EP0303188A2 - Liquid products for cleaning hard surfaces - Google Patents
Liquid products for cleaning hard surfaces Download PDFInfo
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- EP0303188A2 EP0303188A2 EP88112708A EP88112708A EP0303188A2 EP 0303188 A2 EP0303188 A2 EP 0303188A2 EP 88112708 A EP88112708 A EP 88112708A EP 88112708 A EP88112708 A EP 88112708A EP 0303188 A2 EP0303188 A2 EP 0303188A2
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- surfactants
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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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
Definitions
- liquid, manual dishwashing detergents which can usually be used at slightly elevated temperatures, contain as active ingredients essentially mixtures of synthetic anionic surfactants in amounts of about 4 to 60% by weight and, if appropriate, z. B. as foam stabilizers, small amounts of nonionic surfactants, preferably alkanolamides, or amphoteric surfactants such as betaines, and solvents, solubilizers, hydrotropic substances, fragrances and dyes, preservatives, agents for viscosity adjustment, pH adjustment and electrolytes.
- the pH is around 5.5 to 8.0.
- the agents can still contain small amounts of builders or complexing agents, such as hexametaphosphate or ethylenediaminetetraacetate, for use in areas with highly iron-containing water.
- builders or complexing agents such as hexametaphosphate or ethylenediaminetetraacetate
- Also common commercial all-purpose cleaning agents i.e. agents for cleaning various hard surfaces in the household and in commercial premises, preferably contain combinations of anionic and nonionic surfactants in a total amount of about 5 to 15% by weight as well as cleaning-enhancing framework substances in amounts of about 0.1 as active ingredients up to 5% by weight and to increase the cleaning performance as organic polymers polyethylene glycols of the general formula HO- (CH2-CH2-O) n -H, where n can vary between 4,800 and 64,600. These agents are also made up with dyes and fragrances, electrolytes and viscosity regulators.
- British patent application 2 104 091 recommends ampholytic copolymers of anionic and cationic vinyl monomers for increasing the performance in surfactant formulations.
- European patent application 124 367 teaches the use of water-soluble polymers, e.g. B. polysaccharides or xanthan rubber, which are both intended to increase the viscosity of the surfactant formulation and to improve their cleaning performance and foam behavior.
- German Offenlegungsschrift 2,616,404 which also relates to multigrade cleaning agents and is the closest to the invention, claims additions of polymers, namely water-soluble cationic cellulose ethers with a molecular weight of 25,000 to 10,000,000, to improve the flow of liquid from hard surfaces.
- ampholytic cellulose ethers are prepared in a manner known per se by mixed etherification of (alkali) cellulose with monochloroacetic acid sodium and 2-chloroethyldiethylamine with variation of the amounts of the carboxymethylating or aminating agent.
- the degree of substitution of cellulose is 0.4 to 2, preferably 0.6 to 1.2.
- the viscosity (Brookfield) of a 2% by weight aqueous solution of the polymers should be between 3,000 and 120,000 mPas, preferably between 9,000 and 80,000 mPas.
- the liquid compositions according to the invention for cleaning hard surfaces are particularly characterized in that they 1 to 40% by weight, preferably 5 to 25% by weight of anionic surfactants, 0 to 20% by weight, preferably 0.5 to 15% by weight, of nonionic surfactants or amphoteric surfactants 0 to 10% by weight, preferably 0.5 to 5% by weight of builder substances, 1 to 15% by weight, preferably 1.5 to 12% by weight, of solubilizer, 0.01 to 1.5% by weight, preferably 0.03 to 1% by weight, of the polymers according to the invention, and, if appropriate, other customary auxiliaries, in particular fragrances and dyes, preservatives and agents for adjusting the pH, and the remainder up to 100% by weight of water.
- Formulations free of anionic surfactants can contain 0-5% by weight, preferably 0.1-3% by weight, of cationic surfactants, also in mixtures with nonionic surfactants. The rest of the wording above applies.
- Suitable synthetic anionic surfactants are those of the sulfonate, sulfate and synthetic carboxylate type.
- Suitable surfactants of the sulfonate type are C9 ⁇ 15 alkylbenzenesulfonates, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonating group.
- suitable Alkanesulfonates which are obtainable from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
- esters of alpha sulfo fatty acids e.g. B. the alpha-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those secondary alcohols. Sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1-4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.
- Suitable anionic surfactants are the fatty acid esters or amides of hydroxy or amino carboxylic acids or sulfonic acids, such as. B. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates, alpha-sulfosuccinic acid esters and fatty acid cyanamides.
- the carbon chain length range of the hydrophobic residues of the surfactants is generally between 6 and 18, preferably between 8 and 16.
- the anionic surfactants can be present in the form of their alkali, alkaline earth and ammonium salts and as soluble salts of organic bases, such as the mono-, di- or triethanolamine.
- the sodium salts are mostly preferred for cost reasons.
- Addition products of 4-40, preferably 4-20 moles of ethylene oxide or ethylene oxide and propylene oxide with 1 mole of fatty alcohol, alkanediol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants.
- non-fully or not fully water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
- non-ionic surfactants that can be used are the water-soluble adducts of ethylene oxide with polypropylene oxide, alkylene diamine poly-propylene glycol and alkyl polypropylene glycols with 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain functions as a hydrophobic residue, containing polypropylene oxide, alkylene diamine poly-propylene glycol and 10-100 propylene glycol ether groups.
- Nonionic surfactants of the amine oxide type can also be used. Typical representatives are, for example, the compounds N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.
- Alkyl glucosides with 12 to 18, preferably 12 to 14 carbon atoms in the straight-chain or branched alkyl radical and 1 to 4, preferably 1 to 2, glucose units in the molecule are also suitable.
- Suitable addable amphoteric surfactants are those which contain both acidic groups, such as, for. B. carboxyl, sulfonic acid, sulfuric acid half-ester, phosphonic acid and phosphoric acid partial ester groups, as well as basic groups, such as. B. contain primary, secondary, tertiary and quaternary ammonium groups.
- Amphoteric compounds with quaternary ammonium groups belong to the type of betaines or zwitterionic surfactants. These are in particular derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C8-C18 alkyl radical and another contains an anionic, water-solubilizing carboxy, sulfo or sulfato group.
- Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propanesulfonate, 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate, 3- (N-hexadecyl- N, N-bis (2-hydroxyethyl) -ammonio) -2-hydroxypropyl sulfate, 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) propane sulfonate, N-tetradecyl-N, N -dimethyl-ammonioacetate, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate.
- C12-C18-Acylamido-propyldimethylammonium betaines are preferably used.
- the cationic surfactants which may be added contain at least one hydrophobic and at least one basic group which, if appropriate, is present as a salt and makes water-soluble.
- the hydrophobic group is an aliphatic or cycloaliphatic hydrocarbon group with preferably 10-22 carbon atoms or an alkyl or cycloalkylaromatic group with preferably 8-16 aliphatic carbon atoms.
- basic nitrogen atoms primarily basic nitrogen atoms come into question, which can also be present several times in a surfactant molecule; it is preferably quaternary ammonium compounds such as N-dodecyl-N, N, N-trimethylammonium methosulfate, N-hexadecyl or N-octadecyl-N, N, N-trimethylammonium chloride, N, N-dicocosalkyl-N, N-dimethylammonium chloride , N-dodecyl-N, N-dimethyl-N-benzylammonioumbromid, the reaction product of 1 mol tallow alkylamine with 10 mol ethylene oxide, N-dodecyl-N, N ', N'-trimethyl-1,3-diaminopropane, N-hexadecylpyridinium chloride.
- the nitrogen compounds mentioned can be replaced by corresponding compounds with a quaternary phosphorus atom or with a tertiary sulfur atom.
- Cleaning agents containing cationic surfactants are mostly used for disinfectant purposes.
- alkaline inorganic or organic compounds in particular inorganic or organic complexing agents, are used as builders, which are preferably in the form of their alkali or amine salts, in particular the potassium salts.
- the framework substances here also include the alkali metal hydroxides, of which the potassium hydroxide is preferably used.
- the alkaline polyphosphates in particular the tripolyphosphates and the pyrophosphates, are particularly suitable as inorganic complex-forming framework substances. They can be replaced in whole or in part by organic complexing agents. Further inorganic builder substances which can be used according to the invention are, for example, bicarbonates, carbonates, borates, silicates or orthophosphates of the alkalis.
- the organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylene diamine triacetic acid and polyalkylene polyamine N-polycarboxylic acids.
- di- and polyphosphonic acids examples include: methylene diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and Acrylic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxydiphosphonic acid, phosphono succinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid).
