (called “Lot D”) was washed with formulation D (with polybetaine) in 2 liters of tap water; the number of plates in Lot D that can be cleaned is counted, the quantity counted is 22 plates.
  • the polymer B2 thus improves the cleaning capacity of the formulations for washing the dishes by hand.
  • Formulation A (polybetaine-free) was sprayed on the inner surface motility of a fiberglass-reinforced polyester bath and on one half of a tiled wall surface.
  • Formulation B (with polybetaine) was sprayed on the other motility of the inner surface of the fiberglass-reinforced polyester bath and on the other half of the tiled wall surface.
  • the surfaces are then rinsed with tap water.
  • Half of the surface of the cuvette is treated with the commercial formulation, the other half is treated with commercial polybetaine additive formulation.
  • the bowl is rinsed with the flush of the flush.
  • the model stain of the preliminary example 1 is deposited on the entire bowl with a soft brush and allowed to dry for 20 minutes before a new flush stream.
  • the polymer of the invention therefore improves the removal and anti-adhesion of dirt on the toilet bowls.
  • Example 11 Composition for the residual treatment of car bodywork
  • the polymer B7 of the invention is impregnated on sodium carbonate, and the two following formulations are prepared: components Formulation Formulation STPP 60 60 Sodium carbonate 35 35 Nonionic surfactant (Rhodoclean MSC) 2 2 Polymer B7 0 3
  • the powder is then diluted 200 times (i.e. 10 g of powder is dissolved in 2L of water) before being applied to the car using a high pressure jet type Karcher.
  • Half of the car is treated with the reference formulation and the other half with the additive formulation of polymer B7.
  • Example 12 Improved cleaning of kitchen surfaces
  • a crosslinking agent is prepared by mixing 45 g of Isooctane and 1 g of cobalt naphthenate for 30 minutes.
  • the final soil that will be applied to the surface is obtained by pouring 20.0 g of the crosslinking agent into the 90 g of soil. The mixture is stirred for 5 hours at room temperature before application.
  • a solution comprising 0.4% B7 polymer, 0.5% cationic surfactant, 4% ethylene glycol monobutyl ether, 5% isopropanol, 1% trimehylamine.
  • pretreatment solution 0.1ml of pretreatment solution is sprayed on the surface of each square to be evaluated; allowed to dry at room temperature for 5 minutes. A sponge moistened with water is passed three times on each surface, to ensure the homogeneity of the pretreatment.
  • a formulation comprising 0.5% cationic surfactant, 4% ethylene glycol monobutyl ether, 5% isopropanol, 1% trimehylamine.
  • the four squares of the center are numbered 3, 4, 5 and 6; the squares placed at the ends are numbered 1 and 2 on the one hand and 7 and 8 on the other hand.
  • a metal bar is placed above the squares to allow the passage of a cellulose sponge cut to the size of 4cmx4cm, from one side to the other of the squares; the sponge is likely to be applied to the squares at constant pressure using a screw, and to move from one side to the other of squares 1-8 along the guide.
  • the cellulose sponge is then moved from one side to the other of the squares 1 to 8 along the guide. There is 1 sponge passage when it has passed from square 1 to square 8, or vice versa.
  • test is repeated 3 times by changing the squares to evaluate (those numbered from 3 to 6).

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Claims (34)

  1. Zusammensetzung zum Reinigen oder Spülen von harten Oberflächen in wässrigem oder wässrig-alkoholischem Medium, umfassend mindestens ein oberflächenaktives Mittel, mindestens ein Polybetain (B), wobei das Gewichtsverhältnis von Polybetain (B) zu oberflächenaktivem Mittel bzw. oberflächenaktiven Mitteln zwischen 1/1 und 1/1000 liegt, wobei das Polybetain (B) dadurch gekennzeichnet ist, dass es :
    • Betain-Funktionen aufweist, die von Seitengruppen getragen werden,
    • in einem pH-Bereich von 1 bis 14 eine permanente anionische Gesamtladung und eine permanente kationische Gesamtladung trägt, wobei jedes einzelne Betain-Motiv so viele permanente anionische Ladungen wie permanente kationische Ladungen trägt,
    ▪ wobei die permanente kationische Ladung durch ein oder mehrere Onium- oder Inium-Kationen aus der Phosphor-, Schwefel- oder Stickstoff-Familie beigebracht wird,
    ▪ wobei die Betain-Funktionen im Fall der Kationen aus der Stickstoff-Familie durch die folgenden Formeln (I) bis (V) mit einer kationischen Ladung im Zentrum der Funktion und einer anionischen Ladung am Ende der Funktion und die Formel (VI) mit einer anionischen Ladung im Zentrum der Funktion und einer kationischen Ladung am Ende der Funktion wiedergegeben werden :

            -N(+)(R1)(R2)-R-A-O(-)     (I)

            -(R3)C=N(+)(R4)-R-A-O(-)     (II)

            -(R3)(R)C-N(+)(R4)(R5)-R-A-O(-)     (III)

            -N(+)(=R6)-R-A-O(-)     (IV)

            -N(+)(R1)(R2)-R-W(-)     (V)

            -R-A'(-O(-))-R-N(+)(R1)(R2)(R7)     (VI)

