EP1196528A1 - Cleansing composition for hard surfaces - Google Patents
Cleansing composition for hard surfacesInfo
- Publication number
- EP1196528A1 EP1196528A1 EP00953235A EP00953235A EP1196528A1 EP 1196528 A1 EP1196528 A1 EP 1196528A1 EP 00953235 A EP00953235 A EP 00953235A EP 00953235 A EP00953235 A EP 00953235A EP 1196528 A1 EP1196528 A1 EP 1196528A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- water
- composition
- acid
- cleaning
- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
-
- 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 composition intended for the treatment of hard industrial domestic or collective surfaces, in particular of the ceramic, tiling or glass type, aiming to confer on them hydrophilic properties.
- the invention more particularly relates to a cleaning composition intended for the treatment of such a surface which is capable of imparting thereto retentive 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, and optionally sequestering agents and bases to adjust the pH.
- alcohol (s) to facilitate drying
- optionally 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 . In the case of automatic dishwashing
- 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 composition for hard surfaces comprising at least one surfactant and at least one water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
- - Ri is a hydrogen atom or a methyl group, preferably a methyl group
- R 2 , R 3 and R 4 are linear or branched C 1 -C 4 alkyl groups
- - n represents an integer from 1 to 4, in particular the number 3;
- - X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer; (b) at least one hydrophilic monomer chosen from monoethylenically unsaturated C 3 -C 8 carboxylic acids, their anhydrides and their water-soluble salts;
- the molar ratio (a) / (b) is between 25/75 and 70/30
- the molar ratio c / (a + b + c) is advantageously between 0 and 40/100, preferably between 10/100 and 30/100.
- the copolymer according to the invention is preferably random.
- the average charge Q of said copolymer at the pH of the cleaning composition can be determined by any known means, in particular by assay using a polyvinyl sulfate solution or by zetametry.
- 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) confer (s) on the copolymer hydrophilic characteristics which, after anchoring of the copolymer on the surface to be treated, are transmitted thereto.
- 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.
- 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 weight by weight of at least 1000, advantageously at least 10,000; it can go up to 20,000,000, advantageously up to 10,000,000.
- the preferred monomer (a) is MAPTAC of the following formula:
- 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, anhydrides, and the alkali metal and ammonium salts thereof.
- acrylamide vinyl alcohol
- C1-C6 alkyl esters of acrylic acid and methacrylic acid C1-C4 hydroxyalkyl esters of acrylic acid and methacrylic acid, especially pacrylate and methacrylate of ethylene glycol and propylene glycol
- polyalkoxylated esters of acrylic acid and methacrylic acid especially esters of polyethylene glycol and polypropylene glycol.
- X is any suitable counter-anion compatible with the water-soluble or water-dispersible nature of the copolymer, in particular an anion of halogen, sulphate, hydrogen sulphate, phosphate, citrate, formate and acetate.
- copolymers of the invention can be obtained according to known techniques for the radical polymerization of ethylenically unsaturated monomers.
- the cleaning compositions according to the invention advantageously have a weight ratio of water-soluble or water-dispersible copolymer / surfactant of between 1/2 and 1/100, preferably between 1/5 and 1/50.
- a particularly preferred copolymer is the following:
- - x is between 0 and 40%, preferably between 10 and 30%.
- Said copolymer can be introduced into a formulation intended to treat hard surfaces at a content of between 0.001% and 10% by weight relative to the total weight of the formulation, depending on the concentration of active ingredients in the composition.
- composition according to the invention comprises at least one surfactant.
- This is advantageously anionic and / or nonionic. It can also be cationic, amphoteric or zwitterionic.
- soaps such as the C 8 -C 24 fatty acid salts, for example the salts of fatty acids derived from copra and tallow; alkylbenzenesulfonates, including linear alkylbenzenesulfonates C8 latter 3, wherein the alkyl group comprises from 10 to 16 carbon atoms, alcohol-sulfates, the ethoxylated alcohol sufates, the hydroxyalkylsulfonates; alkyl sulfates and sulfonates, in particular C ⁇ 2 -C-i6, monoglycerides-sulfates, and fatty acid chloride condensates with hydroxyalkylsulfonates.