- N- or P-free polycarboxylic acids have also been proposed as builders, many, if not exclusively, of polymers containing carboxyl groups.
- a large number of these polycarboxylic acids have a complexing ability for calcium. These include e.g. B. citric acid, tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid.
- Suitable acidic substances are customary inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid, sulfuric acid, bisulfates or alkalis, aminosulfonic acid, phosphoric acid or other acids of phosphorus, in particular the anhydrous acids of phosphorus or their acidic salts or their acid-reacting solid compounds with urea or other lower carboxylic acid amides, partial amides of phosphoric acids or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid and the like.
- organic or inorganic compounds such as alkanol can also have an alkaline effect amines, namely mono-, di- or triethanolamine or ammonia can be added.
- solubilizers can be incorporated, which in addition to the water-soluble organic solvents such as, in particular, low-molecular aliphatic alcohols with 1-4 carbon atoms, also include the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or cumene sulfonate. They can also be in the form of their sodium and / or potassium and / or alkylamino salts.
- Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., for example the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols.
- These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic monohydric alcohols containing 1 to 4 carbon atoms in the molecule.
- ketones such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols.
- the latter generally have an odor-forming effect at the same time.
- the claimed agents can contain additives of colorants and fragrances, preservatives and, if desired, antimicrobial agents of any kind.
- Suitable antimicrobial agents to be used are, for example, those compounds which are stable and effective in the liquid compositions according to the invention, for example of the quaternary ammonium compound type, for example a benzylalkyldimethylammonium chloride.
- Plates of 14 cm in diameter were soiled with 2 g of beef tallow (melting point 40 to 42 ° C, acid number 9 to 10), stored for 15 hours at + 0 to + 5 ° C and at 50 ° C with tap water of hardness 16 ° d rinsed.
- the test products were used with a dosage of 0.5 g / l water, based on total agent, or 0.15 g individual surfactant / l water.
- the number of plates that are rinsed clean with 5 liters of washing solution number of plates serves as a measure of the cleaning effect.
- the cleaning agent to be tested was placed on an artificially soiled plastic surface.
- a mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling.
- the test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the help of a surface coater and then cut into seven equally large areas of 26 x 4 cm.
- a plastic sponge was impregnated with 6 ml of the undiluted detergent solution to be tested and moved mechanically on the test surface. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, d. that is, the whiteness of the plastic surface thus cleaned was measured with an LF 90 photoelectric colorimeter (Dr. B. Lange). The clean white plastic surface served as the white standard.
- the read values for the cleaned plastic areas were to be equated with the percentage cleaning ability (% RV).
- % RV percentage cleaning ability
- the% -RV values given are the values determined by this method for the cleaning ability of the cleaning agents examined. They each represent mean values from 4-fold determinations (cf. quality standards of the Industry Association for Cleaning and Care Agents (IPP), Frankfurt / Main (1982 version) in "Soaps, Fats, Oils, Waxes", 108 , (1982) 527-528.
- the soiling used to determine the cleaning ability consisted of: Petrol 80/110 - White spirit K 30 44.8 Special black 4 4.8 Coray 34 - Myritol 318 4.8 Vaseline 5.6 Kaolin 20.0 Durcal 2 20.0 (Data% by weight)
- composition of the cleaning agents according to the invention is given in the tables.
- comparative tests according to DE 26 16 404 The difference to 100% by weight in any case consists of water.
- a cationic cellulose ether derivative namely the polymer JR 400 (R) from Union Carbide (cf. US 3,472,840) with an average molecular weight of 400,000 was used.
- ampholytic cellulose ethers according to the invention have a higher performance increase in the detergents than cationic cellulose ethers according to DE 26 16 404.
- Table 2 shows that the ampholytic cellulose ethers according to the invention, incorporated in small proportions in general-purpose or disinfectant cleaning agents, bring about distinct cleaning-enhancing effects.
- ampholytic cellulose ethers Another surprising advantage of the ampholytic cellulose ethers was the removal of fat on newly soiled plates that had already been cleaned in a polymer-containing washing liquor. The following experiment made this advantage clear:
- the plates cleaned in the polymeric washing liquor were - as already described - again soiled with 2 g beef tallow / plate and stored for 15 hours at temperatures of 0 - 5 ° C.
- a plate was then placed horizontally in 5 liters of rinse liquor at 50 ° C. and the time until the grease removal from the plate surface was completed without any additional manual action.
- the cleaning time was approximately 2.5 minutes;
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Abstract
Description
Marktübliche, flüssige, manuell und meist bei leicht erhöhten Temperaturen anwendbare Geschirreinigungsmittel enthalten als Wirkstoffe im wesentlichen Gemische synthetischer anionischer Tenside in Mengen von etwa 4 bis 60 Gew.-%, sowie gegebenenfalls z. B. als Schaumstabilisatoren geringe Mengen an nichtionischen Tensiden, vorzugsweise Alkanolamide, oder Amphotenside wie Betaine, sowie Lösungsmittel, Lösungsvermittler, hydrotrope Substanzen, Duft- und Farbstoffe, Konservierungsmittel, Mittel zur Viskositätseinstellung, zur pH-Einstellung und Elektrolyte. Der pH-Wert liegt aus Hautschutzgründen bei etwa 5,5 bis 8,0. Unter Umständen können die Mittel, was aber nicht typisch ist, für die Anwendung in Gegenden mit stark eisenhaltigem Wasser noch geringe Mengen an Gerüstsubstanzen oder Komplexbildnern wie Hexametaphosphat oder Ethylendiamintetraacetat enthalten. Derartige Mittel sind beispielsweise aus dem europäischen Patent 36 625 bekannt.Commercial, liquid, manual dishwashing detergents, which can usually be used at slightly elevated temperatures, contain as active ingredients essentially mixtures of synthetic anionic surfactants in amounts of about 4 to 60% by weight and, if appropriate, z. B. as foam stabilizers, small amounts of nonionic surfactants, preferably alkanolamides, or amphoteric surfactants such as betaines, and solvents, solubilizers, hydrotropic substances, fragrances and dyes, preservatives, agents for viscosity adjustment, pH adjustment and electrolytes. For skin protection reasons, the pH is around 5.5 to 8.0. Under certain circumstances, but not typical, the agents can still contain small amounts of builders or complexing agents, such as hexametaphosphate or ethylenediaminetetraacetate, for use in areas with highly iron-containing water. Such means are known for example from European patent 36 625.
Ebenfalls marktübliche Allzweckreinigungsmittel, d. h. Mittel zum Reinigen von diversen harten Oberflächen im Haushalt und in Gewerberäumen, enthalten als Wirkstoffe bevorzugt Kombinationen von anionischen und nichtionischen Tensiden in einer Gesamtmenge von etwa 5 bis 15 Gew.-% sowie reinigungsverstärkende Gerüstsubstanzen in Mengen von etwa 0,1 bis 5 Gew.-% und zur Steigerung der Reinigungsleistung als organische Polymere Polyethylenglykole der allgemeinen Formel HO-(CH₂-CH₂-O)n-H, wobei n zwischen 4 800 und 64 600 variieren kann. Diese Mittel werden ebenfalls mit Farb- und Duftstoffen, Elektrolyten und Viskositätsreglern konfektioniert. Ihr pH-Wert liegt vorzugsweise im Bereich von 8,5 bis 11, da das Reinigungsvermögen, das bei diesen Mitteln überwiegend bei Raumtemperatur zur Geltung kommen muß, im alkalischen Milieu im allgemeinen besser ist als im neutralen oder sauren. Derartige Allzweckreinigungsmittel sind beispielsweise aus der deutschen Patentschrift 27 09 690 und aus der europäischen Patentschrift 9 193 bekannt.Also common commercial all-purpose cleaning agents, i.e. agents for cleaning various hard surfaces in the household and in commercial premises, preferably contain combinations of anionic and nonionic surfactants in a total amount of about 5 to 15% by weight as well as cleaning-enhancing framework substances in amounts of about 0.1 as active ingredients up to 5% by weight and to increase the cleaning performance as organic polymers polyethylene glycols of the general formula HO- (CH₂-CH₂-O) n -H, where n can vary between 4,800 and 64,600. These agents are also made up with dyes and fragrances, electrolytes and viscosity regulators. Their pH value is preferably in the range from 8.5 to 11, since the cleaning power, which must be used with these agents predominantly at room temperature, is generally better in an alkaline environment than in a neutral or acidic one. All-purpose cleaning agents of this type are known, for example, from German patent specification 27 09 690 and from European patent specification 9 193.