    Figure imgb0054
    wobei in den Formeln (I) bis (IV)
    - die Symbole R1, R2 und R5 gleich oder verschieden sind und für einen Alkylrest mit 1 bis 7 Kohlenstoffatomen und vorzugsweise 1 bis 2 Kohlenstoffatomen stehen,
    - die Symbole R3 und R4 für Kohlenwasserstoffreste stehen, die mit dem Stickstoffatom einen stickstoffhaltigen Heterocyclus, der gegebenenfalls ein oder mehrere andere Heteroatome, insbesondere Stickstoff-Heteroatome, umfasst, bilden,
    - das Symbol R6 für einen Kohlenwasserstoffrest steht, der mit dem Stickstoffatom einen gesättigten oder ungesättigten stickstoffhaltigen Heterocyclus, der gegebenenfalls ein oder mehrere andere Heteroatome, insbesondere Stickstoff-Heteroatome, umfasst, bildet,
    - das Symbol R für einen linearen oder verzweigten Alkylenrest mit 1 bis 15 Kohlenstoffatomen und vorzugsweise 2 bis 4 Kohlenstoffatomen, der gegebenenfalls durch eine oder mehrere Hydroxygruppen oder einen Benzylenrest substituiert ist, steht,
    - das Symbol A für S(=O)(=O), OP(=O)(=O), OP(=O)(OR'), P(=O)(OR') oder P(=O)(R') steht, wobei R' für einen Alkylrest mit 1 bis 7 Kohlenstoffatomen oder einen Phenylrest steht,
    Figure imgb0054
    wobei in der Formel (V)
    - die Symbole R1, R2 und R wie oben definiert sind,
    - das Symbol W für eine Ethenolat-Funktion der Formel

            O-C(O(-))=C(C≡N)2

            O-C(O)-C(-)(C≡N)2

            O-C(O)-C(-C≡N)(=C=N(-))