- soaps such as the C 8 -C 24 fatty acid salts, for example the salts of fatty acids derived from copra and tallow; alkylbenzenesulfonates, including linear alkylbenzenesulfonates C8 latter 3, wherein the alkyl group comprises from 10 to 16 carbon
- Advantageous anionic surfactants are in particular: - the alkyl esters sulfonates of formula R-CH (SO 3 M) -COOR ', where R represents a C 8-2 o, preferably C10-C16 alkyl radical, R' a radical C1-C ⁇ alkyl, preferably C1-C 3 and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ). Mention may very particularly be made of methyl ester sulfonates whose radicals R is C-14-C16;
- R represents a C 5 -C 2 alkyl or hydroxyalkyl radical, preferably C-10-C-i ⁇
- 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 30 units, preferably from 0.5 to 10 OE and / or OP units;
- alkylamide sulfates of formula RCONHR'OSO 3 M where R represents an alkyl radical in C 2 -C 22 , preferably in C6-C 20 , R 'an alkyl radical in C 2 -C 3 , M representing an atom of hydrogen 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;
- 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; dialkyisulfoxides; 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
- 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 alkyl oxides C-io-Ci ⁇ dimethylamines, alkoxy oxides C ⁇ -C 2 2 ethyl dihydroxy ethylamines;
- Cationic surfactants are in particular alkylammonium salts of formula R 1 R 2 R 3 R 4 N + X " where
- X " represents a halogen ion, CH 3 SO 4 " or C 2 H 5 SO 4 " .
- R 1 and R 2 are similar or different and represent an alkyl radical in CC 2 o, 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 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 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.
- organic "builders” (detergency builders improving the surface properties of surfactants) of the type: 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 (nithloacetic acid, N acid, N- dicarboxymethyl-2-aminopentane dioic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetates, nitrilotriacetates such as NERVANAID NTA Na 3 hydroxy marketed by the company N 2 hydroxyethyl N 3 -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 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 builders improving the surface properties of surfactants of the type: polyphosphates of alkali metals, ammonium or alkanolamines such as RHODIAPHOS HPA3.5 sold by the company RHODIA, (at a rate of 0 to 70% of the total weight of detergent composition expressed as dry matter in the case of a composition for dishwashers);
- 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
- 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);
- auxiliary cleaning agents of the acrylic acid and maleic anhydride copolymer type or homopolymers of acrylic acid at a rate of 0 to 10%, of the total weight of said detergent composition expressed as dry matter in the case of a composition for a dishwasher
- - fillers of the sodium sulfate, sodium chloride type at a rate of 0 to 50% of the total weight of the said composition expressed as dry matter
- 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 (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 0.1 g / 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:
- the pH of the composition is advantageously between 6 and 11.
- the a / b ratio is preferably between 40/60 and 60/40.
- the composition of the invention is also advantageous for cleaning the dishes by hand or in an automatic machine. In the latter case, 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.
- the pH is advantageously between 8 and 12.
- the a / b ratio is preferably between 40/60 and 60/40.
- 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, ethylene oxide-oxide block copolymers 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 include 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 total weight of said composition.
- the pH is advantageously between 4 and 7.
- the a / b ratio is preferably between 30/70 and 55/45.
- 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.
- non-cationic bactericidal agents or disinfectants such as triclosan
- the pH of the composition is advantageously between 6 and 8.
- the a / b ratio is preferably between 40/60 and 60/40.
- 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:
- the minimum amount of surfactant present in type of composition can be at least 1% of the formulation
- the pH is advantageously between 8 and 12.
- the a / b ratio is preferably between 40/60 and 60/40.
- the composition of the invention is also particularly suitable for cleaning hard surfaces other than those described above, in particular of 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 40 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.
- the 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 about 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.
- 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 pH of the composition is advantageously between 3 and 11.
- the a / b ratio is preferably between 30/70 and 60/40.
- 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, having an a / b ratio of between 25/75 and 50/50.
