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EP1196523A1 - Ein wasserlösliches oder wasserdispergierbares polymer enthaltendes reinigungsmittel - Google Patents

Ein wasserlösliches oder wasserdispergierbares polymer enthaltendes reinigungsmittel

Info

Publication number
EP1196523A1
EP1196523A1 EP00945975A EP00945975A EP1196523A1 EP 1196523 A1 EP1196523 A1 EP 1196523A1 EP 00945975 A EP00945975 A EP 00945975A EP 00945975 A EP00945975 A EP 00945975A EP 1196523 A1 EP1196523 A1 EP 1196523A1
Authority
EP
European Patent Office
Prior art keywords
weight
cleaning
acid
water
composition
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
EP00945975A
Other languages
English (en)
French (fr)
Other versions
EP1196523B1 (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
Original Assignee
Rhodia Chimie SAS
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Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1196523A1 publication Critical patent/EP1196523A1/de
Application granted granted Critical
Publication of EP1196523B1 publication Critical patent/EP1196523B1/de
Anticipated expiration legal-status Critical
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
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the subject of the present invention is a cleaning or rinsing composition intended for the treatment of hard industrial, domestic or collective surfaces, in particular of the glass, glass, ceramic, tiling, hard organic polymer, metal, wood ... type intended to give these have hydrophilic properties as well as protective (anticorrosive) properties for glass, dishes and decorations by washing media during repeated washing in an automatic dishwasher.
  • a more particular subject of the invention is a cleaning composition intended for the treatment of a hard surface which is capable of imparting to it persistent hydrophilic 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.
  • a first subject of the invention consists of a cleaning or rinsing composition comprising at least one water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
  • - Ri is a hydrogen atom, a methyl or ethyl group
  • R ⁇ identical or different are alkyl, hydroxyalkyl or aminoalkyl, linear or branched C 1 -C- 6 , preferably C ⁇ -C, - m is an integer from 0 to 10, preferably from 0 to 2;
  • - n is an integer from 1 to 6, preferably 2 to 4;
  • - Z represents a group -C (O) O-, -C (O) NH- or an oxygen atom;
  • - A represents a group (CH 2 ) P , p being an integer from 1 to 6, preferably from 2 to 4;
  • - B represents a linear or branched polymethylene chain of C 2 -C- ⁇ 2 , advantageously C- 3 -C- 6 , optionally interrupted by one or more heteroatoms or heterogroups, in particular O or NH, and optionally substituted by one or more groups hydroxyls or amino, preferably hydroxyls;
  • (c) optionally at least one ethylenically unsaturated monomer compound with neutral charge, copolymerizable with (a) and (b), preferably a hydrophilic monomer compound with ethylenic unsaturation with neutral charge carrying one or more hydrophilic groups, copolymerizable with (a) and B).
  • the monomer (a) can be prepared for example according to the following reaction schemes:
  • H 2 C CZ- (CH 2 ) n
  • H 2 C CZ- (CH 2 ) n , - N r + - EA N + - B R5 m
  • 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) gives the copolymer hydrophilic characteristics which, after anchoring of the copolymer on the surface to be treated, are transmitted thereto.
  • 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 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 go up to 20,000,000, advantageously up to 10,000,000.
  • the copolymer is preferably random.
  • Z represents C (O) O, C (O) NH or O, most preferably C (O) NH;
  • - m ranges from 0 to 2, preferably is equal to 0 or 1, most particularly 0;
  • - Ri to R ⁇ identical or different represent a methyl or ethyl group.
  • the preferred monomer (a) is the DIQUAT of the following formula
  • the anions X are in particular a halogen, preferably chlorine, sulfonate, sulfate, hydrogen sulfate, phosphate, phosphonate, citrate, formate and acetate anion.
  • a halogen preferably chlorine, sulfonate, sulfate, hydrogen sulfate, phosphate, phosphonate, citrate, formate and acetate anion.