Reinigungsmittel mit einem Zusatz an entsprechenden reinigungsverstärkenden Polymeren sind auch in den deutschen Offenlegungsschriften 29 13 049 und 35 12 535, letztere betrifft Mehrbereichsreinigungsmittel, beschrieben, wobei sich wasserlösliche Polyethylenglykole mit einer Molmasse zwischen 3 x 10⁵ und 4 x 10⁶, vorzugsweise 5 x 10⁵ und 1 x 10⁶, als besonders geeignet erwiesen haben. Der Einsatz derartiger Polymerer in Reinigungsmitteln für harte Oberflächen wird in den deutschen Patentschriften 28 40 463 (EP 9193) und 28 40 464 beschrieben.Detergents with the addition of corresponding cleaning-reinforcing polymers are also described in German Offenlegungsschriften 29 13 049 and 35 12 535, the latter relates to multi-range detergents, water-soluble polyethylene glycols having a molecular weight between 3 x 10⁵ and 4 x 10⁶, preferably 5 x 10⁵ and 1 x 10⁶, have proven to be particularly suitable. The use of such polymers in cleaning agents for hard surfaces is described in German patents 28 40 463 (EP 9193) and 28 40 464.
Nach der Lehre der deutschen Offenlegungsschrift 26 17 909 und der europäischen Patentanmeldung 66 342 werden Copolymere von Monovinylmonomeren, z. B. von Styrol oder Vinylmethylether, mit ungesättigten Dicarbonsäuren bzw. deren Anhydriden, z. B. Maleinsäure, in Allzweckreinigungsmitteln eingesetzt. Diese Polymeren sollen hauptsächlich eine Streifenbildung auf den harten Oberflächen unterdrücken.According to the teaching of German Offenlegungsschrift 26 17 909 and European patent application 66 342, copolymers of monovinyl monomers, e.g. B. of styrene or vinyl methyl ether, with unsaturated dicarboxylic acids or their anhydrides, for. B. maleic acid, used in general-purpose cleaning agents. These polymers are primarily intended to suppress streaking on hard surfaces.
In der britischen Patentanmeldung 2 104 091 werden ampholytische Copolymeren aus anionischen und kationischen Vinylmonomeren zur Leistungssteigerung in Tensidformulierungen empfohlen.British patent application 2 104 091 recommends ampholytic copolymers of anionic and cationic vinyl monomers for increasing the performance in surfactant formulations.
Die europäische Patentanmeldung 124 367 lehrt die Verwendung wasserlöslicher Polymeren, z. B. Polysaccharide oder Xanthan gummi, die sowohl die Viskosität der Tensidformulierung erhöhen als auch ihre Reinigungsleistung und das Schaumverhalten verbessern sollen.European patent application 124 367 teaches the use of water-soluble polymers, e.g. B. polysaccharides or xanthan rubber, which are both intended to increase the viscosity of the surfactant formulation and to improve their cleaning performance and foam behavior.
In der deutschen Offenlegungsschrift 2 616 404, die ebenfalls Mehrbereichsreinigungsmittel betrifft und der Erfindung am nächsten steht, werden zwecks Verbesserung des Flüssigkeitsablaufs von harten Oberflächen Zusätze von Polymeren, nämlich von wasserlöslichen kationischen Celluloseethern mit einer Molmasse von 25 000 bis 10 000 000 beansprucht.German Offenlegungsschrift 2,616,404, which also relates to multigrade cleaning agents and is the closest to the invention, claims additions of polymers, namely water-soluble cationic cellulose ethers with a molecular weight of 25,000 to 10,000,000, to improve the flow of liquid from hard surfaces.
Überraschenderweise wurde nun gefunden, daß die Reinigungsleistung von flüssigen Mitteln zum Reinigen harter verschiedenster Oberflächen auf Basis von anionischen Tensiden allein oder in Kombination mit nichtionischen Tensiden und/oder Amphotensiden (Betainen) oder nichtionischen Tensiden allein oder in Kombination mit Kationtensiden, Lösungsvermittlern und Polymeren sowie gegebenenfalls Gerüstsubstanzen, Farbstoffen, Duftstoffen und Konservierungsmitteln durch den Zusatz von ampholytischen Celluloseethern anstelle von kationischen Celluloseethern gemäß der deutschen Offenlegungsschrift 2 616 404 erheblich verbessert werden kann.Surprisingly, it has now been found that the cleaning performance of liquid agents for cleaning hard and varied surfaces based on anionic surfactants alone or in combination with nonionic surfactants and / or amphoteric surfactants (betaines) or nonionic surfactants alone or in combination with cationic surfactants, solubilizers and polymers and optionally Builders, dyes, fragrances and preservatives can be significantly improved by adding ampholytic cellulose ethers instead of cationic cellulose ethers according to German Offenlegungsschrift 2 616 404.
Die ampholytischen Celluloseether werden in an sich bekannter Weise durch Mischveretherung von (Alkali-)Cellulose mit monochloressigsaurem Natrium und 2-Chlorethyldiethylamin unter Variation der Mengen des Carboxymethylierungs- bzw. Aminierungsmittels hergestellt. Der Substitutionsgrad der Cellulose beträgt 0,4 bis 2, vorzugsweise 0,6 bis 1,2. Die Viskosität (Brookfield) einer 2 gew.-%igen wäßrigen Lösung der Polymeren soll zwischen 3 000 und 120 000 mPas, vorzugsweise zwischen 9 000 und 80 000 mPas liegen.The ampholytic cellulose ethers are prepared in a manner known per se by mixed etherification of (alkali) cellulose with monochloroacetic acid sodium and 2-chloroethyldiethylamine with variation of the amounts of the carboxymethylating or aminating agent. The degree of substitution of cellulose is 0.4 to 2, preferably 0.6 to 1.2. The viscosity (Brookfield) of a 2% by weight aqueous solution of the polymers should be between 3,000 and 120,000 mPas, preferably between 9,000 and 80,000 mPas.
Die erfindungsgemäßen flüssigen Mittel zur Reinigung harter Oberflächen sind insbesondere dadurch gekennzeichnet, daß sie
1 bis 40 Gew.-%, vorzugsweise 5 bis 25 Gew.-% anionische Tenside,
0 bis 20 Gew.-%, vorzugsweise 0,5 bis 15 Gew.-% nichtionische Tenside oder Amphotenside
0 bis 10 Gew.-%, vorzugsweise 0,5 bis 5 Gew.-% Gerüstsubstanzen,
1 bis 15 Gew.-%, vorzugsweise 1,5 bis 12 Gew.-% Lösungsvermittler,
0,01 bis 1,5 Gew.-%, vorzugsweise 0,03 bis 1 Gew.-% der erfindungsgemäßen Polymeren,
sowie gegebenenfalls sonstige übliche Hilfsstoffe, insbesondere Duft- und Farbstoffe, Konservierungsmittel und Mittel zur pH-Einstellung sowie als Rest bis 100 Gew.-% Wasser enthalten.The liquid compositions according to the invention for cleaning hard surfaces are particularly characterized in that they
1 to 40% by weight, preferably 5 to 25% by weight of anionic surfactants,
0 to 20% by weight, preferably 0.5 to 15% by weight, of nonionic surfactants or amphoteric surfactants
0 to 10% by weight, preferably 0.5 to 5% by weight of builder substances,
1 to 15% by weight, preferably 1.5 to 12% by weight, of solubilizer,
0.01 to 1.5% by weight, preferably 0.03 to 1% by weight, of the polymers according to the invention,
and, if appropriate, other customary auxiliaries, in particular fragrances and dyes, preservatives and agents for adjusting the pH, and the remainder up to 100% by weight of water.
In aniontensidfreien Rezepturen können 0 - 5 Gew.-%, vorzugsweise 0,1 - 3 Gew.-% kationische Tenside, auch in Gemischen mit nichtionischen Tensiden, enthalten sein. Im übrigen gelten die obigen Formulierungsangaben.Formulations free of anionic surfactants can contain 0-5% by weight, preferably 0.1-3% by weight, of cationic surfactants, also in mixtures with nonionic surfactants. The rest of the wording above applies.
Geeignete synthetische anionische Tenside sind solche vom Typ der Sulfonate, Sulfate und der synthetischen Carboxylate.Suitable synthetic anionic surfactants are those of the sulfonate, sulfate and synthetic carboxylate type.
