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EP1196527A1 - Verwendung eines amphoteren polymeres zur behandlung der harten oberfläche - Google Patents

Verwendung eines amphoteren polymeres zur behandlung der harten oberfläche

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Publication number
EP1196527A1
EP1196527A1 EP00951609A EP00951609A EP1196527A1 EP 1196527 A1 EP1196527 A1 EP 1196527A1 EP 00951609 A EP00951609 A EP 00951609A EP 00951609 A EP00951609 A EP 00951609A EP 1196527 A1 EP1196527 A1 EP 1196527A1
Authority
EP
European Patent Office
Prior art keywords
weight
water
acid
composition
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00951609A
Other languages
English (en)
French (fr)
Other versions
EP1196527B1 (de
Inventor
Eric Aubay
Dominic Yeung
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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Filing date
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Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1196527A1 publication Critical patent/EP1196527A1/de
Application granted granted Critical
Publication of EP1196527B1 publication Critical patent/EP1196527B1/de
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3796—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • 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
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines
    • 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
    • C11D2111/24—Mineral surfaces, e.g. stones, frescoes, plasters, walls or concretes
    • 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
    • C11D3/39—Organic or inorganic per-compounds

Definitions

  • the present invention relates to the cleaning of industrial or domestic industrial hard surfaces, in particular of the ceramic, tiling or glass type, aimed at imparting hydrophilic properties to them.
  • a more particular subject of the invention is the use of polymers having both properties of interaction with the hard surface and hydrophilic properties to give the latter remanent hydrophilization properties so as to avoid the subsequent presence of traces due in particular to the drying of the drops of water deposited on said surface.
  • detergent formulations allow effective cleaning of hard industrial, domestic or community surfaces. They generally consist of an aqueous solution of surfactants, in particular nonionic and anionic surfactants, alcohol (s) to facilitate drying, and optionally sequestering agents and bases to adjust the pH.
  • surfactants in particular nonionic and anionic surfactants
  • alcohol (s) to facilitate drying
  • sequestering agents and bases to adjust the pH.
  • a major shortcoming of these detergent formulations is that the subsequent contact of the hard surface with water can lead to the presence of traces during drying. This contact with water after applying detergent can come, for example, from rainwater in the case of windows, mains water on a bathroom tile, or rinse water when cleaning requires rinsing. They can also come from drying dishes in the open air in the case of detergent formulas for cleaning dishes by hand, or from drying dishes automatically in the case of detergents for dishwashers .
  • said formula can either be used in the cleaning cycle (detergent formula) or during rinsing (rinsing liquid).
  • rinsing liquid rinsing liquid
  • the solution consists in increasing the hydrophilicity of the surface in order to obtain a contact angle as small as possible between the hard surface to be treated and the drop d 'water.
  • EP 522 756 describes ampholyte terpolymers comprising, as polymer units:
  • DADMAC diallyldimethylammonium chloride
  • an anionic monomer in particular acrylic acid
  • - a nonionic monomer in particular acrylamide
  • terpolymers have hydration and protective properties for the skin and nails and are available in compositions intended to be applied to the skin such as after shaving, sunscreens, hand lotions, liquid soaps, bath products. , shaving foams.
  • compositions intended to be applied to the skin such as after shaving, sunscreens, hand lotions, liquid soaps, bath products. , shaving foams.
  • the document also describes a composition for washing dishes by hand, this composition being particularly suitable for protecting and moisturizing the skin.
  • WO 97/22 640 describes aqueous dispersions of polymers having surfactant properties and more particularly foaming properties.
  • the polymers are prepared by polymerization of vinyl monomers (a) having at least one quaternary nitrogen atom with vinyl monomers (b) having at least one amide group and monomers vinyl (c) having both hydrophilic and hydrophobic groups, so as to give the terpolymer detergent properties.
  • the monomers (b) are polyethoxylated and polypropoxylated derivatives of carboxylic acid, such as acrylic acid.
  • EP 835 925 describes a detergent composition for washing dishes in an automatic dishwasher comprising a lipolytic enzyme and a copolymer obtained by polymerization of 50 to 99% by mole of anionic monomer units, in particular acrylic acid, with 1 50% by mole of cationic monomers, in particular DADMAC and 0 to 25% by mole of an anionic, cationic, amphoteric, nonionic monomer or a mixture of these, in particular acrylic acid esters.
  • the combination of the lipolytic enzyme with the polymer prevents the deposit of lime soap on the dishes without having a harmful effect on the action of elimination of fats by lipases.