- 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 agents 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.
- 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 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 oxide ethylene 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 pH of the composition is advantageously between 7 and 11.
- the a / b ratio is preferably between 40/60 and 60/40.
- 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
- the pH of the composition is advantageously between 7 and
- the a / b ratio is preferably between 40/60 and 60/40.
- a subject of the invention is also the use, in a cleaning composition for a hard surface, of at least one water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
- - Ri is a hydrogen atom or a methyl group, preferably a methyl group
- R 2 , R 3 and R 4 are linear or branched C1-C4 alkyl groups
- - n represents an integer from 1 to 4, in particular the number 3;
- - X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer
- the molar ratio (a) / (b) is between 25/75 and 70/30.
- the molar ratio (c) / (a + b + c) is advantageously between 0 and 40/100, preferably between 10/100 and 30/100.
- 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 hard surfaces, of at least one water-soluble or water-dispersible copolymer of general formula I given above, as an agent making it possible to reduce the drying speed of the surface on which said liquid composition has been applied.
- 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 general formula I given above.
- 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 general formula I given above.
- a cleaning composition by incorporating into said composition at least one copolymer of general formula I given above.
- An acrylic acid / MAPTAC / acrylamide copolymer having a 40/40/20 molar ratio is prepared in a manner known per se. Its weight average molecular mass is of the order of 2,000,000.
- Two detergent solutions are prepared, each containing a concentration of 50 ppm of polymer, 0.2 g / l of non-ionic surfactant Symperonic A7 from BASF and the pH of which is adjusted by adding 0.01 molar soda.
- the transmittance of the solution is measured using a photometer.
- the charge of the polymer is determined by assay with a solution of potassium polyvinyl sulfate.
- Each aqueous solution is sprayed onto a black ceramic tile, arranged vertically. After the ceramic tile has dried, pure water is sprayed onto the surface. The flow of water on the surface of the ceramic is observed visually.
- a glass surface is used made up of microscopy slides of dimension 2.5 x 7.5 cm, previously cleaned with ethanol, the composition of which is given below:
- Detergent solutions are prepared, each containing a concentration of 50 ppm of polymer of Example 1 (acrylic acid / MAPTAC / acrylamide copolymer with 40/40/20 molar ratio), 0.2 g / l of nonperionic surfactant Symperonic A7 of BASF and 1 mol / l of KCI salt and whose pH is adjusted by adding 0.01 molar soda.
- the polymer solution is deposited on a glass slide using a centrifugal applicator with:
- 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 31.7 + -1 °.
- Examples 2 to 4 The method of Examples 2 to 4 is used with solutions of polymers in demineralized water at a concentration of 0.5 g / l and on ceramic tiles having a surface similar to toilet bowls.
- the pH of these solutions is 3.8.
- the deprotonation rate of acrylic acid in the polymer is 30%. This value makes it possible to calculate the charge Q of the polymers studied. With these higher polymer concentrations, it is considered that a good result in application corresponds to a contact angle of less than 15 °.
- An aqueous solution is prepared containing 0.5 g / l of nonionic surfactant Symperonic A7 from BASF and 0.2 g / l of acrylic acid / MAPTAC / acrylamide copolymer with a 40/40/20 molar ratio in hard water containing 300 ppm. of CaCO 3 .
- This solution has a pH of 7.
- This solution is used to treat a ceramic tile.
- This tile is arranged vertically and the treatment is done as follows: spraying the detergent solution in order to wet the entire tile; drying for 2 minutes; rinsing by spraying with hard water at 300 ppm in CaCO 3 drying for two hours.
- the tile thus treated is placed on a precise scale at 10 "2 g and 24 drops of water of 3 ⁇ l each are placed on the tile using a multichannel micropipette.
- the drying time of the tile is evaluated by the change in mass, and in particular the time required for 90% of the water to evaporate is noted.
- Tiles treated with a simple surfactant solution require a 90% drying time of 17 minutes.
- the tile treated with the polymer and surfactant solution requires a 90% drying time of 12 minutes.