    steht,
    Figure imgb0054
    wobei in der Formel (VI)
    - die Symbole R1 und R2 wie oben definiert sind,
    - das Symbol R7 mit R1 oder R2 identisch oder davon verschieden ist und für einen Alkylrest mit 1 bis 7 Kohlenstoffatomen und vorzugsweise 1 bis 2 Kohlenstoffatomen steht,
    - das Symbol A' für -O-P(=O)-O- steht,
    • und eine absolute gewichtsmittlere Molmasse (Mw) im Bereich von 5000 bis 3.000.000 g/mol, vorzugsweise 8000 bis 1.000.000 g/mol und ganz speziell zwischen 10.000 und 500.000 g/mol aufweist,
    dadurch gekennzeichnet, dass das Polybetain (B) ausgewählt ist aus
    • Homopolymeren aus Betain-Einheiten, die aus denjenigen der folgenden Formeln (-SPE-), (-SPP-), (-SHPE-) und (-SHPP-) ausgewählt sind :
    Figure imgb0057
    Figure imgb0058
    Figure imgb0059
    Figure imgb0060
    • Homopolymeren von Sulfobetain, das sich von 2-Vinylpyridin der Formel
    Figure imgb0061
     ableitet,
    • Copolymeren aus Betain-Einheiten, von denen mindestens zwei verschieden sind und aus denjenigen der obigen Formeln (-SPE-), (-SPP-), (-SHPE-) und (-SHPP-) ausgewählt sind,
    • Copolymeren aus Betain-Einheiten, die gleich oder verschieden sind und aus denjenigen der obigen Formeln (-SPE-), (-SPP-), (-SHPE-) und (-SHPP-) ausgewählt sind, und Methacrylsäure-Einheiten, wobei die Menge der Methacrylsäure-Einheiten weniger als 50 Mol- %, vorzugsweise weniger als 30 Mol- %, der Copolymere beträgt,
    wobei das Polybetain (B) weniger als 50 Gew.- % Monomereinheiten, die bei dem pH-Wert der Zusammensetzung oder dem pH-Wert der Verwendung der Zusammensetzung nichtionisch, nichtionogen, anionisch oder potentiell anionisch sind, enthält.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass das Polybetain (B) weniger als 30 Mol- % Monomereinheiten, die bei dem pH-Wert der Zusammensetzung oder dem pH-Wert der Verwendung der Zusammensetzung nichtionisch, nichtionogen, anionisch oder potentiell anionisch sind, enthält.
  3. Zusammensetzung nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass das Polybetain (B) keine anderen Monomereinheiten als Betain-Einheiten, die bei einem pH-Wert von 1 bis 14 so viele permanente anionische Ladungen wie permanente kationische Ladungen tragen, oder auch weniger als 50 Mol- % und vorzugsweise weniger als 30 Mol- % andere potentiell anionische Einheiten enthält.
  4. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass das Polybetain (B) aus Homopolymeren oder Copolymeren, die aus Betain-Einheiten, die aus denjenigen der Formeln (-SPE-), (-SPP-), (-SHPE-) und (-SHPP-) ausgewählt sind, gebildet sind oder diese umfassen und eine absolute gewichtsmittlere Molmasse (Mw) im Bereich von 10.000 bis 150.000 g/mol aufweisen, ausgewählt ist.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polybetain (B) 0,001 bis 10 Gew.- % der Zusammensetzung ausmacht.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das oder die oberflächenaktiven Mittel 0,005 bis 60 Gew.- % und vorzugsweise 0,5 bis 40 Gew.- % der Zusammensetzung ausmachen.
  7. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass sie außerdem mindestens ein Additiv umfasst, das aus Chelatbildnern, Sequestriermitteln oder Belagsverhinderern, Gerüststoffen ("Buildern"), Bleichmitteln, Füllstoffen, Bleichkatalysatoren, den pH-Wert beeinflussenden Mitteln, Polymeren, die zur Steuerung der Viskosität der Mischung und/oder der Stabilität der Schäume befähigt sind, Hydrotropika, Hydratisierungs- oder Feuchthaltemitteln, Bioziden oder Desinfektionsmitteln, Lösungsmitteln mit reinigender oder entfettender Wirkung, technischen Reinigungsmitteln, wasserlöslichen organischen Lösungsmitteln mit geringer Reinigungswirkung, Cosolventien, Antischaummitteln, Abrasiva, Enzymen, Duftstoffen, Farbmitteln oder die Korrosion von Metallen inhibierenden Mitteln ausgewählt ist.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie einen pH-Wert von mindestens 7,5 aufweist und 0,001 bis 5 Gew.- % und vorzugweise 0,005 bis 2 Gew.- % Polybetain (B) umfasst.
  9. Zusammensetzung nach Anspruch 8, dadurch gekennzeichnet, dass sie außerdem mindestens ein Additiv umfasst, das aus Sequestriermitteln oder Belagsverhinderern, kationischen Bioziden oder Desinfektionsmitteln, oberflächenaktiven Mitteln, pH-Reglern, Wasser, reinigend oder entfettend wirkenden organischen Lösungsmitteln, Cosolventien, wasserlöslichen organischen Lösungsmitteln mit geringer Reinigungswirkung, Bleichmitteln und Duftstoffen ausgewählt ist.
  10. Zusammensetzung nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass sie zum Reinigen von Küchen bestimmt ist, dass sie Folgendes umfasst :
    • 0,001 bis 1 Gew.- % Polybetain (B),
    • 1 bis 10 Gew.- % wasserlösliches Lösungsmittel, insbesondere Isopropanol,
    • 1 bis 5 Gew.- % reinigend oder entfettend wirkendes Lösungsmittel, insbesondere Butoxypropanol,
    • 0,1 bis 2 Gew.- % Monoethanolamin,
    • 0 bis 5 Gew.- % mindestens eines nichtkationischen, vorzugsweise amphoteren oder nichtionischen, oberflächenaktiven Mittels,
    • 0 bis 1 Gew.- % mindestens eines kationischen oberflächenaktiven Mittels mit Desinfektionseigenschaft (insbesondere Mischung von n-Alkyl-dimethylethylbenzyl-ammoniumchlorid und n-Alkyl-dimethylbenzylammoniumchlorid),
    wobei die Gesamtmenge von oberflächenaktivem Mittel bzw. oberflächenaktivem Mitteln 1 bis 50 Gew.- % ausmacht,
    • 0 bis 2 Gew.- % einer Dicarbonsäure als Belagsverhinderer,
    • 0 bis 5 % eines Bleichmittels
    • 70 bis 98 Gew.- % Wasser,
    und dass sie einen pH-Wert von vorzugsweise 7,5 bis 13 und vorzugsweise 8 bis 12 aufweist.
  11. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie einen pH-Wert von weniger als 5 aufweist und dass sie ein anorganisches oder organisches saures Mittel und 0,001 bis 5 %, vorzugsweise 0,01 bis 2 %, bezogen auf ihr Gewicht, Polybetain (B) umfasst.