  • JP 09169995-A- It has been proposed (JP 09169995-A-) to use in the compositions for the treatment against soiling of toilet bowls, a cationic polymer making it possible to increase the hydrophilicity of the surface to be treated.
  • cationic polymer the homopolymers of DADMAC and the copolymers of DADMAC and of acrylamide, as well as the copolymers of DADMAC and of acrylic acid; the polymers mentioned as preferred are the copolymers of DADMAC and acrylic acid having a DADMAC / acrylic acid weight ratio of 8/2 and most preferably the homopolymers of DADMAC.
  • the work of the inventors having led to the present invention has made it possible to determine that copolymers obtained by copolymerization of monomers having a quaternary ammonium function and two ethylenically unsaturated groups with monomers having a group capable of ionizing in the application medium to form anionic units, having a ratio of the first monomers to the second monomers located in a given range , allowed to give hard surfaces remarkable hydrophilization properties.
  • a first subject of the invention consists in the use of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
  • - Ri and R 4 independently of one another represent a hydrogen atom or a linear or branched Ci-C ⁇ alkyl group
  • R 2 and R 3 independently of one another represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a C 1 -C 6 chain, linear or branched, preferably a methyl group;
  • - n and m are whole numbers between 1 and 3;
  • (c) optionally at least one hydrophilic monomeric compound with ethylenic unsaturation of neutral charge carrying one or more hydrophilic groups, copolymerizable with (a) and (b), in which the molar ratio a / b is between 60/40 and 5 / 95 to give hydrophilic properties to a hard surface.
  • - Ri represents hydrogen
  • - R 2 represents methyl
  • the ion X ′′ is advantageously chosen from halogen sulfate, hydrosulfate, phosphate, citrate, formate and acetate.
  • the monomer (a) gives the copolymer interaction characteristics with the surface to be treated, in particular allowing the copolymer to be anchored on this surface.
  • the monomer (b) and optionally the monomer (c) give the copolymer hydrophilic characteristics which, after anchoring of the copolymer on the surface to be treated, are transmitted to it.
  • This hydrophilization property of the surface also makes it possible to reduce the formation of fogging on the surface; this benefit can be exploited in particular in cleaning formulas for windows and mirrors, in particular in bathrooms.
  • the copolymer according to the invention advantageously has a molecular mass of at least 1,000, advantageously of at least 10,000; it can range up to 20,000,000, advantageously up to 10,000,000. Unless otherwise indicated, when we speak of molecular mass, it will be the molecular mass by weight, expressed in g / mol.
  • the copolymer is preferably random.
  • the monomer (a) has the following structure:
  • H 2 C - CH CH 2 N + CH 2 CH ⁇ CH 2
  • X " being is as defined above.
  • a particularly preferred monomer is that of the above formula in which X " represents CI " , called DADMAC.
  • the monomers (b) are advantageously C 3 -C 8 carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids with water-soluble monoethylenic unsaturation, their anhydrides and their water-soluble salts.
  • acrylic acid methacrylic acid, ⁇ -ethacrylic acid, ⁇ , ⁇ -dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, acid allylacetic, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacroyl-alanine, N-acryloyl-hydroxy-glycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, sulfoethyl methacrylate, styrene sulfonic acid, vinyl sulfonic acid, vinylphosphonic acid, acrylate phosphoethyl, phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl
  • the monomers (c) there may be mentioned acrylamide, vinyl alcohol, CC 4 alkyl esters of acrylic acid and methacrylic acid, C- ⁇ -C hydroxyalkyl esters 4 of acrylic acid and methacrylic acid, in particular ethylene glycol and propylene glycol acrylate and methacrylate, the polyalkoxylated esters of acrylic acid and of acid methacrylic, in particular the polyethylene glycol and polypropylene glycol esters.
  • the level of monomers (a) is advantageously between 5 and 60%, preferably 20 to 50 mol%.
  • the level of monomers (b) is advantageously between
  • the level of monomers (c) is advantageously between 0 and 50%, preferably 5 to 30 mol%.
  • the a / b molar ratio is preferably between 50/50 and 10/90.
  • copolymers of the invention can be obtained according to known techniques for preparing the copolymers, in particular by radical polymerization of the ethylenically unsaturated starting monomers which are known compounds or which can be easily obtained by a person skilled in the art by using classical synthesis methods of organic chemistry.
  • the radical polymerization is preferably carried out in an oxygen-free environment, for example in the presence of an inert gas
  • reaction is carried out in an inert solvent, preferably methanol or ethanol, and more preferably in water.