  • the monomers (b) are advantageously C 3 -C 8 carboxylic, sulphonic, sulfuric, phosphonic or phosphoric acids containing 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, styrene sulfonic acid, vinyl sulfonic acid, vinylphosphonic acid, phosphoethyl acrylate, phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl acrylate, phosphoethyl methacrylate
  • acrylamide vinyl alcohol
  • C1-C4 alkyl esters of acrylic acid and methacrylic acid C1-C4 hydroxyalkyl esters of acrylic acid and methacrylic acid, especially ethylene glycol and propylene glycol acrylate and methacrylate, polyalkoxylated esters of acrylic acid and acid methacrylic, in particular esters of polyethylene glycol and of polypropylene glycol, esters of acrylic acid or of methacrylic acid and of polyethylene glycol or polypropylene glycol mono C 1 -C 25 alkyl ethers, vinyl acetate, vinylpyrrolidone , methylvinylether.
  • the level of monomers (a) is advantageously between 3 and 80 mol%, preferably 10 to 60 mol%.
  • the level of monomers (b) is advantageously between 10 and 95 mol%, preferably 20 to 70 mol%.
  • the level of monomers (c) is advantageously between 0 and 50%, preferably 0 and 30%, very particularly from 5 to 25 mol%.
  • the molar ratio of cationic monomer to anionic monomer (a) / (b) is advantageously between 80/20 and 5/95, preferably between 60/40 and 20/80.
  • 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 environment free of oxygen, for example in the presence of an inert gas (helium, argon, etc.) or nitrogen.
  • the 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 the 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, azo-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 bramates (including inorganic or organic chlorates and / or bramates); reducing agents such
  • 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.
  • a particularly preferred copolymer is the following:
  • x having an average value of 0 to 50%, preferably 0 to 30%, most particularly 5 to 25%
  • y having an average value of 10 to 95%, preferably 20 to 70%
  • z having a average value from 3 to 80%, preferably from 10 to 60%
  • x having an average value of 0 to 50%, preferably from 0 to 30%, very particularly from 5 to 25%
  • y having an average value of 10 to 95%, preferably 20 to 70%
  • z having an average value of 3 to 80%, preferably 10 to 60%
  • the ratio y / z being preferably l '' from 4/1 to 1/2.
  • x having an average value of 0 to 50%, preferably 0 to 30%, most particularly 5 to 25%
  • y having an average value of 10 to 95%, preferably 20 to 70%
  • z having a average value from 3 to 80%, preferably from 10 to 60%, and the ratio y / z being preferably of the order of 4/1 to 1/2.
  • x having an average value of 0 to 50%, preferably 0 to 30%, most particularly 5 to 25%
  • y having an average value of 10 to 95%, preferably 20 to 70%
  • z having a average value from 3 to 80%, preferably from 10 to 60%, and the ratio y / z being preferably of the order of 4/1 to 1/2.
  • x having an average value of 0 to 50%, preferably 0 to 30%, most particularly 5 to 25%
  • y having an average value of 10 to 95%, preferably 20 to 70%
  • z having a average value from 3 to 80%, preferably from 10 to 60%, and the ratio y / z being preferably of the order of 4/1 to 1/2.
  • x having an average value of 0 to 50%, preferably 0 to 30%, most particularly 5 to 25%
  • y having an average value of 10 to 95%, preferably 20 to 70%
  • z having a average value from 3 to 80%, preferably from 10 to 60%, and the ratio y / z being preferably of the order of 4/1 to 1/2.
  • x having an average value of 0 to 50% preferably of 0 to 30%, very particularly of 5 to 25%
  • y having an average value of 10 to 95%, preferably of 20 to 70%
  • z having a value average from 3 to 80%, preferably from 10 to 60%, and the ratio y / z being preferably of the order of 4/1 to 1/2.
  • copolymers according to the invention can be used in particular in cleaning compositions for hard surfaces.
  • the copolymers of the invention are useful for imparting hydrophilization properties to surfaces to which they are applied, in particular for imparting remanent stain or stain resistant properties to surfaces.
  • 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.
  • a subject of the invention is also the new copolymers as defined above.
  • Said copolymer can be introduced into a cleaning or rinsing formulation intended to treat hard surfaces at a content of between 0.0005% and 10%, preferably between 0.001 and 5% by weight relative to the total weight of the formulation, according to the concentration of active ingredients in the composition.
  • the composition according to the invention preferably comprises at least one surfactant. This is advantageously anionic and / or nonionic. It can also be cationic, amphoteric or zwitterionic.