  12. Zusammensetzung nach Anspruch 11, dadurch gekennzeichnet, dass sie außerdem mindestens ein Additiv umfasst, das aus nichtionischen, amphoteren, zwitterionischen oder anionischen oberflächenaktiven Mitteln oder Mischungen davon, kationischen Bioziden oder Desinfektionsmitteln, Verdickungsmitteln, Bleichmitteln, Wasser, Lösungsmitteln, Duftstoffen und Abrasiva ausgewählt ist.
  13. Zusammensetzung nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass sie zum Reinigen von Toilettenschüsseln bestimmt ist, dass sie Folgendes umfasst :
    • 0,05 bis 5 Gew.- %, vorzugsweise 0,01 bis 2 Gew.- %, Polybetain (B),
    • 0,1 bis ungefähr 40 Gew.- % und vorzugsweise zwischen 0,5 und ungefähr 15 Gew.- % mindestens eines sauren Reinigungsmittels,
    • 0,5 bis 10 Gew.- % mindestens eines oberflächenaktiven Mittels, vorzugsweise eines anionischen oder nichtionischen oberflächenaktiven Mittels,
    • gegebenenfalls 0,1 bis 2 Gew.- % mindestens eines kationischen oberflächenaktiven Mittels mit Desinfektionseigenschaft, vorzugsweise eine Mischung von n-Alkyl-dimethyl-ethylbenzyl-ammoniumchlorid und n-Alkyl-dimethylbenzylammoniumchlorid,
    • gegebenenfalls 0,1 bis 3 Gew.- % mindestens eines Verdickungsmittels, vorzugsweise eines Gummis, ganz speziell eines Xanthangummis oder eines Succinoglycans,
    • gegebenenfalls 1 bis 10 Gew.- % mindestens eines Bleichmittels,
    • gegebenenfalls einen Konservierungsstoff, ein Farbmittel, einen Duftstoff oder ein Abrasivum
    • und 50 bis 95 Gew.- % Wasser,
    und dass sie einen pH-Wert von 0,5 bis 4 und vorzugsweise von 1 bis 4 aufweist.
  14. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie zum Reinigen von Fenstern bestimmt ist, dass sie Folgendes umfasst :
    • 0,001 bis 10 Gew.- %, vorzugsweise 0,005 bis 3 Gew.- %, mindestens eines Polybetains (B),
    • 0,005 bis 20 Gew.- %, vorzugsweise 0,5 bis 10 Gew.- %, mindestens eines nichtionischen und/oder anionischen oberflächenaktiven Mittels,
    • 0 bis 10 Gew.- %, vorzugsweise 0,5 bis 5 Gew.- %, mindestens eines amphoteren oberflächenaktiven Mittels,
    • Wasser,
    • 0 bis 30 Gew.- %, vorzugsweise 0,5 bis 15 Gew.- %, mindestens eines Lösungsmittels, vorzugsweise eines Alkohols,
    und dass sie einen pH-Wert von 6 bis 11 aufweist.
  15. Zusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass sie zum Waschen von Geschirr in einem automatischen Geschirrspüler bestimmt ist, dass sie Folgendes umfasst:
    • 0,01 bis 5 Gew.- %, vorteilhafterweise 0,1 bis 3 Gew.- %, mindestens eines Polybetains (B),
    • 0,2 bis 10 Gew.- %, vorteilhafterweise 0,5 bis 5 Gew.- %, mindestens eines oberflächenaktiven Mittels, vorzugsweise eines nichtionischen oberflächenaktiven Mittels, und gegebenenfalls
    • bis zu 90 Gew.- % mindestens eines Gerüststoffs ("Builders"),
    • bis zu 10 Gew.- %, vorzugsweise 1 bis 10 Gew.- %, ganz speziell 2 bis 8 Gew.- %, mindestens eines Hilfsreinigungsmittels, vorzugsweise eines Copolymers von Acrylsäure und Methylpropansulfonsäure,
    • bis zu 30 Gew.- % mindestens eines Bleichmittels, vorzugsweise Perborat oder Percarbonat, gegebenenfalls in Kombination mit einem Bleichaktivator,
    • bis zu 50 Gew.- % mindestens eines Füllstoffs, vorzugsweise Natriumsulfat oder Natriumchlorid,
    und dass sie einen pH-Wert von 8 bis 13 aufweist.
  16. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie zum Spülen von Geschirr in einem automatischen Geschirrspüler bestimmt ist, dass sie Folgendes umfasst:
    • 0,02 bis 10 Gew.- %, vorzugsweise 0,1 bis 5 Gew.- %, mindestens eines Polybetains (B),
    • 0,1 bis 20 Gew.- %, vorteilhafterweise 0,2 bis 15 Gew.- %, mindestens eines oberflächenaktiven Mittels, vorzugsweise eines nichtionischen oberflächenaktiven Mittels,
    • 0 bis 10 Gew.- %, vorteilhafterweise 0,5 bis 5 Gew.- %, mindestens einer Calcium sequestrierenden organischen Säure, vorzugsweise Citronensäure,
    • 0 bis 15 Gew.- %, vorteilhafterweise 0,5 bis 10 Gew.- %, mindestens eines Hilfsgerüststoffs, vorzugsweise eines Copolymers von Acrylsäure und Maleinsäureanhydrid und Acrylsäure-Homopolymeren,
    und dass sie einen pH-Wert von 4 bis 7 aufweist.
  17. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie zum Spülen von Geschirr von Hand bestimmt ist, dass sie Folgendes umfasst :
    • 0,1 bis 10 Gew.- % mindestens eines Polybetains (B),
    • 3 bis 50 Gew.- %, vorteilhafterweise 10 bis 40 Gew.- %, mindestens eines oberflächenaktiven Mittels, vorzugsweise eines anionischen oberflächenaktiven Mittels, und gegebenenfalls
    • mindestens ein nichtionisches oberflächenaktives Mittel,
    • mindestens ein nichtkationisches Bakterizid oder Desinfektionsmittel, vorzugsweise Triclosan,
    • mindestens ein synthetisches kationisches polymeres Mittel,
    • mindestens ein Polymer, das zur Steuerung der Viskosität der Mischung und/oder der Stabilität der Schäume befähigt ist,
    • mindestens ein Hydrotropikum,
    • mindestens ein Hydratisierungs- oder Feuchthaltemittel oder ein Mittel zum Schutz der Haut,
    und dass sie einen pH-Wert von 5 bis 9 aufweist.
  18. Zusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass sie zum Waschen von Motorfahrzeugen von Außen bestimmt ist, dass sie Folgendes umfasst:
    • 0,005 bis 10 Gew.- % mindestens eines Polybetains (B),
    • 0 bis 30 Gew.- %, vorzugsweise 0,1 bis 15 Gew.- %, mindestens eines nichtionischen oberflächenaktiven Mittels,
    • 0 bis 30 Gew.- %, vorzugsweise 0,1 bis 15 Gew.- %, mindestens eines anionischen oberflächenaktiven Mittels,
    • 0 bis 30 Gew.- %, vorzugsweise 0,01 bis 10 Gew.- %, mindestens eines amphoteren und/oder zwitterionischen oberflächenaktiven Mittels,
    • 0 bis 30 Gew.- %, vorzugsweise 0,05 bis 15 Gew.- %, mindestens eines kationischen oberflächenaktiven Mittels,
    wobei die Mindestmenge von oberflächenaktivem Mittel mindestens 0,5 Gew.- % beträgt,
    • 0 bis 99 Gew.- %, vorzugsweise 40 bis 98 Gew.- %, mindestens eines Gerüststoffs ("Builders"),
    • gegebenenfalls ein Hydrotropikum, Füllstoffe, pH-Regler,
    und dass sie einen pH-Wert von 8 bis 13 aufweist.