Als Tenside vom Sulfonattyp kommen C₉₋₁₅-Alkylbenzolsulfonate, Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsgruppe erhält, in Betracht. Weiter eignen sich Alkansulfonate, die aus Alkanen durch Sulfochlorierung oder Sulfoxydation und anschließende Hydrolyse bzw. Neutralisation bzw. durch Bisulfitaddition an Olefine erhältlich sind. Weitere brauchbare Tenside vom Sulfonattyp sind die Ester von alpha-Sulfofettsäuren, z. B. die alpha-Sulfonsäuren aus hydrierten Methyl- oder Ethylestern der Cocos-, Palmkern- oder Talgfettsäure.Suitable surfactants of the sulfonate type are C₉₋₁₅ alkylbenzenesulfonates, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonating group. Further are suitable Alkanesulfonates, which are obtainable from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Other useful surfactants of the sulfonate type are the esters of alpha sulfo fatty acids, e.g. B. the alpha-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
Geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester primärer Alkohole (z. B. aus Cocosfettalkoholen, Talgfettalkoholen oder Oleylalkohol) und diejenigen sekundären Alkohole. Weiterhin eignen sich sulfatierte Fettsäurealkanolamide, Fettsäuremonoglyceride oder Umsetzungsprodukte von 1 - 4 Mol Ethylenoxid mit primären oder sekundären Fettalkoholen oder Alkylphenolen.Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those secondary alcohols. Sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1-4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.
Weitere geeignete anionische Tenside sind die Fettsäureester bzw. -amide von Hydroxy- oder Amino-carbonsäuren bzw. -sulfonsäuren, wie z. B. die Fettsäuresarcoside, -glycolate, -lactate, -tauride oder -isethionate, alpha-Sulfobernsteinsäureester und Fettsäurecyanamide.Other suitable anionic surfactants are the fatty acid esters or amides of hydroxy or amino carboxylic acids or sulfonic acids, such as. B. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates, alpha-sulfosuccinic acid esters and fatty acid cyanamides.
Der Kohlenstoffkettenlängenbereich der hydrophoben Reste der Tenside liegt im allgemeinen zwischen 6 und 18, vorzugsweise zwischen 8 und 16.The carbon chain length range of the hydrophobic residues of the surfactants is generally between 6 and 18, preferably between 8 and 16.
Die anionischen Tenside können in Form ihrer Alkali-, Erdalkali- und Ammoniumsalze sowie als lösliche Salze organischer Basen, wie des Mono-, Di- oder Triethanolamins vorliegen. Die Natriumsalze werden meist aus Kostengründen bevorzugt.The anionic surfactants can be present in the form of their alkali, alkaline earth and ammonium salts and as soluble salts of organic bases, such as the mono-, di- or triethanolamine. The sodium salts are mostly preferred for cost reasons.
Als nichtionische Tenside sind Anlagerungsprodukte von 4 - 40, vorzugsweise 4 - 20 Mol Ethylenoxid oder Ethylenoxid und Propylenoxid an 1 Mol Fettalkohol, Alkandiol, Alkylphenol, Fettsäure, Fettamin, Fettsäureamid oder Alkansulfonamid verwendbar. Beson ders wichtig sind die Anlagerungsprodukte von 5 - 16 Mol Ethylenoxid oder Ethylen- und Propylenoxid an Cocos- oder Talgfettalkohole, an Oleylalkohol oder an sekundäre Alkohole mit 8 - 18, vorzugsweise 12 - 18 C-Atomen, sowie an Mono- oder Dialkylphenole mit 6 - 14 C-Atomen in den Alkylresten. Neben diesen wasserlöslichen Nonionics sind aber auch nicht bzw. nicht vollständig wasserlösliche Polyglycolether mit 1 - 4 Ethylenglycoletherresten im Molekül von Interesse, insbesondere, wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden.Addition products of 4-40, preferably 4-20 moles of ethylene oxide or ethylene oxide and propylene oxide with 1 mole of fatty alcohol, alkanediol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants. Especially importantly, the addition products of 5 - 16 mol ethylene oxide or ethylene and propylene oxide with coconut or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8 - 18, preferably 12 - 18 carbon atoms, as well as with mono- or dialkylphenols with 6 - 14 carbon atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
Weiterhin sind als nichtionische Tenside die wasserlöslichen, 20 - 250 Ethylenglycolethergruppen und 10 - 100 Propylenglycolethergruppen enthaltenden Anlagerungsprodukte von Ethylenoxid an Polyproyplenoxid, Alkylendiaminpoly-propylenglycol und Alkylpolypropylenglycole mit 1 - 10 C-Atomen in der Alkylkette brauchbar, in denen die Polypropylenglycolkette als hydrophober Rest fungiert.Furthermore, the non-ionic surfactants that can be used are the water-soluble adducts of ethylene oxide with polypropylene oxide, alkylene diamine poly-propylene glycol and alkyl polypropylene glycols with 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain functions as a hydrophobic residue, containing polypropylene oxide, alkylene diamine poly-propylene glycol and 10-100 propylene glycol ether groups.
Auch nichtionische Tenside vom Typ der Aminoxide sind verwendbar. Typische Vertreter sind beispielsweise die Verbindungen N-Dodecyl-N,N-dimethylaminoxid, N-Tetradecyl-N,N-dihydroxyethylaminoxid, N-Hexadecyl-N,N-bis-(2,3-dihydroxypropyl)-aminoxid.Nonionic surfactants of the amine oxide type can also be used. Typical representatives are, for example, the compounds N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.
Auch Alkylglucoside mit 12 bis 18, vorzugsweise 12 bis 14 Kohlenstoffatomen im geradkettigen oder verzweigten Alkylrest sowie 1 bis 4, vorzugsweise 1 bis 2 Glucoseeinheiten im Molekül kommen in Betracht.Alkyl glucosides with 12 to 18, preferably 12 to 14 carbon atoms in the straight-chain or branched alkyl radical and 1 to 4, preferably 1 to 2, glucose units in the molecule are also suitable.
Geeignete zusetzbare Amphotenside sind solche, die im Molekül sowohl saure Gruppen, wie z. B. Carboxyl-, Sulfonsäure-, Schwefelsäurehalbester-, Phosphonsäure- und Phosphorsäureteilestergruppen, als auch basische Gruppen, wie z. B. primäre, sekundäre, tertiäre und quartäre Ammoniumgruppen enthalten.Suitable addable amphoteric surfactants are those which contain both acidic groups, such as, for. B. carboxyl, sulfonic acid, sulfuric acid half-ester, phosphonic acid and phosphoric acid partial ester groups, as well as basic groups, such as. B. contain primary, secondary, tertiary and quaternary ammonium groups.
Amphotere Verbindungen mit quartären Ammoniumgruppen gehören zum Typ der Betaine oder zwitterionischen Tenside. Hierbei handelt es sich insbesondere um Derivate aliphatischer quartärer Ammoniumverbindungen, in denen einer der aliphatischen Reste aus einem C₈-C₁₈-Alkylrest besteht und ein weiterer eine anionische, wasserlöslich machende Carboxy-, Sulfo- oder Sulfato-Gruppe enthält. Typische Vertreter derartiger oberflächenaktiver Betaine sind beispielsweise die Verbindungen 3-(N-Hexadecyl-N,N-dimethylammonio)-propansulfonat, 3-(N-Talgalkyl-N,N-dimethylammonio)-2-hydroxypropansulfonat, 3-(N-Hexadecyl-N,N-bis(2-hydroxyethyl)-ammonio)-2-hydroxypropylsulfat, 3-(N-Cocosalkyl-N,N-bis(2,3-dihydroxypropyl)-ammonio)-propansulfonat, N-Tetradecyl-N,N-dimethyl-ammonioacetat, N-Hexadecyl-N,N-bis(2,3-dihydroxypropyl)-ammonioacetat. Bevorzugt eingesetzt werden C₁₂-C₁₈-Acylamido-propyldimethylammoniumbetaine.Amphoteric compounds with quaternary ammonium groups belong to the type of betaines or zwitterionic surfactants. These are in particular derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C₈-C₁₈ alkyl radical and another contains an anionic, water-solubilizing carboxy, sulfo or sulfato group. Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propanesulfonate, 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate, 3- (N-hexadecyl- N, N-bis (2-hydroxyethyl) -ammonio) -2-hydroxypropyl sulfate, 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) propane sulfonate, N-tetradecyl-N, N -dimethyl-ammonioacetate, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate. C₁₂-C₁₈-Acylamido-propyldimethylammonium betaines are preferably used.
