EP0632824B1 - Liquid cleaning products - Google Patents

Liquid cleaning products Download PDF

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Publication number
EP0632824B1
EP0632824B1 EP93906556A EP93906556A EP0632824B1 EP 0632824 B1 EP0632824 B1 EP 0632824B1 EP 93906556 A EP93906556 A EP 93906556A EP 93906556 A EP93906556 A EP 93906556A EP 0632824 B1 EP0632824 B1 EP 0632824B1
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EP
European Patent Office
Prior art keywords
weight
carbon atoms
detergent
copolymer
acrylic
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EP93906556A
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German (de)
French (fr)
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EP0632824A1 (en
Inventor
Dimitrios Ouzounis
Ulrich Eicken
Ortburg Guirr
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • Liquid detergents, dishwashing detergents and cleaning agents are usually aqueous solutions of anionic and / or nonionic surfactants and customary additives.
  • a preferred area of application for such agents is the manual washing of dining utensils and other related equipment.
  • Such cleaning agents are all the more effective the better their fat emulsifying capacity is, because with them e.g. the number of plates that can be cleaned with a given amount of detergent increases.
  • the present invention therefore relates to liquid cleaning agents with improved emulsifying power and increased cleaning power.
  • alkyl ether sulfates that is to say sulfated adducts of about 2 to 5 moles of ethylene oxide with fatty alcohols with about 10 to 16 carbon atoms in the alkyl radical, have a good cleansing power with a mild effect on the skin at the same time.
  • the commercially available dishwashing detergents customary in the market therefore generally represent aqueous solutions of such alkyl ether sulfates in combination with other anionic surfactants such as n-alkylbenzenesulfonates and / or alkanesulfonates, optionally also olefin sulfonates, alkyl sulfates or alkyl sulfosuccinates as well as nonionic surfactants, solubilizers, colorants and fragrances.
  • anionic surfactants such as n-alkylbenzenesulfonates and / or alkanesulfonates
  • olefin sulfonates alkyl sulfates or alkyl sulfosuccinates
  • nonionic surfactants solubilizers, colorants and fragrances.
  • alkyl ether sulfate mixture consisting of 50% by weight of a C 12 alkyl ether sulfate and 50% by weight of a C 14 alkyl ether sulfate with 1 to 5, preferably 2 to 4, ethylene oxide groups as an ether component compared to the commonly used alkyl ether sulfate mixture, which contains the same components in a weight ratio of 70:30, leads to an unexpected further reduction in skin irritation without changing the known good cleaning power of such agents.
  • European patent application 89 213 describes a thickened surfactant preparation which consists of water and 5 to 40% by weight of anionic, nonionic or amphoteric surfactants and contains a copolymer which is soluble in alkaline and is prepared by emulsion polymerization. However, this copolymer is used as a thickener.
  • the European patent application gives no information about a cleaning-enhancing effect.
  • French patent application 2294231 relates to a floor cleaning agent which contains 5 to 20% by weight of a copolymer which, on the other hand, is insoluble in acid in alkali and which has a molecular weight between 100,000 and 2.5 million. Surfactants and other ingredients are also present. Although quite high molecular weights are mentioned here, it is not clear to the person skilled in the art that in the extreme molecular weight range such as that due to intrinsic viscosities of more than 400 ml. g -1 is to be defined, a drastic increase in the cleaning performance and the emulsifying capacity can be determined.
  • amphoteric surfactants of the betaine type usually have a mild effect on the skin or that their use can achieve a significant increase in cleansing effectiveness. Liquid, manual dishwashing detergents containing the above-mentioned components are therefore often used.
  • the present invention now relates to a liquid cleaning agent, in particular for manual dishwashing, based on an aqueous solution of anionic surfactants, optionally together with nonionic and / or amphoteric surfactants, solvents, solubilizers, corrosion inhibitors, preservatives, thickeners and colorants and fragrances, which is characterized in that it additionally contains 0.001 to 1% by weight of a cleaning-enhancing, water-soluble, anionic, practically uncrosslinked copolymer of a) esters of acrylic and / or methacrylic acid with 1 to 8 carbon atoms in the alcohol radical and b) contains unsaturated, aliphatic carboxylic acids with 3 to 5 carbon atoms in the acyl residue with an intrinsic viscosity [n] ⁇ 400ml ⁇ g -1 , measured in tetrohydrofuran (THF) at 20 ° C.
  • anionic surfactants optionally together with nonionic and / or amphoteric surfactants, solvents,