  19. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie zum Reinigen von Keramikoberflächen, insbesondere in Badezimmern, bestimmt ist, dass sie Folgendes umfasst :
    • 0,02 bis 5 Gew.- % mindestens eines Polybetains (B),
    • 0 bis 30 Gew.- %, vorzugsweise 0 bis 20 Gew.- %, mindestens eines nichtionischen oberflächenaktiven Mittels,
    • 0 bis 30 Gew.- %, vorzugsweise 0 bis 20 Gew.- %, mindestens eines anionischen oberflächenaktiven Mittels,
    wobei die Gesamtmenge von oberflächenaktivem Mittel 0,5 bis 50 Gew.- %, vorzugsweise 1 bis 30 Gew.- %, spezieller 2 bis 20 Gew.- %, ausmacht;
    • 0 bis 25 Gew.- %, vorzugsweise 0,1 bis 25 Gew.- %, mindestens eines Gerüststoffs ("Builders"),
    • 0 bis 2 Gew.- %, vorzugsweise 0,005 bis 2 Gew.- %, ganz speziell 0,5 bis 2 Gew.- %, eines Schaumreglers,
    und dass sie einen pH-Wert von 2 bis 12 aufweist.
  20. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie zum Spülen von Duschwänden bestimmt ist, dass sie Folgendes umfasst :
    • 0,02 bis 5 Gew.- %, vorzugsweise 0,05 bis 1 Gew.- %, mindestens eines Polybetains (B),
    • 0,5 bis 5 Gew.- % mindestens eines nichtionischen oberflächenaktiven Mittels, vorzugsweise eines polyethoxylierten Fettsäureesters,
    • Wasser,
    • gegebenenfalls mindestens einen niederen Alkohol,
    • gegebenenfalls 0,01 bis 5 Gew.- % mindestens eines Metallchelatbildners,
    und dass sie einen pH-Wert von 7 bis 11 aufweist.
  21. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie zum Reinigen von Glaskeramikplatten bestimmt ist, dass sie Folgendes umfasst :
    • 0,01 bis 5 Gew.- % mindestens eines Polybetains (B),
    • 0,1 bis 1 Gew.- % mindestens eines Verdickungsmittels, vorzugsweise Xanthangummi,
    • 10 bis 60 Gew.- % mindestens eines Abrasivums, vorzugsweise Calciumcarbonat oder Siliciumdioxid,
    • 1 bis 10 Gew.- % mindestens eines nichtionischen oberflächenaktiven Mittels,
    • 0 bis 7 Gew.- % mindestens eines Lösungsmittels, vorzugsweise Butyldiglykol,
    • gegebenenfalls Alkalisierungs- oder Sequestriermittel,
    und dass sie einen pH-Wert von 7 bis 12 aufweist.
  22. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie zum Reinigen von Reaktoren bestimmt ist, dass sie Folgendes umfasst:
    • 0,02 bis 5 Gew.- % mindestens eines Polybetains (B),
    • 1 bis 50 Gew.- % mindestens eines Alkalisalzes, vorzugsweise eines Phosphats, Carbonats oder Silikats von Natrium oder Kalium,
    • 1 bis 30 Gew.- % einer Mischung von oberflächenaktiven Mitteln, vorzugsweise nichtionischen und anionischen oberflächenaktiven Mitteln, ganz speziell ethoxylierten Fettalkoholen und Laurylbenzolsulfonat,
    • 0 bis 30 Gew.- % mindestens eines Lösungsmittels, vorzugsweise Diisobutylester,
    und dass sie einen pH-Wert von 8 bis 14 aufweist.
  23. Verwendung mindestens eines Polybetains (B) gemäß einem der Ansprüche 1 bis 4 in einer mindestens ein oberflächenaktives Mittel umfassenden Zusammensetzung zum Reinigen oder Spülen von harten Oberflächen in wässrigem oder wässrig-alkoholischem Medium als Mittel, das es ermöglicht, den Oberflächen Antiablagerungs- und/oder Antihafteigenschaften hinsichtlich Anschmutzungen, die sich auf den Oberflächen ablagern können, zu verleihen.
  24. Verwendung nach Anspruch 23, dadurch gekennzeichnet, dass das Polybetain (B) in einer Menge von 0,001 bis 10 Gew.- % der Zusammensetzung eingesetzt wird.
  25. Verwendung nach einem der Ansprüche 23 bis 24, dadurch gekennzeichnet, dass das Polybetain (B) in einer Zusammensetzung gemäß einem der Ansprüche 6 bis 22 eingesetzt wird.
  26. Verfahren zur Verbesserung der Eigenschaften von mindestens ein oberflächenaktives Mittel umfassenden Zusammensetzungen zum Reinigen oder Spülen von harten Oberflächen in wässrigem oder wässrig-alkoholischem Medium durch Zugabe mindestens eines Polybetains (B) gemäß einem der Ansprüche 1 bis 4 zu den Zusammensetzungen.
  27. Verfahren nach Anspruch 26, dadurch gekennzeichnet, dass das Polybetain (B) in einer Menge zugegeben wird, die ausreicht, um den Oberflächen Antiablagerungs- und/oder Antihafteigenschaften hinsichtlich Anschmutzungen, die sich auf den Oberflächen ablagern können, zu verleihen.
  28. Verfahren nach einem der Ansprüche 26 bis 27, dadurch gekennzeichnet, dass das Polybetain in einer Menge von 0,001 bis 10 Gew.- % der Zusammensetzung eingesetzt wird.
  29. Verfahren nach einem der Ansprüche 26 bis 28, dadurch gekennzeichnet, dass das Polybetain (B) in einer Zusammensetzung gemäß einem der Ansprüche 6 bis 22 eingesetzt wird.
  30. Verfahren zur Erleichterung des Reinigens oder Spülens von harten Oberflächen durch Inberührungbringen der Oberflächen mit einer Zusammensetzung in wässrigem oder wässrig-alkoholischem Medium, die mindestens ein oberflächenaktives Mittel und mindestens ein Polybetain (B) umfasst, wobei das Polybetain (B) wie in einem der Ansprüche 1 bis 4 definiert ist.
  31. Verfahren nach Anspruch 30, dadurch gekennzeichnet, dass das Polybetain (B) in einer Menge vorliegt, die ausreicht, um den Oberflächen Antiablagerungs- und/oder Antihafteigenschaften hinsichtlich Anschmutzungen, die sich auf den Oberflächen ablagern können, zu verleihen.
  32. Verfahren nach einem der Ansprüche 30 bis 31, dadurch gekennzeichnet, dass das Polybetain in einer Menge von 0,001 bis 10 Gew.- % der Zusammensetzung eingesetzt wird.
  33. Verfahren nach einem der Ansprüche 30 bis 32, dadurch gekennzeichnet, dass das Polybetain (B) in einer Zusammensetzung gemäß einem der Ansprüche 6 bis 22 eingesetzt wird.
  34. Verfahren nach einem der Ansprüche 30 bis 33, dadurch gekennzeichnet, dass die Zusammensetzung in einer solchen Menge eingesetzt wird, dass die auf der Oberfläche abgelagerte Menge an Polybetain (B) nach fakultativem Spülen und Trocknen 0,0001 bis 10 mg/m2 und vorzugsweise 0,001 bis 1 mg/m2 behandelte Oberfläche beträgt.
EP03799667.5A 2003-02-20 2003-12-19 Spül- und reinigungsmittel für harte oberflächen Expired - Lifetime EP1594945B1 (de)