- Formulations A and B are used as such by spraying onto the surface of the panes to be cleaned (6 to 8 sprays, ie 3 to 5 g of formulation per m 2 of surface.
- the table below gives cleaning formulations for cleaning hard surfaces.
- the glass hydrophilization test by contact angle described for Examples 2 to 4 is used with the detergent formula after dilution. As in examples 2 to 4, the glass slide is rinsed with pure water after application of the detergent solution.
- Formulations D and E are diluted before use, at a rate of 10 g of formulation in 1 liter of water.
- Example D is given for comparison.
- the contact angle results obtained on formulas D and E show that the polymer provides in the formula a persistent hydrophilization of the glass surface.
- a glass hydrophilization test by contact angle is used under the following conditions:
- the glass slides are placed in an automatic dishwasher and the powdered detergent formula is placed in the tank provided for this purpose, with a dosage of 32 g. No rinsing liquid is used in this test. These glass slides are washed with the "normal" program which gives a maximum washing temperature of 65 ° C. At the end of washing, the dishwasher is kept closed for 3 hours.
- hydrophilicity of the glass slides thus treated is then characterized by the technique of contact angles, described in Examples 2 to 4.
- Examples 16 and 17 are given by way of comparison
- the contact angle results obtained on formulations 14 and 15 show that the polymer provides in the formula a persistent hydrophilization of the glass surface in the dishwasher, which is not found with the comparative examples.
- Example 17 is given for comparison.
- the glass hydrophilization test by contact angle described for Examples 2 to 4 is used with the detergent formula after dilution to 1 g / l. As in Examples 2 to 4, the glass slide is rinsed with pure water after application of the detergent solution.
- Example 20 is given for comparison.
- the contact angle results obtained on formulas 21 and 22 show that the polymer provides a residual hydrophilization of the glass surface in the dishwasher in the formulation, a property which is not found with the formulation of Example 20 .
- hydrophilization test of the glass by contact angle described for examples 2 to 4 is used with the detergent formula after dilution to 1 g / l but it is carried out on black ceramic tiles.
- the support is rinsed with pure water after application of the detergent solution.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Cosmetics (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9909184 | 1999-07-15 | ||
FR9909184A FR2796391B1 (en) | 1999-07-15 | 1999-07-15 | CLEANING COMPOSITION FOR HARD SURFACES |
PCT/FR2000/002040 WO2001005922A1 (en) | 1999-07-15 | 2000-07-13 | Cleansing composition for hard surfaces |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1196528A1 true EP1196528A1 (en) | 2002-04-17 |
EP1196528B1 EP1196528B1 (en) | 2010-08-25 |
Family
ID=9548136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00953235A Expired - Lifetime EP1196528B1 (en) | 1999-07-15 | 2000-07-13 | Cleansing composition for hard surfaces |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1196528B1 (en) |
AT (1) | ATE478935T1 (en) |
AU (1) | AU6575900A (en) |
DE (1) | DE60044875D1 (en) |
FR (1) | FR2796391B1 (en) |
WO (1) | WO2001005922A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2851573A1 (en) * | 2003-02-20 | 2004-08-27 | Rhodia Chimie Sa | Compositions for cleaning or rinsing hard surfaces, e.g. floors, toilet bowls or glass, containing polybetaine compounds to impart lasting soil deposition and/or adhesion inhibiting properties |
FR2851572A1 (en) * | 2003-02-20 | 2004-08-27 | Rhodia Chimie Sa | Compositions for cleaning or rinsing hard surfaces, e.g. floors, toilet bowls or glass, containing polybetaine compounds to impart lasting soil deposition and/or adhesion inhibiting properties |