  • a preferred copolymer consists of approximately 80-20, in particular approximately 60-40% by weight of a) and approximately 20-80, in particular 40-60% by weight b).
  • the alcohol residue of the esters a) preferably contains 1 to 4, in particular 1 to 2, carbon atoms.
  • the copolymers can also be used in minor amounts of up to about 5% by weight of other radically polymerizable vinyl monomers such as e.g. Contain ayrolamides or (meth) acrylates.
  • the copolymer is an acidic dispersion and can advantageously be used in this form.
  • the cleaning agents which generally have a neutral to slightly alkaline pH, the copolymers are partially or completely neutralized and dissolved so that they are no longer in dispersion form.
  • the water-soluble anionic copolymers used according to the invention are prepared in a known manner by emulsion polymerization, as described, for example, in US Pat. No. 4,795,772 or EP 184,785.
  • the unsaturated carboxylic acids used for this purpose are preferably acrylic or methacrylic acid.
  • the intrinsic viscosity is determined according to the method described in B. Vollmert: "Floor plan of macromolecular chemistry", Volume III, page 55 ff, E. Vollmert Verlag, Düsseldorf, 1988.
  • the specific viscosity increases proportionally with the concentration at high concentrations, while at low concentrations the viscosity can decrease with increasing concentration.
  • the intrinsic viscosities of these copolymers are determined with the aid of diagrams in which the concentration is plotted on the abscissa and the specific viscosity is plotted on the ordinate by extrapolation of the part which rises linearly at high concentrations to the concentration 0.
  • alkyl ether sulfates can also be used as further anionic surfactants, just like n-alkylbenzenesulfonates with 9 to 16, preferably 12 carbon atoms in the alkyl radical, alkanesulfonates with 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical, olefin sulfonates with 12 to 16, preferably 12 up to 14 carbon atoms in the n-alkyl radical and alkyl sulfates with 8 to 18, preferably 8 to 14 carbon atoms in the alkyl radical, individually or as mixtures with one another or with one another.
  • Betaine compounds of the formula can be used as amphoteric surfactants are used in which R 1 is an alkyl radical with 8 to 20, preferably 10 to 18 carbon atoms, which is optionally interrupted by heteroatoms or heteroatom groups, and R 2 and R 3 are identical or different alkyl radicals with 1 to 3 carbon atoms.
  • R 1 is an alkyl radical with 8 to 20, preferably 10 to 18 carbon atoms, which is optionally interrupted by heteroatoms or heteroatom groups
  • R 2 and R 3 are identical or different alkyl radicals with 1 to 3 carbon atoms.
  • C 10 -C 18 -Alkyldimethylcarboxymethylbetaine and C 11 -C 17 -Alkylamidopropyldimethylcarboxymethylbetaine are preferred.
  • adducts are from 4 to 20, preferably from 4 to 10, mol of alkylene oxide, preferably ethylene oxide to C 8 -C 12 alkylbenzenes, C 10 -C 20 -, preferably C 12 -C 18 -alkanols, C 10 -C 18 -, carboxylic acid alkanolamides, but also the addition products of ethylene oxide and polypropylene glycols, which have become known under the name Pluronics (R) , and addition products of 1 to 7 mol of ethylene oxide with C 12 -C 18 reacted with 1 to 5 mol of propylene oxide -Alcanole suitable.
  • C 8 -C 18 preferably C 8 -C 12 alkyl polyglucosides with 1 to 10, preferably 1 to 2 and in particular 1.1 to 1.4 glucose units in the molecule are particularly suitable.
  • the solvents to be added if necessary are low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol.
  • Solubilizers for example for dyes and perfume oils, can be used, for example, as alkanolamines, polyols such as ethylene glycol, 1,2-propylene glycol, glycerol and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical.
  • the preferred thickeners include urea, sodium chloride, ammonium chloride and magnesium chloride, which can also be used in combination.
  • Corrosion inhibitors and preservatives include, for example, sodium benzoate, formaldehyde and sodium sulfite.
  • the cleaning agents can also contain conventional disinfectants.
  • liquid cleaning agents according to the invention of the following examples were obtained by stirring the individual constituents in any order and leaving the mixture to stand until there were no bubbles.
  • the sodium salts were used as anionic surfactants.
  • a polymer emulsion was made 55 g Ethyl acrylate, 25 g Methacrylic acid, 20 g Acrylic acid and the same amounts of other ingredients as in Example A. It also had a polymer content of 20% by weight.
  • the emulsion was then poured into a 250 ml measuring cylinder with a diameter of 3.6 cm (2 ml graduation, industrial standard) and the aqueous phase which separated out was determined after 1 hour and after 4 hours.
  • the data relate to% by weight of the pure active ingredient (AS).