  • the polymer weight ratio of formula I / surfactant is between 1/2 and 1/100, advantageously 1/5 and 1/50.
  • soaps such as the fatty acid salts of C8-C 2 4, for example the salts of fatty acids derived from coconut and tallow; alkylbenzenesulfonates, in particular linear C 8 -C 3 alkyl alkyl benzenesulfonates, in which the alkyl group comprises from 10 to 16 carbon atoms, alcohol sulfates, ethoxylated alcohol sulfates, hydroxyalkyl sulfonates; alkyl sulfates and sulfonates, especially C12-C16, monoglycerides-sulfates, and fatty acid chloride condensates with hydroxyalkylsulfonates.
  • soaps such as the fatty acid salts of C8-C 2 4, for example the salts of fatty acids derived from coconut and tallow; alkylbenzenesulfonates, in particular linear C 8 -C 3 alkyl alkyl benzenesulfonates, in which the
  • R represents an alkyl radical in C ⁇ -20, preferably in C-10-C-i ⁇
  • R' an alkyl radical in C C ⁇ , preferably in C 1 -C 3
  • M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine , diethanolamine, triethanolamine ).
  • Mention may very particularly be made of methyl ester sulfonates whose radicals R is CuC-ie;
  • R represents an alkyl or hydroxyalkyl radical, C 5 -C 2 4, preferably C1 -C1 8 0, M representing a hydrogen atom or a cation with the same definition as above above, as well 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;
  • RCONHROSO 3 M where R represents an alkyl radical in C2-C22, preferably in C 6 -C 2 o, R 'an alkyl radical in C 2 -C 3 , M representing a hydrogen atom or a similar cation 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;
  • C 8 -C 24 saturated or unsaturated fatty acids preferably C14-C20.
  • alkyl glycerol sulfonates sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, alkyl glycoside sulfates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ... ) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...);
  • RHODAFAC RA600 alkylated or alkylarylated ester phosphates
  • RHODAFAC PA15 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-114, 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 C 10 -C 18 alkyl dimethylamine oxides, C8-C22 alkoxy ethyl dihydroxy ethylamine oxides;
  • Cationic surfactants are in particular alkylammonium salts of formula
  • X " represents a halogen ion, CH3SO4 " or C 2 H 5 SO 4 "
  • R 1 and R 2 are similar or different and represent a C1-C20 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, an aryl or benzyl radical or an ethylene and / or propylene oxide condensate (CH 2 CH 2 O) x - (CH 2 CHCH 3 ⁇ ) yH, where x and y range from 0 to 30 and are never zero together, such as cetyltrimethylammonium bromide, RHODAQUAT® TFR sold by the company RHODIA.
  • 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 alkylamidopropyldimethyl betaines, alkyldimethylsulfobetaines or alkylamidopropyldimethylsulfobetaines
  • MIRATAINE CBS sold by the company RHODIA, 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 AMPHIONIC 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, if necessary, at a rate of 0.005 to 60%, in particular from 0.5 to 40% by weight depending on the nature of the surfactant (s) and the destination of the cleaning or rinsing composition.
  • 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 marketed by the company RHODethyl -nitrilodiacetates), (at a rate of 0 to 10% of the total weight of detergent composition expressed as dry matter in the case of a dishwasher composition); . salts of succinic C 5 -C 20 alkyl acids. polyacetal carboxylic esters. salts of polyaspartic or polyglutamic acids.
  • citric acid, gluconic acid or tartaric acid or their salts at a rate of 0 to 10% of the total weight of detergent composition expressed as dry matter in the case of a composition for dishwasher
  • - mineral "builders" detergency additives improving the surface properties of surfactants
  • polyphosphates of alkali metals, ammonium or alkanolamines such as RHODIAPHOS HPA3.5 sold by the company RHODIA, (at the rate of 0 to 70% of the total weight of detergent composition expressed as dry matter in the case of 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
  • 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 hypochlorites type, (at a rate of 0 to 30% of the total weight of said detergent composition expressed as dry matter in the case of a dishwasher composition);
  • 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;
  • cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxy-methylguar, carboxymethylhydroxypropyl-guar ).
  • 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 0.1g / m 2 of surface to be treated.
  • the cleaning composition according to the invention is used for the treatment of glass surfaces, in particular of panes.