Die gegebenenfalls zusetzbaren kationischen Tenside enthalten wenigstens eine hydrophobe und wenigstens eine basische, gegebenenfalls als Salz vorliegende wasserlöslich machende Gruppe. Bei der hydrophoben Gruppe handelt es sich um eine aliphatische oder cycloaliphatische Kohlenwasserstoffgruppe mit vorzugsweise 10 - 22 C-Atomen oder um eine alkyl- bzw. cycloalkylaromatische Gruppe mit vorzugsweise 8 - 16 aliphatischen C-Atomen. Als basische Gruppen kommen in erster Linie basische Stickstoffatome in Frage, die auch mehrfach in einem Tensidmolekül vorhanden sein können; bevorzugt handelt es sich um quartäre Ammoniumverbindungen wie beispielsweise N-Dodecyl-N,N,N-trimethylammoniummethosulfat, N-Hexadecyl- bzw. N-Octadecyl-N,N,N-trimethylammoniumchlorid, N,N-Dicocosalkyl-N,N-dimethylammoniumchlorid, N-Dodecyl-N,N-dimethyl-N-benzylammonioumbromid, das Umsetzungsprodukt von 1 Mol Talgalkylamin mit 10 Mol Ethylenoxid, N-Dodecyl-N,N',N'-trimethyl-1,3-diaminopropan, N-Hexadecylpyridiniumchlorid.The cationic surfactants which may be added contain at least one hydrophobic and at least one basic group which, if appropriate, is present as a salt and makes water-soluble. The hydrophobic group is an aliphatic or cycloaliphatic hydrocarbon group with preferably 10-22 carbon atoms or an alkyl or cycloalkylaromatic group with preferably 8-16 aliphatic carbon atoms. As basic groups, primarily basic nitrogen atoms come into question, which can also be present several times in a surfactant molecule; it is preferably quaternary ammonium compounds such as N-dodecyl-N, N, N-trimethylammonium methosulfate, N-hexadecyl or N-octadecyl-N, N, N-trimethylammonium chloride, N, N-dicocosalkyl-N, N-dimethylammonium chloride , N-dodecyl-N, N-dimethyl-N-benzylammonioumbromid, the reaction product of 1 mol tallow alkylamine with 10 mol ethylene oxide, N-dodecyl-N, N ', N'-trimethyl-1,3-diaminopropane, N-hexadecylpyridinium chloride.
Die genannten Stickstoffverbindungen lassen sich durch entsprechende Verbindungen mit quartärem Phosphoratom oder mit tertiärem Schwefelatom ersetzen.The nitrogen compounds mentioned can be replaced by corresponding compounds with a quaternary phosphorus atom or with a tertiary sulfur atom.
Reinigungsmittel mit einem Gehalt an kationischen Tensiden werden meist für desinfizierende Zwecke verwendet.Cleaning agents containing cationic surfactants are mostly used for disinfectant purposes.
Als Gerüstsubstanzen werden in ihrer Gesamtheit alkalisch reagierende anorganische oder organische Verbindungen, insbesondere anorganische oder organische Komplexbildner eingesetzt, die bevorzugt in Form ihrer Alkali- oder Aminsalze, insbesondere der Kaliumsalze vorliegen. Zu den Gerüstsubstanzen zählen hier auch die Alkalihydroxide, von denen bevorzugt das Kaliumhydroxid eingesetzt wird.As a whole, alkaline inorganic or organic compounds, in particular inorganic or organic complexing agents, are used as builders, which are preferably in the form of their alkali or amine salts, in particular the potassium salts. The framework substances here also include the alkali metal hydroxides, of which the potassium hydroxide is preferably used.
Als anorganische komplexbildende Gerüstsubstanzen eignen sich besonders die alkalisch reagierenden Polyphosphate, insbesondere die Tripolyphosphate sowie die Pyrophosphate. Sie können ganz oder teilweise durch organische Komplexbildner ersetzt werden. Weitere erfindungsgemäß brauchbare anorganische Gerüstsubstanzen sind beispielsweise Bicarbonate, Carbonate, Borate, Silikate oder Orthophosphate der Alkalien.The alkaline polyphosphates, in particular the tripolyphosphates and the pyrophosphates, are particularly suitable as inorganic complex-forming framework substances. They can be replaced in whole or in part by organic complexing agents. Further inorganic builder substances which can be used according to the invention are, for example, bicarbonates, carbonates, borates, silicates or orthophosphates of the alkalis.
Zu den organischen Komplexbildnern vom Typ der Aminopolycarbonsäuren gehören unter anderem die Nitrilotriessigsäure, Ethylendiamintetraessigsäure, N-Hydroxyethyl-ethylen-diamintriessigsäure und Polyalkylen-polyamin-N-polycarbonsäuren. Als Beispiele für Di- und Polyphosphonsäuren seien genannt: Methylendiphosphonsäure, 1-Hydroxyethan-1,1-diphosphonsäure, Propan-1,2,3-triphosphonsäure, Butan-1,2,3,4-tetraphosphonsäure, Polyvinylphosphonsäure, Mischpolymerisate aus Vinylphosphonsäure und Acrylsäure, Ethan-1,2-dicarboxy-1,2-diphosphonsäure, Ethan-1,2-dicarboxy-1,2-dihydroxydiphosphonsäure, Phosphono bernsteinsäure, 1-Aminoethan-1,1-diphosphonsäure, Aminotri-(methylenphosphonsäure), Methyl-amino- oder Ethylamino-di-(methylenphosphonsäure) sowie Ethylendiamin-tetra-(methylenphosphonsäure). Auch verschiedenste, meist N- oder P-freie Polycarbonsäuren als Gerüstsubstanzen sind vorgeschlagen worden, wobei es sich vielfach, wenn auch nicht ausschließlich, um Carboxylgruppen enthaltende Polymerisate handelt. Eine große Zahl dieser Polycarbonsäuren besitzen ein Komplexbildungsvermögen für Calcium. Hierzu gehören z. B. Citronensäure, Weinsäure, Benzolhexacarbonsäure, Tetrahydrofurantetracarbonsäure.The organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylene diamine triacetic acid and polyalkylene polyamine N-polycarboxylic acids. Examples of di- and polyphosphonic acids are: methylene diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and Acrylic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxydiphosphonic acid, phosphono succinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid). Various, mostly N- or P-free polycarboxylic acids have also been proposed as builders, many, if not exclusively, of polymers containing carboxyl groups. A large number of these polycarboxylic acids have a complexing ability for calcium. These include e.g. B. citric acid, tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid.
Da Reinigungsmittel für den Haushalt im allgemeinen fast neutral bis schwach alkalisch eingestellt sind, d. h. ihre unverdünnten Konzentrate oder ihre wäßrigen Gebrauchslösungen bei Anwendungskonzentrationen von 2 - 20, vorzugsweise von 5 - 15 g/l Wasser oder wäßriger Lösung einen pH-Wert im Bereich von 7,0 - 10,5, vorzugsweise 7,5 - 9,5, besitzen sollen, kann zur Regulierung des pH-Wertes ein Zusatz saurer oder alkalischer Komponenten erforderlich sein.Since household cleaning agents are generally almost neutral to slightly alkaline, i. H. their undiluted concentrates or their aqueous working solutions at application concentrations of 2 - 20, preferably 5 - 15 g / l water or aqueous solution have a pH in the range of 7.0 - 10.5, preferably 7.5 - 9.5, acidic or alkaline components may be required to regulate the pH.
Als saure Substanzen eignen sich übliche anorganische oder organische Säuren oder saure Salze, wie beispielsweise Salzsäure, Schwefelsäure, Bisulfate oder Alkalien, Aminosulfonsäure, Phosphorsäure oder andere Säuren des Phosphors, insbesondere die anhydrischen Säuren des Phosphors bzw. deren saure Salze oder deren sauer reagierende feste Verbindungen mit Harnstoff oder anderen niederen Carbonsäureamiden, Teilamide der Phosphorsäuren oder der anhydrischen Phosphorsäure, Citronensäure, Weinsäure, Milchsäure und dergleichen.Suitable acidic substances are customary inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid, sulfuric acid, bisulfates or alkalis, aminosulfonic acid, phosphoric acid or other acids of phosphorus, in particular the anhydrous acids of phosphorus or their acidic salts or their acid-reacting solid compounds with urea or other lower carboxylic acid amides, partial amides of phosphoric acids or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid and the like.
Sofern der Gehalt an alkalischen Gerüstsubstanzen nicht zur Regulierung des pH-Wertes ausreicht, können auch noch alkalisch wirkende organische oder anorganische Verbindungen wie Alkanol amine, nämlich Mono-, Di- oder Triethanolamin oder Ammoniak zugesetzt werden.If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as alkanol can also have an alkaline effect amines, namely mono-, di- or triethanolamine or ammonia can be added.