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FR0309527A FR2851572B1 (fr) 2003-02-20 2003-08-01 Composition nettoyante ou rincante pour surfaces dures
FR0309527 2003-08-01
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Families Citing this family (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009514807A (ja) * 2005-10-17 2009-04-09 イサグロ リチェルカ ソシエタ ア レスポンサビリタ リミタータ 植物病原体の制御のための化合物および関連する使用
ITMI20051957A1 (it) * 2005-10-17 2007-04-18 Isagro Ricerca Srl Composti e relativo uso per il controllo di fitoparogeni
FR2894585B1 (fr) * 2005-12-14 2012-04-27 Rhodia Recherches Et Tech Copolymere comprenant des unites zwitterioniques et d'autres unites, composition comprenant le copolymere, et utilisation
DE102005060431A1 (de) * 2005-12-15 2007-06-21 Henkel Kgaa Maschinelles Geschirrspülmittel
FR2898067B1 (fr) * 2006-03-03 2008-05-30 Rhodia Recherches & Tech Modification de surfaces solides par des associations de polymeres
US20070267447A1 (en) * 2006-05-16 2007-11-22 Timothy James Kennedy Flammable propellants in plastic aerosols
WO2007146956A2 (en) 2006-06-12 2007-12-21 Rhodia Inc. Hydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate
JP2010500431A (ja) * 2006-08-10 2010-01-07 ビーエーエスエフ ソシエタス・ヨーロピア 食器洗い機用の洗浄調製物
JP2008169361A (ja) * 2007-01-15 2008-07-24 Nicca Chemical Co Ltd 樹脂表面用洗浄剤及び樹脂表面の洗浄方法
US8673365B2 (en) * 2007-01-30 2014-03-18 Arkema Inc. Hard surface cleaning and disinfecting composition
WO2008103416A1 (en) * 2007-02-21 2008-08-28 Capps Charles L Synergistic enhancement of calcium propionate
EP2142628B1 (de) 2007-05-04 2018-09-12 Ecolab Inc. Reinungsverfahren enthaltend wasserlösliche magnesiumverbindungen
US7524800B2 (en) 2007-06-12 2009-04-28 Rhodia Inc. Mono-, di- and polyol phosphate esters in personal care formulations
AU2008261700B2 (en) 2007-06-12 2014-06-05 Rhodia Inc. Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US7557072B2 (en) 2007-06-12 2009-07-07 Rhodia Inc. Detergent composition with hydrophilizing soil-release agent and methods for using same
WO2008157197A1 (en) 2007-06-12 2008-12-24 Rhodia Inc. Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
DE602007013890D1 (de) * 2007-07-26 2011-05-26 Procter & Gamble Reinigungszusammensetzung für harte Oberflächen
US7741265B2 (en) * 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
ES2556127T3 (es) 2007-08-31 2016-01-13 The Procter & Gamble Company Composición limpiadora de superficies duras ácida líquida
EP2075324A1 (de) 2007-12-27 2009-07-01 The Procter and Gamble Company Flüssiges Reinigungssäuremittel für harte Oberflächen
EP3184620A1 (de) 2007-12-28 2017-06-28 Colgate-Palmolive Company Saure reinigungszusammensetzungen mit einem polymer
ES2560869T3 (es) 2008-12-23 2016-02-23 The Procter & Gamble Company Composición limpiadora de superficies duras ácida líquida
US7829513B2 (en) * 2009-03-12 2010-11-09 Greenology Products, Inc. Organic cleaning composition
WO2010118530A1 (en) * 2009-04-14 2010-10-21 Uniboard Canada Inc Process for reducing the content of water soluble volatile organic compounds in a gas
UA109772C2 (uk) * 2009-07-02 2015-10-12 Агент для підвищення гідрофільності ґрунту і способи його застосування
US20110150817A1 (en) 2009-12-17 2011-06-23 Ricky Ah-Man Woo Freshening compositions comprising malodor binding polymers and malodor control components
GB0917740D0 (en) 2009-10-09 2009-11-25 Reckitt Benckiser Nv Detergent composition
JP5752140B2 (ja) 2009-10-22 2015-07-22 エス．シー． ジョンソン アンド サン、インコーポレイテッド フォギング防止効果およびクリーニング効果をもたらす低揮発性有機成分含有の硬表面処理剤組成物
EP2336282B1 (de) 2009-12-17 2014-07-30 The Procter and Gamble Company Flüssiges Reinigungssäuremittel für harte Oberflächen
US20120071379A1 (en) * 2010-09-21 2012-03-22 Denis Alfred Gonzales Liquid cleaning composition
JP2013543020A (ja) * 2010-09-21 2013-11-28 ザ プロクター アンド ギャンブル カンパニー 液体洗浄組成物
US20130261044A1 (en) 2010-10-01 2013-10-03 Rhodia Operations Cleaning Composition for Hard Surface