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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)
  • Fluid-Pressure Circuits (AREA)
  • Lubricants (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

Liquid cleaning products based on an aqueous solution of surface-active agents, solvents, solubilizers, corrosion inhibitors, preservatives, thickeners, colorants and perfumes, to which is added a copolymer of acrylic or methacrylic acid esters with 1 to 8 C atoms in the alcohol residue and unsaturated aliphatic carboxylic acids with 3 to 5 C atoms, have a limiting viscosity number [n] equal to or higher than 100 ml . g?-1, measured in tetrahydrofurane at 20 C.

Description

Flüssige Wasch-, Spül- und Reinigungsmittel stellen meist wäßrige Lösungen von anionischen und/oder nichtionischen Tensiden und üblichen Zusatzstoffen dar. Ein bevorzugtes Anwendungsgebiet derartiger Mittel ist das manuelle Spülen von Eßgeschirr und anderen damit verwandten Gerätschaften. Solche Reinigungsmittel sind um so wirkungsvoller, je besser ihr Fettemulgiervermögen ist, weil damit z.B. die Zahl der Teller steigt, die sich mit einer vorgegebenen Reinigungsmittelmenge säubern läßt. Die vorliegende Erfindung betrifft daher flüssige Reinigungsmittel mit verbessertem Emulgiervermögen und verstärkter Reinigungskraft.Liquid detergents, dishwashing detergents and cleaning agents are usually aqueous solutions of anionic and / or nonionic surfactants and customary additives. A preferred area of application for such agents is the manual washing of dining utensils and other related equipment. Such cleaning agents are all the more effective the better their fat emulsifying capacity is, because with them e.g. the number of plates that can be cleaned with a given amount of detergent increases. The present invention therefore relates to liquid cleaning agents with improved emulsifying power and increased cleaning power.

Es ist bekannt, daß sogenannte Alkylethersulfate, das heißt sulfatierte Anlagerungsprodukte von etwa 2 bis 5 Mol Ethylenoxid an Fettalkohole mit etwa 10 bis 16 Kohlenstoffatomen im Alkylrest, eine gute Reinigungskraft bei gleichzeitiger milder Wirkung auf die Haut besitzen. Die marktüblichen, manuell anzuwendenden Geschirrspülmittel stellen daher im allgemeinen wäßrige Lösungen solcher Alkylethersulfate in Verbindung mit anderen anionischen Tensiden wie n-Alkylbenzolsulfonaten und/oder Alkansulfonaten, gegebenenfalls auch Olefinsulfonaten, Alkylsulfaten oder Alkylsulfosuccinaten sowie nichtionischen Tensiden, Lösungsvermittlern, Farb- und Duftstoffen dar.It is known that so-called alkyl ether sulfates, that is to say sulfated adducts of about 2 to 5 moles of ethylene oxide with fatty alcohols with about 10 to 16 carbon atoms in the alkyl radical, have a good cleansing power with a mild effect on the skin at the same time. The commercially available dishwashing detergents customary in the market therefore generally represent aqueous solutions of such alkyl ether sulfates in combination with other anionic surfactants such as n-alkylbenzenesulfonates and / or alkanesulfonates, optionally also olefin sulfonates, alkyl sulfates or alkyl sulfosuccinates as well as nonionic surfactants, solubilizers, colorants and fragrances.