  • the polymerization is initiated by the addition of a polymerization initiator.
  • the initiators used are the free radical initiators commonly used in the art. Examples include organic peresters (t-butylperoxypivalate, t-amylperoxypivalate, t-butylperoxy-oc-ethylhexanoate, etc.); azo-type organic compounds, for example azo-bis-amidino-propane hydrochloride, azo-bis-isobutyronitrile, Pazo-bis-2,4-dimethylvaleronitrile, etc.); inorganic and organic peroxides, for example hydrogen peroxide, benzyl peroxide and butyl peroxide, etc; redox initiator systems, for example those comprising oxidizing agents, such as persulfates (in particular ammonium or alkali metal persulfates, etc.); chlorates and bromates (including inorganic or organic chlorates and / or bromates); reducing agents such as
  • Preferred initiators are water soluble initiators. Particular preference is given to sodium persulfate and azo-bis-amidinopropane hydrochloride.
  • the polymerization can be initiated by irradiation using ultraviolet light.
  • the amount of initiators used is generally a sufficient amount will be able to initiate the polymerization.
  • the initiators are present in an amount ranging from 0.001 to about 10% by weight relative to the total weight of the monomers, and preferably are included in an amount less than 0.5% by weight relative to the total weight of the monomers , a preferred amount being in the range of 0.005 to 0.5% by weight based on the total weight of the monomers.
  • the initiator is added to the polymerization mixture, either continuously or discontinuously.
  • the polymerization is carried out under effective reaction conditions to polymerize the monomers (a), the monomers (b) and optionally the monomers (c) in an oxygen-free atmosphere.
  • the reaction is carried out at a temperature ranging from about 30 ° to about 100 ° and preferably between 60 ° and 90 ° C.
  • the oxygen-free atmosphere is maintained for the duration of the reaction, for example by maintaining a nitrogen purge throughout the reaction.
  • copolymers are very particularly preferred: - DADMAC / acrylic acid / acryiamide copolymer; - DADMAC / maleic acid copolymer;
  • the copolymers of the invention are useful for imparting hydrophilization properties to surfaces to which they are applied, in particular for imparting persistent anti-stain or anti-trace properties to surfaces, as well as anti-fogging properties.
  • anti-fingerprint or residual anti-stain properties it is meant that the treated surface retains these properties over time, including after subsequent contact with water, whether it is rainwater , water from the distribution network or rinse water with or without rinse aid added.
  • copolymers described above are particularly advantageous in cleaning compositions for hard surfaces.
  • the cleaning composition according to the invention intended for treating hard surfaces comprises at least one copolymer as described above at a content of between 0.001% and 10% by weight relative to the total weight of the composition, depending on the concentration of ingredients assets of it.
  • copolymers of the invention are intended to be incorporated into compositions for cleaning dishes in a dishwasher or by hand, windows, ceramics such as bathrooms, sinks, car bodies, shower walls , toilet bowls, ceramic hobs.
  • composition according to the invention generally comprises at least one surfactant.
  • This is advantageously anionic and / or nonionic. It can also be cationic, amphoteric or zwitterionic.
  • soaps such as the Cs-C 24 fatty acid salts, for example the salts of fatty acids derived from coconut and tallow; alkylbenzenesulfonates, in particular alkyl C 8- ci 3 linear alkyl benzenesulfonates, in which the alkyl group comprises from 10 to 16 carbon atoms, the alcohol- sulfates, ethoxylated alcohol sulfates, hydroxyalkyl sulfonates; alkyl sulfates and sulfonates, especially C 12 -C 16 , monoglycerides sulfates, and fatty acid chloride condensates with hydroxyalkyl sulfonates.
  • soaps such as the Cs-C 24 fatty acid salts, for example the salts of fatty acids derived from coconut and tallow; alkylbenzenesulfonates, in particular alkyl C 8- ci 3 linear alkyl benzenesulfon
  • R represents an alkyl radical in Cs-2 0 , preferably in C10-C1 6
  • R' an alkyl radical in C- ⁇ -C 6 , preferably in C1-C 3 and M
  • an alkaline cation sodium, potassium, lithium
  • substituted or unsubstituted ammonium methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium
  • Mention may very particularly be made of methyl ester sulfonates whose radicals R is C ⁇ 4 -C 16 ;
  • alkyl sulphates of formula ROSO3M where R represents a C 5 -C 2 alkyl or hydroxyalkyl radical, preferably C ⁇ 0 -C ⁇ 8 , M representing a hydrogen atom or a cation of the same definition as above, thus as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 30 units, preferably from 0.5 to 10 OE and / or OP units;
  • the sulphated alkylamides of formula RCONHR'OSO 3 M where R represents an alkyl radical in C 2 -C 2 2, preferably in C6-C20, R 'an alkyl radical in C2-C3, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 60 OE and / or OP units;
  • RHODAFAC RA600 RHODAFAC PA15 or RHODAFAC PA23 marketed by the company RHODIA.