JP5631797B2 (ja) * 2011-03-31 2014-11-26 花王株式会社 自動食器洗浄機用洗浄剤組成物
US10252210B2 (en) 2011-05-10 2019-04-09 The Procter & Gamble Company Methods for reducing particulates in the air
US20120288466A1 (en) * 2011-05-10 2012-11-15 Nwachukwu Chisomaga Ugochi Compositions For Reducing Particulates In The Air
US10259987B2 (en) * 2011-12-21 2019-04-16 Rhodia Operations Amine adducts, derivatives thereof, methods for making such adducts and derivatives, and methods for using such adducts and derivatives
GB2501341B (en) * 2011-12-29 2014-10-22 Byotrol Plc Anti-microbial composition
US8658588B2 (en) 2012-01-09 2014-02-25 S.C. Johnson & Son, Inc. Self-adhesive high viscosity cleaning composition
JP2014012818A (ja) * 2012-06-27 2014-01-23 Rohm & Haas Co 硬表面をクリーニングおよびコーティングするための縞模様のつかない配合物
FR3011005B1 (fr) * 2013-09-26 2016-08-19 Ge Energy Products France Snc Agents de nettoyage mineraux mis en oeuvre sous forme de suspensions
JP6193102B2 (ja) * 2013-11-29 2017-09-06 花王株式会社 硬質表面用液体処理剤組成物
JP6188556B2 (ja) * 2013-11-29 2017-08-30 花王株式会社 硬質表面用処理剤組成物
JP6525559B2 (ja) * 2013-11-29 2019-06-05 花王株式会社 硬質表面用処理剤組成物
JP6231364B2 (ja) * 2013-11-29 2017-11-15 花王株式会社 硬質表面用処理剤組成物
JP6368132B2 (ja) * 2014-04-23 2018-08-01 花王株式会社 硬質表面用洗浄剤組成物
JP6320834B2 (ja) * 2014-04-23 2018-05-09 花王株式会社 硬質表面用洗浄剤組成物
US9381147B2 (en) 2014-10-20 2016-07-05 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic ester ammonioalkanoates
US9533951B2 (en) 2014-10-20 2017-01-03 Eastman Chemical Company Heterocyclic amphoteric compounds
US9943816B2 (en) 2014-10-20 2018-04-17 Eastman Chemical Company Amphoteric ester sulfonates
JP6401582B2 (ja) * 2014-11-20 2018-10-10 花王株式会社 親水化処理剤
JP6401597B2 (ja) * 2014-12-11 2018-10-10 花王株式会社 親水化処理剤
JP6504922B2 (ja) * 2015-05-28 2019-04-24 花王株式会社 硬質表面用洗浄剤組成物
US11414380B2 (en) 2015-09-17 2022-08-16 Eastman Chemical Company Amphoteric compounds
US9993408B2 (en) 2015-09-17 2018-06-12 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic alkyl-alkanoylamides and/or alkyl alkanoates
CN106701351A (zh) 2015-11-12 2017-05-24 艺康美国股份有限公司 低起泡器皿清洗清洁剂，含增强含油污垢除去的混合的阳离子/非离子表面活性剂体系
JP7036508B2 (ja) * 2016-03-18 2022-03-15 スリーエム イノベイティブ プロパティズ カンパニー 金属表面をコーティングするための双性イオン性ポリマー含有組成物、方法、及び物品
EP3290503A3 (de) 2016-09-01 2018-05-30 The Procter & Gamble Company Reinigungszusammensetzung zum automatischen geschirrspülen
EP3519545B1 (de) * 2016-10-03 2019-11-13 Unilever N.V. Waschmittelzusammensetzung mit einem amphoteren polymer
CN106701341A (zh) * 2016-11-29 2017-05-24 枞阳县铭瑞电子科技有限公司 一种玻璃洗涤液
CN106884172A (zh) * 2017-01-19 2017-06-23 南京百丝胜新材料科技有限公司 一种环保型金属表面清洗剂及活化方法
US11052431B2 (en) * 2017-03-27 2021-07-06 Clear Solutions USA, LLC Compositions and methods for GRAS compliant cleaners for ethanol production equipment
JP6942523B2 (ja) * 2017-05-26 2021-09-29 花王株式会社 硬質表面用液体洗浄剤組成物
JP6938222B2 (ja) * 2017-05-26 2021-09-22 花王株式会社 硬質表面用液体洗浄剤組成物
JP6887726B2 (ja) * 2017-05-26 2021-06-16 花王株式会社 硬質表面用液体洗浄剤組成物
MX2020006295A (es) 2017-12-19 2020-09-10 Colgate Palmolive Co Composicion de limpieza para proporcionar repelencia al agua duradera en las superficies.
US20190211285A1 (en) * 2018-01-08 2019-07-11 Douglas Alexie Exterior cleaning composition for a vehicle
US20210230329A1 (en) * 2018-06-04 2021-07-29 Rhodia Operations Methods for reducing or preventing colloids adhesion and/or fouling on a substrate, compositions, and copolymers useful therefor
CN112912458B (zh) 2018-11-22 2023-10-03 花王株式会社 亲水化处理剂组合物
US20220089972A1 (en) 2019-02-13 2022-03-24 Kao Corporation Hydrophilization treatment agent composition
WO2021003663A1 (en) * 2019-07-09 2021-01-14 Rhodia Operations Methods for resisting frost on a substrate, compositions, and copolymers useful therefor
WO2021072175A1 (en) 2019-10-11 2021-04-15 Packers Sanitation Services, Inc., Ltd. Condensation reduction treatment
TW202406753A (zh) * 2022-03-16 2024-02-16 日商Ｔｏｔｏ股份有限公司 構件