Außerdem kann man an sich bekannte Lösungsvermittler einarbeiten, wozu außer den wasserlöslichen organischen Lösungsmitteln wie insbesondere niedermolekularen aliphatischen Alkoholen mit 1 - 4 Kohlenstoffatomen auch die sogenannten hydrotropen Stoffe vom Typ der niederen Alkylarylsulfonate beispielsweise Toluol-, Xylol- oder Cumolsulfonat gehören. Sie können auch in Form ihrer Natrium- und/oder Kalium- und/oder Alkylaminosalze vorliegen. Als Lösungsvermittler sind weiterhin wasserlösliche organische Lösungsmittel verwendbar, insbesondere solche mit Siedepunkten oberhalb von 75° C wie beispielsweise die Ether aus gleich- oder verschiedenartigen mehrwertigen Alkoholen oder die Teilether aus mehrwertigen Alkoholen. Hierzu gehören beispielsweise Di- oder Triethylenglycolpolyglycerine sowie die Teilether aus Ethylenglycol, Propylenglycol, Butylenglycol oder Glycerin mit aliphatischen, 1 - 4 Kohlenstoffatome im Molekül enthaltenden einwertigen Alkoholen.In addition, known solubilizers can be incorporated, which in addition to the water-soluble organic solvents such as, in particular, low-molecular aliphatic alcohols with 1-4 carbon atoms, also include the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or cumene sulfonate. They can also be in the form of their sodium and / or potassium and / or alkylamino salts. Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., for example the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic monohydric alcohols containing 1 to 4 carbon atoms in the molecule.
Als wasserlösliche oder mit Waser emulgierbare organische Lösungsmittel kommen auch Ketone, wie Aceton, Methylethylketon sowie aliphatische, cycloaliphatische, aromatische und chlorierte Kohlenwasserstoffe, ferner die Terpenalkohole in Betracht. Letztere wirken im allgemeinen gleichzeitig geruchsbildend.Also suitable as water-soluble or water-emulsifiable organic solvents are ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols. The latter generally have an odor-forming effect at the same time.
Zur Regulierung der Viskosität empfiehlt sich gegebenenfalls ein Zusatz von höheren Polyglycolethern mit Molgewichten bis etwa 600 oder Polyglycerin. Weiterhin empfiehlt sich zur Regulierung der Viskosität ein Zusatz an Natriumchlorid und/oder Harnstoff.To regulate the viscosity, it may be advisable to add higher polyglycol ethers with molecular weights up to about 600 or polyglycerol. It is also recommended to add sodium chloride and / or urea to regulate the viscosity.
Außerdem können die beanspruchten Mittel Zusätze an Farb- und Duftstoffen, Konservierungsmitteln und gewünschtenfalls auch antimikrobiell wirksamen Mitteln beliebiger Art enthalten.In addition, the claimed agents can contain additives of colorants and fragrances, preservatives and, if desired, antimicrobial agents of any kind.
Als zu verwendende antimikrobielle Wirkstoffe kommen beispielsweise solche Verbindungen in Betracht, die in den erfindungsgemäßen flüssigen Mitteln stabil und wirksam sind, etwa vom Typ der quaternären Ammoniumverbindungen, beispielsweise ein Benzylalkyldimethylammoniumchlorid.Suitable antimicrobial agents to be used are, for example, those compounds which are stable and effective in the liquid compositions according to the invention, for example of the quaternary ammonium compound type, for example a benzylalkyldimethylammonium chloride.
Zur Beurteilung der Reinigungsleistung wurden folgende Prüfmethoden eingesetzt:The following test methods were used to assess the cleaning performance:
Zum Nachweis des Reinigungseffektes der erfindungsgemäß eingesetzten Mittel beim manuellen Geschirrspülen wurde der sogenannte Tellertest durchgeführt. Die Methodik ist in der Zeitschrift "Fette, Seifen, Anstrichmittel", 74, (1972), Seiten 163 bis 165 beschrieben.The so-called plate test was carried out to demonstrate the cleaning effect of the agents used according to the invention in manual dishwashing. The methodology is described in the journal "Fette, Seifen, Anstrichmittel", 74 , (1972), pages 163 to 165.
Teller von 14 cm Durchmesser wurden mit je 2 g Rindertalg (Schmelzpunkt 40 bis 42 °C, Säurezahl 9 bis 10) angeschmutzt, 15 Stunden lang bei + 0 bis + 5 °C gelagert und bei 50 °C mit Leitungswasser der Härte 16 °d gespült. Die Prüfprodukte wurden mit einer Dosierung von 0,5 g/l Wasser, bezogen auf Gesamtmittel, oder 0,15 g Einzeltensid/l Wasser eingesetzt. Als Maß für die Reinigungswirkung dient die Anzahl an Tellern, die mit 5 Liter Spülflotte sauber gespült werden = Tellerzahl.Plates of 14 cm in diameter were soiled with 2 g of beef tallow (melting point 40 to 42 ° C, acid number 9 to 10), stored for 15 hours at + 0 to + 5 ° C and at 50 ° C with tap water of hardness 16 ° d rinsed. The test products were used with a dosage of 0.5 g / l water, based on total agent, or 0.15 g individual surfactant / l water. The number of plates that are rinsed clean with 5 liters of washing solution = number of plates serves as a measure of the cleaning effect.
Das zu prüfende Reinigungsmittel wurde auf eine künstlich angeschmutzte Kunststoffoberfläche gegeben. Als künstliche Anschmutzung wurde ein Gemisch aus Ruß, Maschinenöl, Triglycerid gesättigter Fettsäuren und niedersiedendem aliphatischem Kohlenwasserstoff verwendet. Die Testfläche von 26 x 28 cm wurde mit Hilfe eines Flächenstreichers gleichmäßig mit 2 g der künstlichen Anschmutzung beschichtet und anschließend in sieben gleichgroße Flächen von 26 x 4 cm zerschnitten.The cleaning agent to be tested was placed on an artificially soiled plastic surface. A mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling. The test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the help of a surface coater and then cut into seven equally large areas of 26 x 4 cm.
Ein Kunststoffschwamm wurde jeweils mit 6 ml der zu prüfenden unverdünnten Reinigungsmittellösung getränkt und maschinell auf der Testfläche bewegt. Nach 10 Wischbewegungen wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungswirkung, d. h., der Weißgrad der so gereinigten Kunststoffoberfläche, wurde mit einem photoelektrischen Farbmeßgerät LF 90 (Dr. B. Lange) gemessen. Als Weiß-Standard diente die saubere weiße Kunststoffoberfläche.A plastic sponge was impregnated with 6 ml of the undiluted detergent solution to be tested and moved mechanically on the test surface. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, d. that is, the whiteness of the plastic surface thus cleaned was measured with an LF 90 photoelectric colorimeter (Dr. B. Lange). The clean white plastic surface served as the white standard.
Da bei der Messung der sauberen Oberfläche auf 100 % eingestellt und die angeschmutzte Fläche mit 0 angezeigt wurde, waren die abgelesenen Werte bei den gereinigten Kunststoff-Flächen mit dem Prozentgehalt Reinigungsvermögen (% RV) gleichzusetzen. Bei den nachstehenden Versuchen sind die angegebenen %-RV-Werte die nach dieser Methode ermittelten Werte für das Reinigungsvermögen der untersuchten Reinigungsmittel. Sie stellen jeweils Mittelwerte aus 4fachen Bestimmungen dar (vgl. Qualitätsnormen des Industrieverbandes Putz- und Pflegemittel e.V. (IPP), Frankfurt/Main (Fassung 1982) in "Seifen, Fette, Öle, Wachse", 108, (1982) 527-528.Since the measurement of the clean surface was set to 100% and the soiled area was displayed with 0, the read values for the cleaned plastic areas were to be equated with the percentage cleaning ability (% RV). In the experiments below, the% -RV values given are the values determined by this method for the cleaning ability of the cleaning agents examined. They each represent mean values from 4-fold determinations (cf. quality standards of the Industry Association for Cleaning and Care Agents (IPP), Frankfurt / Main (1982 version) in "Soaps, Fats, Oils, Waxes", 108 , (1982) 527-528.