  • 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:
  • nonionic surfactant for example an amine oxide
  • anionic for example an amine oxide
  • the window cleaning formulations comprising said polymer may also contain:
  • composition of the invention is also advantageous for cleaning the dishes by hand or in an automatic machine.
  • 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 include 30 to 95% of an agent builder, chosen among 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 0.2 to 15%, preferably 0.5 to 5% by weight relative to the total weight of said composition of 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, ethylene oxide-oxide block copolymers propylene, optionally polyoxyethylenated carboxylic amides ....
  • They also comprise from 0 to 40%, preferably from 3 to 30% by weight relative to the total weight of the composition of an organic acid sequestering with calcium, preferably citric acid.
  • They may 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 to 10% by weight relative to the total weight of said composition.
  • the invention also relates to 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) ...
  • 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
  • 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.
  • bactericidal or disinfectant agents such as triclosan
  • Another subject of the invention consists of a cleaning composition 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%, preferably 0.5 to 15% of the formulation),
  • the minimum amount of surfactant present in type of composition can be at least 1% of the formulation
  • composition 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.
  • 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.
  • composition of the invention can also be implemented by cleaning the 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.
  • a mineral acid such as phosphoric, sulfamic, hydrochloric, hydrofluoric, sulfuric, nitric, chromic acid and mixtures thereof
  • organic acid in particular acetic, hydroxyacetic, adipic, citric, formic, fumaric, gluconic, glutaric, glycolic, malic, maleic, lactic, malonic,
  • the amount of acidic ingredients is preferably between 0.1 to about 40%, and preferably between 0.5 and about 15% by weight relative to the total weight of the composition.
  • 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 to 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.
  • composition 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.
  • EDTA ethylenediaminetetraacetic acid
  • 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 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.
  • 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.
  • composition according to the invention can also be used for cleaning ceramic hobs.
  • formulations for cleaning ceramic hobs of the invention include:
  • a thickener such as a xanthan gum
  • an abrasive agent such as calcium carbonate or silica
  • Another subject of the invention consists of an aqueous biocidal cleaning composition for the treatment of hard surfaces comprising:
  • nonionic, amphoteric, zwitterionic, preferably nonionic surfactant optionally at least one nonionic, amphoteric, zwitterionic, preferably nonionic surfactant.
  • the biocide is preferably present in the aqueous biocidal cleaning composition at a concentration of the order of 0.1% to 20% by weight, preferably of the order of 0.5% to 5% by weight.
  • the copolymer according to the invention can be present in the aqueous biocidal cleaning composition at a concentration of the order of 0.01% to 20% by weight, preferably of the order of 0.05 to 5% by weight. Said copolymer, in itself, generally does not have a biocidal activity.
  • biocidal agents which may be present, there may be mentioned:
  • R 1 represents a benzyl group optionally substituted by a chlorine atom or a CC 4 alkylbenzyl group
  • R 2 represents a C ⁇ -C 2 4 alkyl group
  • R 3 and R 4 identical or different, represent an alkyl or hydroxyalkyl group having 1 to 4 C
  • X " is a solubilizing anion such as halide (for example chloride, bromide, iodide), sulphate or methyl sulphate,
  • R 1 and R 2 ' similar or different, represent a C 8 -C 24 alkyl group
  • R 3' and R 4 ' similar or different, represent a C 1 -C 4 alkyl group
  • X " is a solubilizing anion such that halide (for example chloride, bromide, iodide), sulphate or methyl sulphate,
  • R 1 " represents a C8-C24 alkyl group
  • R 2 " , R 3" and R 4 " which are similar or different, represent a C 1-4 alkyl group