Family Cites Families (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1221019B (de) * 1964-02-06 1966-07-14 Bayer Ag Verfahren zur Herstellung von Acrylnitril-Copolymerisaten
US3549605A (en) * 1965-04-21 1970-12-22 Eastman Kodak Co Novel polymers and their use in photographic applications
US3520818A (en) * 1966-12-20 1970-07-21 Procter & Gamble Abrasive liquid detergent compositions
US3671305A (en) * 1970-01-30 1972-06-20 Rohm & Haas Method of treating shaped articles with betaine-type polymers and the articles thereby obtained
US3671502A (en) * 1970-11-12 1972-06-20 Kendall & Co Betaine copolymers with hydroxyalkylacrylates and hydroxyalkylmethacrylates
US4287080A (en) 1979-09-17 1981-09-01 The Procter & Gamble Company Detergent compositions which contain certain tertiary alcohols
PH17245A (en) 1980-11-28 1984-07-03 Procter & Gamble Detergents compositions containing low levels of amine oxides
CA1142900A (en) * 1981-05-06 1983-03-15 Armand Dale Emergency descent device
JPS5973560A (ja) * 1982-06-15 1984-04-25 Nippon Paint Co Ltd 重合性スルホベタイン化合物ならびにその製法
EP0112592B1 (de) * 1982-12-23 1989-08-23 THE PROCTER & GAMBLE COMPANY Zwitterionische Polymere mit Fleckenentfernungs- und Anti-Wiederabsetz-Eeigenschaften, verwendbar in Detergenszusammensetzungen
US4557853A (en) 1984-08-24 1985-12-10 The Procter & Gamble Company Skin cleansing compositions containing alkaline earth metal carbonates as skin feel agents
US4607076A (en) * 1985-01-02 1986-08-19 Exxon Research And Engineering Co. Betaine copolymers-viscosifiers for water and brine
US4742135A (en) * 1985-12-30 1988-05-03 Exxon Research And Engineering Company Terpolymers of acrylamide, alkylacrylamide and betaine monomers
US4882405A (en) * 1985-12-30 1989-11-21 Exxon Research And Engineering Company Terpolymers of acrylamide, alkylacrylamide and betaine monomers
DE3614336A1 (de) * 1986-04-28 1987-10-29 Henkel Kgaa Fluessige waessrige reinigungsmittel fuer harte oberflaechen
JP2523837B2 (ja) * 1988-11-25 1996-08-14 花王株式会社 水洗トイレ用清浄剤組成物
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
DE69117270T2 (de) 1990-11-30 1996-11-14 Rhone Poulenc Chimie Gerüststoff auf Basis von Alkalimetallsilikaten für Reinigungsmittelzusammensetzungen
EP0810239B1 (de) 1991-07-05 2000-09-20 Biocompatibles Limited Polymere Oberflächenbeschichtungszusammensetzungen
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
US5710119A (en) * 1993-07-23 1998-01-20 The Procter & Gamble Company Detergent compositions inhibiting dye transfer comprising copolymers of N-vinylimidazole and N-vinylpyrrolidone
US5536452A (en) 1993-12-07 1996-07-16 Black; Robert H. Aqueous shower rinsing composition and a method for keeping showers clean
US5476660A (en) * 1994-08-03 1995-12-19 Lever Brothers Company, Division Of Conopco, Inc. Deposition of materials to surfaces using zwitterionic carrier particles
ATE209245T1 (de) 1995-02-02 2001-12-15 Procter & Gamble Verfahren zur entfernung von teeflecken in geschirrspülern mit zusammensetzungen enthaltend kobalt (iii)- katalysator
CA2212115C (en) 1995-02-02 2001-04-24 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt catalysts
JPH10513214A (ja) 1995-02-02 1998-12-15 ザ、プロクター、エンド、ギャンブル、カンパニー コバルトキレート化触媒を含む自動皿洗い組成物
US5559261A (en) 1995-07-27 1996-09-24 The Procter & Gamble Company Method for manufacturing cobalt catalysts
US5863880A (en) * 1997-09-19 1999-01-26 Isp Investments Inc. Laundry detergent compositions containing water soluble dye complexing polymers
CA2248476A1 (en) 1997-10-01 1999-04-01 Unilever Plc Bleach activation
JPH11349826A (ja) 1998-06-09 1999-12-21 Nippon Shokubai Co Ltd 高分子吸収体の製造方法
EP1094706A1 (de) * 1998-07-09 2001-05-02 Rhodia Chimie Verfahren zur biozide behandlung von oberflächen
JP4156113B2 (ja) * 1998-12-25 2008-09-24 日油株式会社 防曇剤組成物
US6191098B1 (en) * 1999-04-28 2001-02-20 National Starch And Chemical Investment Holding Corporation Polyvinylpyridinium derivatives as anti-dye transfer agents
JP2001072998A (ja) * 1999-06-28 2001-03-21 Nof Corp 洗浄剤組成物
FR2796392B1 (fr) 1999-07-15 2003-09-19 Rhodia Chimie Sa Composition nettoyante comprenant un polymere hydrosoluble ou hydrodispersable
FR2796391B1 (fr) * 1999-07-15 2003-09-19 Rhodia Chimie Sa Composition nettoyante pour surfaces dures
FR2796390B1 (fr) 1999-07-15 2001-10-26 Rhodia Chimie Sa Utilisation d'un polymere amphotere pour traiter une surface dure
JP3677675B2 (ja) * 2000-03-27 2005-08-03 ライオン株式会社 硬表面用防汚洗浄剤組成物
JP2001181601A (ja) * 1999-12-27 2001-07-03 Lion Corp 防汚組成物
US6391995B2 (en) * 2000-02-09 2002-05-21 Reilly Industries, Inc. Polymer compositions useful as dye complexing agents, and processes for preparing same
JP2002069178A (ja) * 2000-06-12 2002-03-08 Mitsui Chemicals Inc 重合体及びその製造方法
FR2813312B1 (fr) * 2000-08-25 2006-07-14 Rhodia Chimie Sa Composition a base de nanolatex de polymeres pour le soin du linge
JP4694719B2 (ja) * 2001-05-31 2011-06-08 日油株式会社 繊維用防汚性及び耐洗濯性付与剤及び組成物
JP4723117B2 (ja) * 2001-05-31 2011-07-13 日油株式会社 繊維用防汚性及び耐洗濯性付与剤及び組成物
CN1298830C (zh) * 2002-02-22 2007-02-07 花王株式会社 用于硬表面的防污洗涤剂
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
DE102007039652A1 (de) * 2006-12-05 2008-06-12 Henkel Kgaa Mittel zur Behandlung harter Oberflächen
AU2008261700B2 (en) * 2007-06-12 2014-06-05 Rhodia Inc. Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
WO2009059878A1 (fr) * 2007-11-06 2009-05-14 Rhodia Operations Copolymere pour le traitement ou la modification de surfaces

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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CA2516405C (fr) 2012-02-14
WO2004083354A1 (fr) 2004-09-30
US7923428B2 (en) 2011-04-12
CA2516405A1 (fr) 2004-09-30
FR2851572A1 (fr) 2004-08-27
BR0318128B1 (pt) 2013-08-27
JP2010100861A (ja) 2010-05-06
BR0318128A (pt) 2006-02-07
US20060217286A1 (en) 2006-09-28
AU2003299381A1 (en) 2004-10-11
EP1594945A1 (de) 2005-11-16
ES2626984T3 (es) 2017-07-26
FR2851572B1 (fr) 2007-04-06
JP2006514150A (ja) 2006-04-27

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