Die zur Bestimmung des Reinigungsvermögens eingesetzte Anschmutzung bestand aus:
Benzin 80/110 -
Testbenzin K 30 44,8
Spezialschwarz 4 4,8
Coray 34 -
Myritol 318 4,8
Vaseline 5,6
Kaolin 20,0
Durcal 2 20,0
(Angaben Gew.-%)
The soiling used to determine the cleaning ability consisted of:
Petrol 80/110 -
White spirit K 30 44.8
Special black 4 4.8
Coray 34 -
Myritol 318 4.8
Vaseline 5.6
Kaolin 20.0
Durcal 2 20.0
(Data% by weight)
Die Zusammensetzung der erfindungsgemäßen Reinigungsmittel ist in den Tabellen angegeben. Daneben finden sich gekennzeichnete Vergleichsversuche gemäß der DE 26 16 404. Die Differenz auf 100 Gew.-% besteht in jedem Falle aus Wasser.The composition of the cleaning agents according to the invention is given in the tables. In addition, there are marked comparative tests according to DE 26 16 404. The difference to 100% by weight in any case consists of water.
Die Bezeichnungen der meist als Natriumsalze vorliegenden Bestandteile in den Tabellen bedeuten, soweit sie nicht aus sich selbst heraus verständlich sind:
ABS : C₁₂₋₁₄-Alkylbenzolsulfonat
Texapon N(R) : C₁₂₋₁₄-Alkyl-(EO)₂-sulfat
Texapon LS(R) : C₁₂₋₁₄-Alkylsulfat
alpha-Sulfosuccinat : alpha-Sulfobernsteinsäuredioctylester
Alkylglucosid : C₁₂₋₁₄-Fettalkoholglucosid mit 1,4 Glucoseeinheiten
alpha-Sulfofettsäureester : alpha-Sulfo-C₁₂₋₁₆-fettsäuremethylester
Dehypon LT 5 : C₁₂₋₁₄-Fettalkohol + 5 Mol Ethylenoxid
Dehypon LS 54 : C₁₂₋₁₄-Fettalkohol + 5 Mol Ethylenxoxid + 4 Mol Propylenoxid
SAS : sek. C₁₃₋₁₅-Alkansulfonat
Amidseife : C₁₂₋₁₄-Fettsäurecyanamid
Comperlan KD(R) : C₁₂₋₁₄-Fettsäurediethanolamid
Dodigen 1611 : C₁₂₋₁₄-Alkyldimethylbenzylammoniumchlorid
Epicol G2G 10 : Umsetzungsprodukt von 1 Mol C₁₂₋₁₄-Alkylepoxid mit 1 Mol Ethylenglykol und 10 Mol Ethylenoxid
EDTA : Ethylendiamintetraessigsäure
EO : Ethylenoxid
Kenndaten für die erfindungsgemäß eingesetzten Celluloseether (statistische Mittelwerte):
ABS: C₁₂₋₁₄ alkylbenzenesulfonate
Texapon N (R) : C₁₂₋₁₄ alkyl (EO) ₂ sulfate
Texapon LS (R) : C₁₂₋₁₄ alkyl sulfate
alpha-sulfosuccinate: alpha-sulfosuccinic acid dioctyl ester
Alkyl glucoside: C₁₂₋₁₄ fatty alcohol glucoside with 1.4 glucose units
alpha-sulfo fatty acid ester: alpha-sulfo-C₁₂₋₁₆-fatty acid methyl ester
Dehypon LT 5: C₁₂₋₁₄ fatty alcohol + 5 moles of ethylene oxide
Dehypon LS 54: C₁₂₋₁₄ fatty alcohol + 5 moles of ethylene oxide + 4 moles of propylene oxide
SAS: sec. C₁₃₋₁₅ alkanesulfonate
Amide soap: C₁₂₋₁₄ fatty acid cyanamide
Comperlan KD (R) : C₁₂₋₁₄ fatty acid diethanolamide
Dodigen 1611: C₁₂₋₁₄ alkyldimethylbenzylammonium chloride
Epicol G2G 10: reaction product of 1 mole of C₁₂₋₁₄ alkyl epoxide with 1 mole of ethylene glycol and 10 moles of ethylene oxide
EDTA: ethylenediaminetetraacetic acid
EO: ethylene oxide
Characteristic data for the cellulose ethers used according to the invention (statistical mean values):
Für ein Vergleichsbeispiel gemäß der DE 26 16 404 wurde ein kationaktives Celluloseetherderivat, nämlich das Polymer JR 400(R)der Union Carbide (vgl. US 3 472 840) mit einem mittleren Molgewicht von 400 000 verwendet.
Wie die Ergebnisse in Tabelle 1 zeigen, weisen die erfindungsgemäßen ampholytischen Celluloseether eine höhere Leistungssteigerung der Spülmittel auf als kationische Cellulosether gemäß DE 26 16 404.As the results in Table 1 show, the ampholytic cellulose ethers according to the invention have a higher performance increase in the detergents than cationic cellulose ethers according to DE 26 16 404.
Tabelle 2 zeigt, daß die erfindungsgemäßen ampholytischen Celluloseether, in kleinen Anteilen in Allzweck- bzw. Desinfektionsreinigungsmitteln eingearbeitet, deutliche reinigungsverstärkende Wirkungen herbeiführen.Table 2 shows that the ampholytic cellulose ethers according to the invention, incorporated in small proportions in general-purpose or disinfectant cleaning agents, bring about distinct cleaning-enhancing effects.
Ein weiterer überraschender Vorteil der ampholytischen Celluloseether zeigte sich bei der Fettentfernung auf erneut angeschmutzten Tellern, die zuvor bereits in einer polymerenhaltigen Spülflotte gereinigt wurden. Folgender Versuch machte diesen Vorteil deutlich:Another surprising advantage of the ampholytic cellulose ethers was the removal of fat on newly soiled plates that had already been cleaned in a polymer-containing washing liquor. The following experiment made this advantage clear:
Die in der polymerenhaltigen Spülflotte gereinigten Teller wurden - wie schon beschrieben - erneut mit 2 g Rindertalg/Teller angeschmutzt und 15 Stunden lang bei Temperaturen von 0 - 5 °C gelagert. Ein Teller wurde dann waagerecht in 5 Liter Spülflotte von 50 °C gelegt und die Zeit gemessen, bis zu der die Fettentfernung von der Telleroberfläche ohne manuelle Zusatzeinwirkung abgeschlossen war. Bei Tellern, die vor ihrer Wiederanschmutzung mit Rindertalg in einer polymerenhaltigen Spülflotte gespült worden waren, betrug die Reinigungszeit ungefähr 2,5 Minuten; bei Tellern, die vor ihrer Wiederanschmutzung mit Rindertalg in einer polymerenfreien Spülflotte gespült wurden, konnte auch nach wesentlich längeren Zeiten keine vollständige Fettentfernung erreicht werden.