  • X " is a solubilizing anion such as halide (for example chloride, bromide, iodide), sulphate or methyl sulphate
  • coco-alkyl benzyl dimethylammonium chlorides C12-C14 alkyl benzyl dimethylammonium, coco-alkyl dichlorobenzyl dimethylammonium, tetradecyl benzyl dimethylammonium, didecyl dimethylammonium, dioctyl dimethylammonium chlorides
  • heterocyclic monoquatine amines such as. laurylpyridinium, cetylpyridinium, C-12-14 alkyl benzyl imidazolium chlorides
  • amphoteric biocides such as derivatives of N- (N'-C8-Ci8alkyl-3-aminopropyl) -glycine, of N- (N '- (N "-C8-C-
  • nonionic surfactants such as, ethylene oxide - propylene oxide block polymers, polyethoxylated sorbitan esters, sorbitan fatty esters, ethoxylated fatty esters (containing 1 to 25 units of ethylene oxide ), polyethoxylated C8-C22 alcohols (containing 1 to 25 ethylene oxide units), polyethoxylated C6-C22 alkylphenols (containing 5 to 25 ethylene oxide units), alkylpolyglycosides, amine oxides (such as C ⁇ rj-C-18 alkyldimethylamines oxides, C8-C22 alkoxyethyl dihydroxyethylamine oxides)
  • ethylene oxide - propylene oxide block polymers polyethoxylated sorbitan esters, sorbitan fatty esters, ethoxylated fatty esters (containing 1 to 25 units of ethylene oxide ), polyethoxylated C8-C22 alcohols (containing 1 to 25 ethylene oxide units),
  • amphoteric or zwitterionic surfactants such as C6-C20 alkylamphoacetates or amphodiacetates (such as cocoamphoacetates), C-10-C18 alkyldimethylbetaines, C10-C18 alkylamidopropyldimethylbetaines, C10-C-I8 alkyldimethyl-sulfobethyl C-alkylbethalimethyl sulfide.
  • aqueous biocidal cleaning composition can be present in an amount of 1 to 25%, preferably of the order of 2 to 10% by weight of the aqueous biocidal cleaning composition.
  • main constituents of the aqueous biocidal system of the invention can be present, and this in an advantageous manner.
  • other constituents such as chelating agents, can be present, and this in an advantageous manner.
  • aminocarboxylates ethylenediaminetetraacetates, nitrilotriacetates, N, N-bis (carboxymethyl) glutamates, citrates
  • alcohols ethanol, isopropanol, glycols
  • detergency builders phosphates, silicates
  • dyes perfumes ... .
  • Said biocidal cleaning composition can be used for the disinfection of floors, walls, work surfaces, equipment, furniture, instruments, ... in industry, the food industry, domestic areas (kitchens, bathrooms ...) and in community.
  • surfaces that can be treated there may be mentioned those in ceramic, glass, polyvinyl chloride, formica or other hard organic polymer, stainless steel, aluminum, wood ...
  • the cleaning and disinfection operation consists in applying said biocidal cleaning composition, possibly diluted from 1 to 1000 times, preferably from 1 to 100 times, on the hard surface to be treated.
  • the quantity of biocidal system which can be favorably implemented is that corresponding to a deposit of 0.01 to 10 g, preferably from 0.1 to 1 g of biocide per m 2 of surface and to a deposit of 0.001 to 2 g, preferably from 0.01 to 0.5 g of copolymer of the invention per m 2 of surface.
  • Gram negative bacteria such as: Pseudomonas aeruginosa; Escherichia coli; Proteus mirabilis
  • Gram positive bacteria such as: Staphylococcus aureus; Streptococcus faecium
  • yeasts such as: Saccharomvces cerevisiae; Candida albicans. mushrooms such as: Asperqillus ni ⁇ er; Fusarium solani; Pencillium chrvsoqenum
  • algae such as: Chlorella saccharophilia; Chlorella emersonii; Chlorella vul ⁇ aris; Chlamvdomonas eu ⁇ ametos
  • the biocidal system of the invention is particularly effective on Gram-negative microorganisms Pseudomonas aero ⁇ inosa. Gram positive Staphylococcus aureus. the fungus Asperqillus niger.
  • the invention also relates to the use of a water-soluble or water-dispersible copolymer as defined above for cleaning or rinsing a hard surface, in particular to give a hard surface hydrophilization properties.
  • 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.
  • 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 according to the invention.
  • Another object of the invention consists in the use, in a detergent composition for washing dishes in an automatic dishwasher, of a copolymer according to the invention as an agent for eliminating or reducing corrosion of glass and decorations. present on the glass or the dishes during repeated washing.
  • the invention finally relates to a process for the protection of glass, dishes and decorations, by washing the glass and the dishes in an automatic dishwasher, using a cleaning composition comprising at least one copolymer according to the invention.