  • nonionic surfactants there may be mentioned in particular the condensates of alkylene oxide, in particular of ethylene oxide with alcohols, polyols, alkylphenols, esters of fatty acids, acid amides fatty and fatty amines; amine oxides, sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, in particular sucrose monopalmitate; long chain tertiary phosphine oxides; dialkylsulfoxides; polyoxyethylene and polyoxypropylene block copolymers; 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 ).
  • alkylene oxide in particular of ethylene oxide with alcohols, polyols, alkylphenols, esters of fatty acids, acid amides fatty
  • polyoxyalkylenated polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated alkylphenols in which the alkyl substituent is C 6 -C 12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the Triton X-45, X-1 14, X-100 or X-102 sold by Rohm & Haas Cy. ; . glucosamides, glucamides, glycerolamides;
  • TERGITOL 15-S-9 TERGITOL 24-L-6 NMW sold by Union Carbide Corp.
  • NEODOL 45-9 NEODOL 23-65, NEODOL 45-7
  • NEODOL 45-4 marketed by Shell Chemical Cy.
  • RHODASURF IDO60, RHODASURF LA90, RHODASURF IT070 marketed by the company RHODIA. .
  • amine oxides such as alkyl oxides C 10 -C ⁇ 8 dimethylamines, alkoxy oxides C 8 -C 22 ethyl dihydroxy ethylamines; . the alkylpolyglycosides described in US-A-4,565,647; . amides of C 8 -C 2 o fatty acids; . ethoxylated fatty acids;
  • Cationic surfactants are in particular alkylammonium salts of formula
  • R 1 and R 2 are similar or different and represent a C 1 -C 20 alkyl radical. an aryl or benzyl radical
  • R 3 and R 4 are similar or different and represent a C 1 -C 20 alkyl radical.
  • zwitterionic surfactants include aliphatic quaternary ammonium derivatives, including 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-sulfonate and 3- (N, N-dimethyl-N-hexadecyl -ammonio) 2-hydroxypropane 1 -sulfonate.
  • amphoteric surfactants include betaines, sulfobetaines and carboxylates and sulfonates of fatty acids and imidazole.
  • alkyldimethylbetaines alkylamidopropyldimethylbetaines, alkyldimethylsulfobetaines or alkylamidopropyldimethylsulfobetaines such as MIRATAINE CBS sold by the company
  • RHODIA the condensation products of fatty acids and protein hydrolysates
  • alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms the amphoteric derivatives of alkylpolyamines such as PAMPHIONIC XL® marketed by RHODIA, AMPHOLAC 7T / X® and AMPHOLAC 7C / X® marketed by BEROL NOBEL
  • surfactants are compounds generally used as surfactants designated in the well-known manuals "Surface Active Agents", volume I by Schwartz and Perry and “Surface Active Agents and Detergents", volume II by Schwartz, Perry and Berch.
  • the surfactants can be present in an amount of 0.005 to 60%, especially from 0.5 to 40% by weight depending on the nature of the surfactant (s) and the destination of the cleaning composition.
  • the copolymer weight ratio of general formula 1, surfactant is between 1/2 and 1/100, advantageously 1/5 and 1/50.
  • organic "builders” detergency builders improving the surface properties of surfactants
  • organic phosphonates like those in the range
  • DEQUEST® from MONSANTO, (at a rate of 0 to 2% of the total weight of detergent composition expressed as dry matter in the case of a dishwasher composition);
  • polycarboxylic acids or their water-soluble salts and the water-soluble salts of carboxylic polymers or copolymers such as. polycarboxylate or hydroxypolycarboxylate ethers.