Es ist weiterhin bekannt (DE 30 11 550), daß der Einsatz eines Alkylethersulfatgemisches, bestehend aus 50 Gew.-% eines C12-Alkylethersulfats und 50 Gew.-% eines C14-Alkylethersulfats mit 1 bis 5, vorzugsweise 2 bis 4 Ethylenoxidgruppen als Etherkomponente gegenüber dem üblicherweise eingesetzten Alkylethersulfatgemisch, das die gleichen Komponenten im Gewichtsverhältnis 70 : 30 enthält, zu einer unerwarteten weiteren Verminderung der Hautirritation führt, ohne die bekannt gute Reinigungskraft derartiger Mittel zu verändern.It is also known (DE 30 11 550) that the use of an alkyl ether sulfate mixture consisting of 50% by weight of a C 12 alkyl ether sulfate and 50% by weight of a C 14 alkyl ether sulfate with 1 to 5, preferably 2 to 4, ethylene oxide groups as an ether component compared to the commonly used alkyl ether sulfate mixture, which contains the same components in a weight ratio of 70:30, leads to an unexpected further reduction in skin irritation without changing the known good cleaning power of such agents.

Aus der europäischen Patentanmeldung EP 215 451 sind Fußbodenreinigungsmittel bekannt, die neben Tensiden, Komplexbildnern und fakultativen Zusatzstoffen 0,1 bis 4,5 Gew.-% eines alkalilöslichen, nichtmetallvernetzenden Polymers mit einer minimalen Filmbildungstemperatur zwischen 0 und 70 °C enthalten. Die europäische Patentanmeldung macht jedoch keine Aussagen über Vorteile, die mit höhermolekularen Produkten zu erzielen sind.From European patent application EP 215 451, floor cleaning agents are known which, in addition to surfactants, complexing agents and optional additives, contain 0.1 to 4.5% by weight of an alkali-soluble, non-metal-crosslinking polymer with a minimum film-forming temperature between 0 and 70 ° C. However, the European patent application makes no statements about the advantages that can be achieved with higher molecular weight products.

Die europäische Patentanmeldung 89 213 beschreiben eine verdickte Tensidzubereitung, die aus Wasser sowie 5 bis 40 Gew.-% anionischer, nichtionischer oder amphoterer Tenside besteht und ein Copolymer enthält, das im Alkalischen löslich ist und durch Emulsionspolymerisation hergestellt ist. Dieses Copolymer ist jedoch als Verdickungsmittel eingesetzt. Die europäische Patentanmeldung macht keine Angaben über eine reinigungsverstärkende Wirkung.European patent application 89 213 describes a thickened surfactant preparation which consists of water and 5 to 40% by weight of anionic, nonionic or amphoteric surfactants and contains a copolymer which is soluble in alkaline and is prepared by emulsion polymerization. However, this copolymer is used as a thickener. The European patent application gives no information about a cleaning-enhancing effect.

Die französische Patentanmeldung 2294231 schließlich betrifft ein Bodenreinigungsmittel, daß 5 bis 20 Gew.-% eines Copolymers enthält, das im Sauren unlöslich im Alkalischen hingegen löslich ist und welches ein Molekulargewicht zwischen 100 000 und 2,5 Mio. aufweist. Weiterhin sind Tenside und andere Bestandteile zugegen. Wenngleich hier recht hohe Molekulargewichte genannt sind, so ist für den Fachmann doch nicht zu entnehmen, daß im extremen Molekulargewichtsbereich wie er durch Grenzviskositäten von mehr als 400 ml . g-1 zu definieren ist, eine drastische Verstärkung der Reinigungsleistung und des Emulgiervermögens festzustellen ist.Finally, French patent application 2294231 relates to a floor cleaning agent which contains 5 to 20% by weight of a copolymer which, on the other hand, is insoluble in acid in alkali and which has a molecular weight between 100,000 and 2.5 million. Surfactants and other ingredients are also present. Although quite high molecular weights are mentioned here, it is not clear to the person skilled in the art that in the extreme molecular weight range such as that due to intrinsic viscosities of more than 400 ml. g -1 is to be defined, a drastic increase in the cleaning performance and the emulsifying capacity can be determined.