  • the resulting mixture is gently heated to a pH of about 2.6 under a gentle nitrogen purge at 75 ° C. After 30 minutes, when the temperature reaches 75 ° C., an initiator solution based on sodium persulfate (0.1 g in 1.0 g of demineralized water) all at once in the reactor. Cooling is necessary to maintain the temperature at 75 ° C, and the mixture becomes viscous after about 45 minutes. Two additional portions of initiator solution based on persulfate are added after one and two hours of reaction respectively. Then, the reaction mixture is heated to a temperature of 85 ° C. and maintained at this temperature for two additional hours before being cooled to 25 ° C. The viscosity of the resulting polymer solution 1 is about 29,500 cps with a total solids content of about 20.5%. The pH of the 10% solution is approximately 2.2. The residual acrylamide is less than 0.1% by weight.
  • the process is the same as that of Examples 1 to 5, except that the acrylic acid is replaced by N- (1-sulfo-2-isobutyl) acrylamide.
  • 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.
  • a basic detergent formula is prepared from the compounds given in the table below:
  • This simplified glass corrosion test reproduces certain washing conditions for dishwasher machines, in particular washing, rinsing and drying cycles.
  • the glass used is made up of microscopy slides measuring 2.5 x 7.5 cm, previously cleaned with ethanol, slides whose composition given below is close to that of table glasses:
  • 200 ml of an aqueous washing solution containing 6 g / l of product to be tested are introduced into a container.
  • the container is introduced and kept in an oven at 65 ° C for 1 hour.
  • a glass slide is completely immersed in an inclined position.
  • the container is then closed, then placed in an oven at 65 ° C.
  • the blade is taken out of the container after 72 hours, rinsed twice on each side with permuted water using a wash bottle, flicked with the finger to remove the film that may have formed, dried in ambient air for 2 hours.
  • the slide is weighed after cooling to room temperature and the change in relative mass (in% x 1000) is calculated. The test is repeated another time to confirm the results.
  • Corrosion visible to the eye is evaluated, compared with a reference blade not subjected to the test.
  • the corrosion evaluation is done visually with a scale ranging from 1 to 5 points, taking as reference the glasses in new condition, by 9 trained people.
  • Points are distributed as follows:. 1 point corresponds to a perfect state.
  • Examples 15, 16 and 17 show that the polymers of the invention provide effective protection of the glass against corrosion, which is not obtained with Examples 12, 13 and 14.
  • Rhodaquat RP50 biocide is a 50% aqueous solution of active ingredient of C12-C14 chloride, alkyl benzyl dimethyl ammonium marketed by Rhodia.
  • Example 26 The formulation of Example 26 is tested on a white ceramic tile according to the following protocol:
  • the neutralizing medium contains 3% Tween 80 polysorbate and 2% soy lecithin.
  • a control test is carried out by carrying out steps 1. to 7. on the surface of a white ceramic tile (5cmx5cm) previously sterilized but not treated with the biocidal system.
  • logio of reduction log-jo N / n N being the number of bacteria (in CFU / ml) surviving in the control test
  • n being the number of bacteria (in CFU / ml) survivors in the test using the biocidal system.

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EP00945975A 1999-07-15 2000-06-19 Ein wasserlösliches oder wasserdispergierbares polymer enthaltendes reinigungsmittel Expired - Lifetime EP1196523B1 (de)

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AU781101B2 (en) 2005-05-05
US6569261B1 (en) 2003-05-27
ATE276343T1 (de) 2004-10-15
EP1196523B1 (de) 2004-09-15
AU5989000A (en) 2001-02-05
ES2226878T3 (es) 2005-04-01
DE60013837T2 (de) 2005-10-06
JP4005357B2 (ja) 2007-11-07
WO2001005920A1 (fr) 2001-01-25
DE60013837D1 (de) 2004-10-21
JP2003505534A (ja) 2003-02-12
FR2796392B1 (fr) 2003-09-19
FR2796392A1 (fr) 2001-01-19
BR0012487A (pt) 2002-12-31
CA2378195C (fr) 2012-05-22
BR0012487B1 (pt) 2011-03-22
USRE44058E1 (en) 2013-03-12
CA2378195A1 (fr) 2001-01-25

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