  • polyacetic acids or their salts nitriloacetic acid, N acid, N-dicarboxymethyl-2-aminopentane dioic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetates, nitrilotriacetates such as NERVANAID NTA Na 3 sold by the company RHODIA, N- (2 hydroxyethyl) -nitrilodiacetates), (at a rate of 0 to 10% of the total weight of detergent composition expressed as dry matter in the case a dishwasher composition);
  • alkali metal pyrophosphates zeolites
  • silicates in an amount which can range up to approximately 50% of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition
  • borates, carbonates, bicarbonates, alkali or alkaline earth sesquicarbonates in an amount which can range up to approximately 50% of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition
  • cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) described in EP-A-488 868, such as NABION 15 sold by the company RHODIA in an amount which can range up to approximately 50% by weight total of said detergent composition expressed as dry matter in the case of a dishwasher composition); (the total amount of organic and / or mineral "builders", which may represent up to 90% of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition);
  • acetylated bleaching activators such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED) or chlorinated products of the chloroisocyanurate type, or chlorinated products of the alkali metal hypoch
  • alkalizing additives soluble in the washing medium alkali metal phosphates, carbonates, perborates, hydroxides or acidifying additives soluble in the washing medium (carboxylic acids or polycarboxylic, bicarbonates and sesquicarbonates of alkali metals, phosphoric and polyphosphoric acids, sulfonic acids, etc.) or enzymes or perfumes, dyes, metal corrosion inhibiting agents;
  • MIRAPOL A550® MIRAPOL A15® marketed by RHODIA
  • MERQUAT 550® marketed by CALGON .
  • cellulose or guar derivatives used to control the viscosity of the mixture and / or the stability of the foams formed in use, such as cellulose or guar derivatives
  • hydrotropic agents such as C 2 -C 8 short alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol, ...
  • - moisturizing or humectants for the skin such as glycerol, urea or skin protective agents, such as proteins or protein hydrolysates, cationic polymers such as cationic guar derivatives (JAGUAR C13S®, JAGUAR C162®, HICARE 1000® marketed by RHODIA,
  • compositions according to the invention can be diluted (in water) from 1 to 10,000 times, preferably from 1 to 1,000 times before use.
  • the cleaning composition according to the invention is applied to the surface to be treated in an amount such that it allows, after rinsing if necessary, and after drying, a deposit of copolymer according to the invention from 0.0001 to 1g / m 2 , of preferably 0.001 to 0.1 g / m 2 of surface to be treated.
  • the copolymer described above is used for cleaning the dishes by hand or in an automatic machine to give the dishes hydrophilization properties as described above.
  • said copolymer may be present, either in the detergent formula used in the washing cycle, or in the rinsing liquid.
  • Detergent formulations for washing dishes in automatic dishwashers advantageously comprise from 0.1 to 5%, preferably 0.2 to 3% by weight of water-soluble or water-dispersible copolymer relative to the total weight of dry matter of the composition .
  • the 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 said detergent composition expressed as dry matter, the remainder being constituted by various additives and fillers, as already mentioned above.
  • These formulas generally comprise 30 to 95% of a builder agent, chosen from silicates, phosphates, carbonates. They also include an oxidizing system, introduced at a content of between 3 and 25%.
  • Formulations for rinsing dishes in an automatic dishwasher advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5% by weight of copolymer relative to the total weight of the composition.
  • They also comprise from 0.5 to 20%, preferably 0.5 to 15% by weight relative to the total weight of said composition of a surfactant, preferably nonionic or a mixture of nonionic and anionic surfactant.
  • a surfactant preferably nonionic or a mixture of nonionic and anionic 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, block copolymers of ethylene oxide - oxide of propylene, optionally polyoxyethylenated carboxylic amides ....
  • They also 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 with calcium, preferably citric acid.
  • They can also comprise an auxiliary agent of the copolymer type of acrylic acid and maleic anhydride or homopolymers of acrylic acid in an amount of 0 to 15%, preferably 0.5 to 10% by weight relative to the weight total of said composition.
  • the invention also relates to the use of the polymer according to the invention in a cleaning composition for washing dishes by hand.
  • Preferred detergent formulations of this type comprise from 0.1 to 5 parts by weight of copolymer of the invention 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 at least one surfactant, preferably anionic, chosen in particular from sulphates of aliphatic alcohols saturated with C 5 -C 24 , preferably with C 10 -C 16 , optionally condensed with approximately 0.5 to 30, preferably 0.5 to 5, very particularly 0.5 to 3 moles of ethylene oxide, in acid form or in the form of a salt, in particular alkaline (sodium), alkaline earth (calcium, magnesium) ...
  • the present invention relates more particularly to aqueous detergent foaming liquid formulations for washing dishes by hand.
  • Said formulations may also contain other additives, in particular other surfactants, such as:
  • nonionic surfactants such as amine oxides, alkylglucamides, oxyalkylene derivatives of fatty alcohols, alkylamides, alkanolamides, amphoteric or zwitterionic surfactants.