Schließlich ist allgemein bekannt, daß amphotere oberflächenaktive Mittel vom Betaintyp meist eine milde Wirkung auf die Haut ausüben oder durch ihren Einsatz eine signifikante Steigerung der Reinigungswirksamkeit erzielt werden kann. Man verwendet daher gern flüssige, manuell anwendbare Geschirreinigungsmittel mit den vorstehend angeführten Bestandteilen.Finally, it is generally known that amphoteric surfactants of the betaine type usually have a mild effect on the skin or that their use can achieve a significant increase in cleansing effectiveness. Liquid, manual dishwashing detergents containing the above-mentioned components are therefore often used.

Gegenstand der vorliegenden Erfindung ist nun ein flüssiges Reinigungsmittel, insbesondere für das manuelle Geschirrspülen, auf Basis einer wäßrigen Lösung von anionischen Tensiden, gegebenenfalls zusammen mit nichtionischen und/oder amphoteren Tensiden, Lösungsmitteln, Lösungsvermittlern, Korrosionsinhibitoren, Konservierungsmitteln, Verdickungsmitteln sowie Farb- und Duftstoffen, das dadurch gekennzeichnet ist, daß es zusätzlich 0,001 bis 1Gew.-% eines reinigungsverstärkenden, wasserlöslichen, anionischen, praktisch unvernetztes Co-Polymerisats aus a) Estern der Acryl- und/oder der Methacrylsäure mit 1 bis 8 C-Atomen im Alkoholrest und b) ungesättigten, aliphatischen Carbonsäuren mit 3 bis 5 C-Atomen im Acylrest mit einer Grenzviskosität [n] ≥ 400ml · g-1, gemessen in Tetrohydrofuran (THF) bei 20 °C, enthält. Ein bevorzugtes Co-Polymerisat besteht aus etwa 80 - 20, insbesondere etwa 60 - 40 Gew.-% an a) und etwa 20 - 80, insbesondere 40 - 60 Gew.-% b). Der Alkoholrest der Ester a) enthält vorzugsweise 1 bis 4, insbesondere 1 bis 2 C-Atome.The present invention now relates to a liquid cleaning agent, in particular for manual dishwashing, based on an aqueous solution of anionic surfactants, optionally together with nonionic and / or amphoteric surfactants, solvents, solubilizers, corrosion inhibitors, preservatives, thickeners and colorants and fragrances, which is characterized in that it additionally contains 0.001 to 1% by weight of a cleaning-enhancing, water-soluble, anionic, practically uncrosslinked copolymer of a) esters of acrylic and / or methacrylic acid with 1 to 8 carbon atoms in the alcohol radical and b) contains unsaturated, aliphatic carboxylic acids with 3 to 5 carbon atoms in the acyl residue with an intrinsic viscosity [n] ≥ 400ml · g -1 , measured in tetrohydrofuran (THF) at 20 ° C. A preferred copolymer consists of approximately 80-20, in particular approximately 60-40% by weight of a) and approximately 20-80, in particular 40-60% by weight b). The alcohol residue of the esters a) preferably contains 1 to 4, in particular 1 to 2, carbon atoms.