WO2008154617A2 (en) | 2007-06-12 | 2008-12-18 | Rhodia Inc. | Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces |
US8658586B2 (en) | 2008-08-26 | 2014-02-25 | Rhodia Operations | Copolymer for surface processing or modification |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GT200600375A (en) | 2005-08-17 | 2007-03-14 | ACID CLEANING COMPOSITION CONTAINING A HYDROPHILIZATION POLYMER | |
US7807766B2 (en) | 2005-09-21 | 2010-10-05 | Cognis Ip Management Gmbh | Polymers for use in cleaning compositions |
US8993506B2 (en) | 2006-06-12 | 2015-03-31 | Rhodia Operations | Hydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate |
US7524800B2 (en) | 2007-06-12 | 2009-04-28 | Rhodia Inc. | Mono-, di- and polyol phosphate esters in personal care formulations |
WO2008157197A1 (en) | 2007-06-12 | 2008-12-24 | Rhodia Inc. | Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same |
US7557072B2 (en) | 2007-06-12 | 2009-07-07 | Rhodia Inc. | Detergent composition with hydrophilizing soil-release agent and methods for using same |
EP2212409B1 (en) | 2007-11-06 | 2017-08-16 | Rhodia Opérations | Copolymer for treatment of laundry or hard surface |
DE102008060469A1 (en) | 2008-12-05 | 2010-06-10 | Henkel Ag & Co. Kgaa | Automatic dishwashing tablet |
GB201107885D0 (en) | 2011-05-12 | 2011-06-22 | Reckitt Benckiser Nv | Improved composition |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5813700A (en) * | 1981-07-17 | 1983-01-26 | 花王株式会社 | Detergent composition |
DE3614336A1 (en) * | 1986-04-28 | 1987-10-29 | Henkel Kgaa | LIQUID, AQUEOUS CLEANER FOR HARD SURFACES |
CA2072319C (en) * | 1991-06-28 | 2005-11-22 | Shih-Ruey T. Chen | Ampholyte terpolymers providing superior conditioning properties in skin and nail care products |
DE19545630A1 (en) * | 1995-12-07 | 1997-06-12 | Henkel Kgaa | Detergent for hard surfaces |
EP0835925A3 (en) * | 1996-09-09 | 1999-01-27 | Unilever N.V. | Machine dishwashing composition containing amphoteric polymers |
EP0998548B1 (en) * | 1997-07-23 | 2004-09-29 | Unilever N.V. | Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers |
-
1999
- 1999-07-15 FR FR9909184A patent/FR2796391B1/en not_active Expired - Fee Related
-
2000
- 2000-07-13 EP EP00953235A patent/EP1196528B1/en not_active Expired - Lifetime
- 2000-07-13 WO PCT/FR2000/002040 patent/WO2001005922A1/en active Application Filing
- 2000-07-13 AU AU65759/00A patent/AU6575900A/en not_active Abandoned
- 2000-07-13 DE DE60044875T patent/DE60044875D1/en not_active Expired - Lifetime
- 2000-07-13 AT AT00953235T patent/ATE478935T1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO0105922A1 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2851573A1 (en) * | 2003-02-20 | 2004-08-27 | Rhodia Chimie Sa | Compositions for cleaning or rinsing hard surfaces, e.g. floors, toilet bowls or glass, containing polybetaine compounds to impart lasting soil deposition and/or adhesion inhibiting properties |
FR2851572A1 (en) * | 2003-02-20 | 2004-08-27 | Rhodia Chimie Sa | Compositions for cleaning or rinsing hard surfaces, e.g. floors, toilet bowls or glass, containing polybetaine compounds to impart lasting soil deposition and/or adhesion inhibiting properties |
WO2004083354A1 (en) * | 2003-02-20 | 2004-09-30 | Rhodia Chimie | Composition for cleaning or rinsing hard surfaces |
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 |
US8658586B2 (en) | 2008-08-26 | 2014-02-25 | Rhodia Operations | Copolymer for surface processing or modification |
Also Published As
Publication number | Publication date |
---|---|
AU6575900A (en) | 2001-02-05 |
DE60044875D1 (en) | 2010-10-07 |
EP1196528B1 (en) | 2010-08-25 |
FR2796391A1 (en) | 2001-01-19 |
FR2796391B1 (en) | 2003-09-19 |
WO2001005922A1 (en) | 2001-01-25 |
ATE478935T1 (en) | 2010-09-15 |
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