  • non-cationic bactericidal agents or disinfectants such as triclosan
  • the copolymer according to the invention is also useful for window treatments.
  • This treatment can be carried out by various known techniques. Mention may in particular be made of window cleaning techniques by spraying with a water jet using Karcher® type devices.
  • the amount of polymer introduced will generally be such that, when using the cleaning composition, after possible dilution, the concentration is between 0.001 g / l and 2 g / l, preferably 0.005 g / l and 0, 5 g / l.
  • the window cleaning composition according to the invention comprises:
  • the window cleaning formulations comprising said polymer may also contain:
  • Another object of the invention consists in the use of a polymer as defined above for the external cleaning, in particular of the bodywork, of motor vehicles.
  • the copolymer according to the invention can be present either in a detergent formula used for the washing operation, or in a rinsing product.
  • the cleaning composition for motor vehicles advantageously comprises from 0.05 to 5% by weight of copolymer according to the invention relative to the total weight of said composition as well as: - nonionic surfactants (at a rate of 0 to 30%, of preferably from 0.5 to 15% of the formulation),
  • organic or mineral detergency builders .
  • the minimum amount of surfactant present in type of composition can be at least 1% of the formulation
  • the copolymer of the invention is also particularly suitable for cleaning hard surfaces other than those described above, in particular ceramics (tiles, baths, sinks, etc.).
  • the cleaning formulation advantageously comprises from 0.02 to 5% by weight of copolymer relative to the total weight of said composition as well as at least one surfactant.
  • nonionic surfactants are preferred, in particular the compounds produced by condensation of alkylene oxide groups as described above which are of hydrophilic nature with a hydrophobic organic compound which may be of aliphatic or alkyl-aromatic 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 (HBL).
  • the amount of nonionic surfactants in the composition of the invention is generally from 0 to 30% by weight, preferably from 0 to 20% by weight.
  • An anionic surfactant can optionally be present in an amount of 0 to 30%, advantageously 0 to 20% by weight.
  • amphoteric, cationic or zwitterionic detergents in the composition of the present invention for cleaning hard surfaces.
  • the total amount of surfactant compounds used in this type of composition is generally between 1.5 and 50%, preferably between 5 and 30% by weight, and more particularly between 10 and 20% by weight relative to the total weight of the composition.
  • the hard surface cleaning composition of the present invention may also contain other minority ingredients which are cleaning additives.
  • composition can contain organic or inorganic detergency builders as mentioned above.
  • the detergency builder is used in an amount between 0.1 and 25% by weight relative to the total weight of the composition.
  • Another optional ingredient of the hard surface cleaning compositions of the invention is a foam control agent, which can be used in compositions having a tendency to produce excess foam when in use.
  • An example of these materials are soaps.
  • the soaps are salts of fatty acids and include the soaps of alkali metals, in particular the sodium, potassium, ammonium and alkanol ammonium salts of higher fatty acids containing approximately from 8 to 24 carbon atoms, and preferably d '' about 10 to about 20 carbon atoms.
  • Particularly useful are the sodium, potassium and mono-, di- and triethanolamine salts or mixtures of fatty acids derived from coconut oil and ground nut oil.
  • the amount of soap can be at least 0.005% by weight, preferably from 0.5% to 2% by weight relative to the total weight of the composition.
  • Additional examples of foam control materials are organic solvents, hydrophobic silica, silicone oil and hydrocarbons.
  • the hard surface cleaning compositions of the present invention may also contain in addition to the above-mentioned ingredients, other optional ingredients such as pH regulating agents, dyes, optical brighteners, soil suspending agents, detergent enzymes, compatible bleaches, gel formation regulators, freeze-thaw stabilizers, bactericides, preservatives, solvents, fungicides, insect repellents, hydrotropic agents, fragrances and opacifiers or pearlescent.
  • the polymer of the invention can also be used for cleaning toilet bowls.
  • a composition particularly suitable for this purpose comprises from 0.05 to 5% by weight of copolymer according to the invention.
  • composition for cleaning toilet bowls according to the invention also comprises an acid cleaner which can consist of a mineral acid such as phosphoric, sulfamic, hydrochloric, hydrofluoric, sulfuric, nitric, chromic acid and mixtures thereof or an organic acid, in particular acetic, hydroxyacetic, adipic, citric, formic, fumaric, gluconic, glutaric, glycolic, malic, maleic, lactic, malonic, oxalic, succinic and tartaric acid as well as mixtures thereof, salts of acids such as sodium bisulfate and mixtures thereof.