Claims (4)
1 bis 40 Gew.-%, vorzugsweise 5 bis 25 Gew.-% anionische Tenside,
0 bis 20 Gew.-%, vorzugsweise 0,5 bis 15 Gew.-% nichtionische Tenside oder Amphotenside,
0 bis 10 Gew.-%, vorzugsweise 0,5 bis 5 Gew.-% Gerüstsubstanzen,
1 bis 15 Gew.-%, vorzugsweise 1,5 bis 12 Gew.-% Lösungsvermittler,
0,01 bis 1,5 Gew.-%, vorzugsweise 0,03 bis 1 Gew.-% der erfindungsgemäßen Polymeren,
sowie gegebenenfalls sonstige übliche Hilfsstoffe, insbesondere Duft- und Farbstoffe, Konservierungsmittel und Mittel zur pH-Einstellung sowie als Rest bis 100 Gew.-% Wasser enthalten.2. Liquid composition according to claim 1, characterized in that it
1 to 40% by weight, preferably 5 to 25% by weight of anionic surfactants,
0 to 20% by weight, preferably 0.5 to 15% by weight, of nonionic surfactants or amphoteric surfactants,
0 to 10% by weight, preferably 0.5 to 5% by weight of builder substances,
1 to 15% by weight, preferably 1.5 to 12% by weight, of solubilizer,
0.01 to 1.5% by weight, preferably 0.03 to 1% by weight, of the polymers according to the invention,
and, if appropriate, other customary auxiliaries, in particular fragrances and dyes, preservatives and agents for adjusting the pH, and the remainder up to 100% by weight of water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3726912 | 1987-08-13 | ||
| DE19873726912 DE3726912A1 (en) | 1987-08-13 | 1987-08-13 | LIQUID MEDIUM TO CLEAN HARD SURFACES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0303188A2 true EP0303188A2 (en) | 1989-02-15 |
| EP0303188A3 EP0303188A3 (en) | 1989-05-24 |
Family
ID=6333623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88112708A Withdrawn EP0303188A3 (en) | 1987-08-13 | 1988-08-04 | Liquid products for cleaning hard surfaces |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4976885A (en) |
| EP (1) | EP0303188A3 (en) |
| JP (1) | JPS6466299A (en) |
| DE (1) | DE3726912A1 (en) |
| DK (1) | DK446888A (en) |
| TR (1) | TR23342A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0875555A1 (en) * | 1997-04-30 | 1998-11-04 | The Procter & Gamble Company | Use of polysaccharide polymer in liquid acidic composition |
| WO2008155068A2 (en) * | 2007-06-20 | 2008-12-24 | Clariant Finance (Bvi) Limited | Surfactant mixtures with synergistic characteristics |
| WO2009016060A1 (en) * | 2007-07-31 | 2009-02-05 | Henkel Ag & Co. Kgaa | Textile care agent having cellulose ether comprising amine groups |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8811953D0 (en) * | 1988-05-20 | 1988-06-22 | Unilever Plc | General-purpose cleaning compositions |
| DE3827778A1 (en) * | 1988-08-16 | 1990-02-22 | Henkel Kgaa | PASTE-SHAPED DETERGENT AND CLEANING AGENT AND METHOD FOR PRODUCING THE SAME |
| JP2526105B2 (en) * | 1988-09-20 | 1996-08-21 | 花王株式会社 | Detergent composition |
| JPH0721154B2 (en) * | 1988-10-15 | 1995-03-08 | 三洋化成工業株式会社 | Cleaning composition |
| US5118440A (en) * | 1990-03-05 | 1992-06-02 | The Procter & Gamble Company | Light-duty liquid dishwashing detergent composition containing alkyl polysaccharide and alpha-sulfonated fatty acid alkyl ester surfactants |
| DE4114491A1 (en) * | 1991-05-03 | 1992-11-05 | Henkel Kgaa | LIQUID DETERGENT |
| US5523024A (en) * | 1992-02-07 | 1996-06-04 | The Clorox Company | Reduced residue hard surface cleaner |
| US5585342A (en) * | 1995-03-24 | 1996-12-17 | The Clorox Company | Reduced residue hard surface cleaner |
| US5252245A (en) * | 1992-02-07 | 1993-10-12 | The Clorox Company | Reduced residue hard surface cleaner |
| US5468423A (en) * | 1992-02-07 | 1995-11-21 | The Clorox Company | Reduced residue hard surface cleaner |
| US5817615A (en) * | 1992-02-07 | 1998-10-06 | The Clorox Company | Reduced residue hard surface cleaner |
| US5308531A (en) * | 1992-08-31 | 1994-05-03 | Henkel Corporation | Pine-oil containing hard surface cleaning composition |
| DE4319287A1 (en) * | 1993-06-11 | 1994-12-15 | Henkel Kgaa | Pourable liquid aqueous detergent concentrates |
| US5494611A (en) * | 1993-11-24 | 1996-02-27 | Armor All Products Corporation | Dual-purpose cleaning composition for painted and waxed surfaces |
| ZA955295B (en) * | 1994-06-27 | 1996-02-13 | Diversey Corp | Non-silicated soft metal safe product |
| DE4439570A1 (en) * | 1994-11-05 | 1996-05-09 | Henkel Kgaa | Laundry after-treatment agent |
| GB2309974A (en) * | 1996-02-08 | 1997-08-13 | Procter & Gamble | Use of cellulose ethers for soil removal |
| US6384011B1 (en) | 1997-09-15 | 2002-05-07 | The Procter & Gamble Company | Laundry detergent compositions with cellulosic based polymers to provide appearance and integrity benefits to fabrics laundered therewith |
| HUP0004929A3 (en) * | 1997-09-15 | 2003-03-28 | Procter & Gamble | Cellulosic based polymers, detergent and laundry additive composition containing the same |
| US6017872A (en) * | 1998-06-08 | 2000-01-25 | Ecolab Inc. | Compositions and process for cleaning and finishing hard surfaces |
| US5935921A (en) * | 1999-01-26 | 1999-08-10 | Colgate-Palmolive Co. | Liquid descaling composition |
| US6653274B1 (en) * | 1999-09-27 | 2003-11-25 | The Proctor & Gamble Company | Detergent composition comprising a soil entrainment system |
| US20020183235A1 (en) * | 2001-03-26 | 2002-12-05 | Sprague Sherman Jay | Polymer cleaner formulation |
| DE10154103A1 (en) * | 2001-11-02 | 2003-05-15 | Cognis Deutschland Gmbh | Biodegradable compositions |
| US7563753B2 (en) * | 2001-12-12 | 2009-07-21 | Hynix Semiconductor Inc. | Cleaning solution for removing photoresist |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU401676A1 (en) * | 1972-01-28 | 1973-10-12 | METHOD OF OBTAINING AMFOLITES |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3472840A (en) * | 1965-09-14 | 1969-10-14 | Union Carbide Corp | Quaternary nitrogen-containing cellulose ethers |
| US3676423A (en) * | 1969-09-29 | 1972-07-11 | Hubinger Co | Amphoteric cellulose and process for the preparation thereof |
| GB1553201A (en) * | 1975-04-18 | 1979-09-26 | Colgate Palmolive Co | Method of cleaning glass or glazed articles |
| GB1506427A (en) * | 1975-04-29 | 1978-04-05 | Unilever Ltd | Liquid detergent |
| DE2709690B1 (en) * | 1977-03-05 | 1978-05-11 | Henkel Kgaa | Liquid detergent |
| DE2840464C3 (en) * | 1978-09-16 | 1981-04-09 | Henkel KGaA, 4000 Düsseldorf | Cleaning agents for windows, mirrors and reflective surfaces |
| DE2840463C2 (en) * | 1978-09-16 | 1983-12-22 | Henkel KGaA, 4000 Düsseldorf | Using a liquid agent to clean hard surfaces |
| DE2913049A1 (en) * | 1979-03-31 | 1980-10-16 | Henkel Kgaa | LIQUID DETERGENT |
| DE3011550A1 (en) * | 1980-03-26 | 1981-10-01 | Henkel KGaA, 4000 Düsseldorf | LIQUID CLEANING AGENTS |
| US4383062A (en) * | 1981-01-28 | 1983-05-10 | General Electric | Waterborne coating compositions |
| PH17613A (en) * | 1981-05-29 | 1984-10-05 | Unilever Nv | General-purpose cleaning composition |
| JPS5813700A (en) * | 1981-07-17 | 1983-01-26 | 花王株式会社 | Detergent composition |
| GB8311854D0 (en) * | 1983-04-29 | 1983-06-02 | Unilever Plc | Detergent compositions |
| DE3512535A1 (en) * | 1985-04-06 | 1986-10-16 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR MANUAL CLEANING OF OBJECTS WITH HARD SURFACES |
-
1987
- 1987-08-13 DE DE19873726912 patent/DE3726912A1/en not_active Withdrawn
-
1988
- 1988-06-08 TR TR414/88A patent/TR23342A/en unknown
- 1988-08-04 EP EP88112708A patent/EP0303188A3/en not_active Withdrawn
- 1988-08-10 DK DK446888A patent/DK446888A/en unknown
- 1988-08-12 US US07/231,799 patent/US4976885A/en not_active Expired - Fee Related
- 1988-08-12 JP JP63202601A patent/JPS6466299A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU401676A1 (en) * | 1972-01-28 | 1973-10-12 | METHOD OF OBTAINING AMFOLITES |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 81, 1974, Seite 104, Nr. 79600z, Columbus, Ohio, US; & SU-A-401 676 (INSTITUTE OF GENERAL AND INORGANIC CHEMISTRY, ACADEMY OF SCIENCES, BELORUSSIAN S.S.R.) 12-10-1973 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0875555A1 (en) * | 1997-04-30 | 1998-11-04 | The Procter & Gamble Company | Use of polysaccharide polymer in liquid acidic composition |
| WO2008155068A2 (en) * | 2007-06-20 | 2008-12-24 | Clariant Finance (Bvi) Limited | Surfactant mixtures with synergistic characteristics |
| WO2008155068A3 (en) * | 2007-06-20 | 2009-02-26 | Clariant Int Ltd | Surfactant mixtures with synergistic characteristics |
| WO2009016060A1 (en) * | 2007-07-31 | 2009-02-05 | Henkel Ag & Co. Kgaa | Textile care agent having cellulose ether comprising amine groups |
Also Published As
| Publication number | Publication date |
|---|---|
| US4976885A (en) | 1990-12-11 |
| TR23342A (en) | 1989-12-14 |
| DK446888A (en) | 1989-02-14 |
| EP0303188A3 (en) | 1989-05-24 |
| DE3726912A1 (en) | 1989-02-23 |
| DK446888D0 (en) | 1988-08-10 |
| JPS6466299A (en) | 1989-03-13 |
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