  • the amount of acidic ingredients is preferably between
  • the preferred amount depends on the type of acid cleaner used: for example with sulfamic acid. It is between approximately 0.2 and approximately 1%, with hydrochloric acid between approximately 1 and approximately 5%, with citric acid between approximately 2 and approximately 10%, with formic acid, between approximately 5 and approximately 15% and with phosphoric acid, between about 5 and about 30% by weight.
  • the amount of acid agent is generally such that the final pH of the composition is from about 0.5 to about 4, preferably 1 to 3.
  • the toilet bowl cleaning composition also comprises from 0.5 to 10% by weight of a surfactant so as to contribute to the removal of soiling or so as to provide foaming or wetting characteristics or to increase the cleaning effectiveness of the composition.
  • the surfactant is preferably an anionic or nonionic surfactant.
  • Cationic surfactants can also be added to the composition for cleaning toilet bowls according to the invention for provide germicidal properties. Those skilled in the art will see that amphoteric surfactants can also be used. Mixtures of various surfactants can be used if desired.
  • the toilet bowl cleaning composition according to the invention can also comprise a gum type thickener, in particular a xanthan gum introduced at a concentration of 0.1 to 3%, as well as one or more of the following minority ingredients: a preservative intended to prevent the growth of microorganisms in the product, a dye, a perfume, and / or an abrasive.
  • a gum type thickener in particular a xanthan gum introduced at a concentration of 0.1 to 3%
  • a preservative intended to prevent the growth of microorganisms in the product a dye, a perfume, and / or an abrasive.
  • the polymer according to the invention is also suitable for rinsing the walls of the showers.
  • aqueous compositions for rinsing the walls of the showers comprise from 0.02% to 5% by weight, advantageously from 0.05 to 1% of the copolymer of the invention.
  • the other main active components of the aqueous shower rinse compositions of the present invention are at least one surfactant present in an amount ranging from 0.5 to 5% by weight and optionally a metal chelating agent present in an amount ranging from 0 , 01 to 5% by weight.
  • Preferred metal chelating agents are ethylenediaminetetraacetic acid (EDTA) and its analogs.
  • the aqueous rinsing compositions for showers advantageously contain water with optionally at least a lower alcohol in the majority proportion and additives in the minority proportion (between approximately 0.1 and approximately 5% by weight, more advantageously between approximately 0.5% and approximately 3% by weight, and even more preferably between approximately 1% and approximately 2% by weight).
  • Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan mono-oleates and castor oil polyethoxylated.
  • Particular 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 an 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 of 12.0) and EL-719® (HLB of 13.6 ) respectively).
  • the degree of ethoxylation is preferably sufficient to obtain a surfactant having an HLB greater than 13.
  • Other surfactants such as alkylpolyglucosides are also well suited to these compositions.
  • the polymer according to the invention can also be used for cleaning ceramic hobs.
  • the formulations for cleaning ceramic hobs of the invention comprise: - 0.05 to 5% by weight of the copolymer of the invention
  • a thickener such as a xanthan gum
  • an abrasive agent such as calcium carbonate or silica
  • a glycol such as butyldiglycol
  • a subject of the invention is also the use of a water-soluble or water-dispersible copolymer as defined above for cleaning a hard surface, in particular for imparting hydrophilization properties to a hard surface.
  • the hydrophilization properties imparted by the copolymer of the invention are in particular "anti-flow”, “anti-fog” properties and “anti-stain” and / or “anti-trace” properties.
  • the subject of the invention is also the use, in a liquid cleaning composition for a hard surface, of at least one water-soluble or water-dispersible copolymer of the invention, as an agent making it possible to reduce the drying speed of the surface on which was applied said liquid composition.
  • It likewise relates to a process for improving the hydrophilicity of a hard surface, by treatment of said surface with the aid of a cleaning composition comprising at least one copolymer of the invention.
  • It also relates to a method for improving the drying speed of a hard surface after cleaning thereof using a cleaning composition, by incorporating into said composition at least one copolymer of the invention .
  • copolymers of Examples 1 to 3 and Comparative Examples 4 to 6 are evaluated for their capacity to impart hydrophilization properties to a glass plate.
  • a glass surface consisting of microscopy slides of dimension 2.5 x 7.5 cm, previously cleaned with ethanol, the composition of which is given below: If 21-43% by weight
  • the polymer and surfactant solution is deposited on a glass slide using a centrifugal applicator with:
  • the contact angle between water and treated glass is measured on a Ramé-Hart assembly and is expressed in degrees. Eight to ten measurements are made per glass slide. Two to three glass slides are prepared for each polymer and the results therefore correspond to the average of 20 to 30 measurements.
  • the contact angle obtained on a blade having undergone the treatment described with an aqueous solution (demineralized water) without polymer gives a contact angle of 16 °.
  • the values before rinsing give information on the hydrophilic or hydrophobic nature of the polymer. But the most interesting data corresponds to the contact angle after rinsing, which characterizes both the hydrophilicity and the strength of the polymer / glass interactions. For the application of cleaning hard surfaces, a low value of this contact angle with rinsing is sought.
  • a polymer having a contact angle of less than 12 ° and more particularly of 10 ° will give good performance in the applications mentioned above.
  • the formulations of Examples 7 to 9 are used as such by spraying on the surface of the panes to be cleaned (6 to 8 sprays, ie 3 to 5 g of formulation per m 2 of surface.
  • EXAMPLES 10 to 11 Cleaning formulations for hard surfaces such as tiles, ceramics, sinks, baths.
  • a basic detergent formula is prepared from the compounds given in the table below:

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EP00951609A 1999-07-15 2000-06-19 Verwendung eines amphoteren polymeres zur behandlung ausgewählter harter oberflächen Expired - Lifetime EP1196527B1 (de)

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FR9909183A FR2796390B1 (fr) 1999-07-15 1999-07-15 Utilisation d'un polymere amphotere pour traiter une surface dure
PCT/FR2000/001689 WO2001005921A1 (fr) 1999-07-15 2000-06-19 Utilisation d'un polymere amphotere pour traiter une surface dure

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7923428B2 (en) 2003-02-20 2011-04-12 Rhodia Chimie Composition for cleaning or rinsing hard surfaces
WO2008154617A2 (en) 2007-06-12 2008-12-18 Rhodia Inc. Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
EP2025742A1 (de) 2007-08-31 2009-02-18 The Procter and Gamble Company Flüssiges Reinigungssäuremittel für harte Oberflächen
EP2075325A1 (de) 2007-12-27 2009-07-01 The Procter & Gamble Company Flüssiges Reinigungssäuremittel für harte Oberflächen
EP2075324A1 (de) 2007-12-27 2009-07-01 The Procter and Gamble Company Flüssiges Reinigungssäuremittel für harte Oberflächen
US8658586B2 (en) 2008-08-26 2014-02-25 Rhodia Operations Copolymer for surface processing or modification
WO2010075120A1 (en) 2008-12-23 2010-07-01 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
EP2206766A1 (de) 2008-12-23 2010-07-14 The Procter and Gamble Company Flüssiges saures Reinigungsmittel für harte Oberflächen
EP2586855A1 (de) 2008-12-23 2013-05-01 The Procter & Gamble Company Flüssiges saures Reinigungsmittel für harte Oberflächen
EP2944685A1 (de) 2008-12-23 2015-11-18 The Procter and Gamble Company Flüssiges saures reinigungsmittel für harte oberflächen
EP2336282A1 (de) 2009-12-17 2011-06-22 The Procter & Gamble Company Flüssiges Reinigungssäuremittel für harte Oberflächen
WO2011075466A1 (en) 2009-12-17 2011-06-23 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
WO2011084577A1 (en) 2009-12-17 2011-07-14 The Procter & Gamble Company Hard surface cleaning composition having a malodor control component and methods of cleaning hard surfaces

Also Published As

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JP2008266653A (ja) 2008-11-06
JP2003505535A (ja) 2003-02-12
AU6449300A (en) 2001-02-05
ATE288956T1 (de) 2005-02-15
JP4857309B2 (ja) 2012-01-18
BR0012499B1 (pt) 2011-03-22
US6593288B2 (en) 2003-07-15
FR2796390B1 (fr) 2001-10-26
US20030083223A1 (en) 2003-05-01
WO2001005921A1 (fr) 2001-01-25
FR2796390A1 (fr) 2001-01-19
ES2234646T3 (es) 2005-07-01
CA2378198C (fr) 2012-09-04
CA2378198A1 (fr) 2001-01-25
US20030203826A1 (en) 2003-10-30
US6767410B2 (en) 2004-07-27
JP4215982B2 (ja) 2009-01-28
DE60018068D1 (de) 2005-03-17
AU780845B2 (en) 2005-04-21
BR0012499A (pt) 2002-04-02
EP1196527B1 (de) 2005-02-09
DE60018068T2 (de) 2005-12-29

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