Die Co-Polymerisate können auch noch in untergeordneten Mengen von bis zu etwa 5 Gew.-% andere radikalisch polymerisierbare Vinylmonomere wie z.B. Ayrolamide oder (Meth)acrylate enthalten. Das Co-Polymerisat ist eine saure Dispersion und kann zweckmäßig in dieser Form eingesetzt werden. Bei der Einarbeitung in die Reinigungsmittel, die im allgemeinen einen neutralen bis leicht alkalischen pH-Wert aufweisen, tritt eine teilweise oder vollständige Neutralisation und Lösung der Co-Polymeren ein, so daß sie nicht mehr in Dispersionsform vorliegen.The copolymers can also be used in minor amounts of up to about 5% by weight of other radically polymerizable vinyl monomers such as e.g. Contain ayrolamides or (meth) acrylates. The copolymer is an acidic dispersion and can advantageously be used in this form. During incorporation into the cleaning agents, which generally have a neutral to slightly alkaline pH, the copolymers are partially or completely neutralized and dissolved so that they are no longer in dispersion form.

Die Zusammensetzung der erfindungsgemäßen wäßrigen Reinigungsmittellösung bewegt sich dabei vorzugsweise etwa in folgendem Rahmen:

5 bis 65,
insbesondere 10 bis 40 Gew.-% eines Gemisches, bestehend aus wenigstens zwei der nachfolgenden Tenside
0 bis 40,  insbesondere 4 bis 20 Gew.-% eines Gemisches aus je 50 Teilen eines sulfatierten Anlagerungsproduktes von 1 bis 5, vorzugsweise 2 bis 4 Mol Ethylenoxid an ein n-C12-Alkanol und an ein n-C14-Alkanol,
0 bis 40,  insbesondere 5 bis 20 Gew.-% eines oder mehrerer weiterer anionischer Tenside,
0 bis 20,  insbesondere 1 bis 5 Gew.-% eines oberflächenaktiven Betains,
0 bis 20,  insbesondere 0 bis 5 Gew.-% eines nichtionischen Tensids,
0,001 bis 1,
insbesondere 0,005 bis 0,5 Gew.-% eines reinigungsverstärkenden Co-Polymerisats aus etwa 80 - 20, insbesondere etwa 60 - 40 Gew.-% an Estern der Acryl-und/oder der Methacrylsäure mit 1 bis 4, insbesondere 1 bis 2 C-Atomen im Alkoholrest und etwa 20 - 80, insbesondere etwa 40 - 60 Gew.-% ungesättigten, aliphatischen Carbonsäuren mit 3 bis 5 C-Atomen im Acylrest Grenzviskosität [n] ≥ 400 ml · g-1, gemessen in THF bei 20 °C,
0 bis 20,
insbesondere 2 bis 10 Gew.-% eines Lösungsmittels,
0 bis 10,
insbesondere 0,2 bis 5 Gew.-% eines Lösungsvermittlers,
0 bis 10,
insbesondere 0,5 bis 8 Gew.-% eines Verdickungsmittels,
0 bis 5,
insbesondere 0,1 bis 2 Gew.-% Korrosionsinhibitoren und Konservierungsmittel,
0 bis 0,1
Gew.-% Farbstoff,
0 bis 1,0
Gew.-% Parfümöl und
Rest bis 100 Gew.-% Wasser.The composition of the aqueous cleaning agent solution according to the invention is preferably in the following range:
5 to 65,
in particular 10 to 40% by weight of a mixture consisting of at least two of the following surfactants
0 to 40, especially 4 to 20 wt .-% of a mixture of each 50 parts of a sulfated adduct of 1 to 5, preferably 2 to 4, moles of ethylene oxide to an nC 12 alkanol and to an nC 14 alkanol,
0 to 40, in particular 5 to 20% by weight of one or more further anionic surfactants,
0 to 20, in particular 1 to 5% by weight of a surface-active betaine,
0 to 20, in particular 0 to 5% by weight of a nonionic surfactant,
0.001 to 1,
in particular 0.005 to 0.5% by weight of a cleaning-reinforcing copolymer of about 80-20, in particular about 60-40% by weight of esters of acrylic and / or methacrylic acid with 1 to 4, in particular 1 to 2 C. -Atoms in the alcohol residue and about 20 - 80, in particular about 40 - 60 wt .-% unsaturated, aliphatic carboxylic acids with 3 to 5 carbon atoms in the acyl residue intrinsic viscosity [n] ≥ 400 ml · g -1 , measured in THF at 20 ° C,
0 to 20,
in particular 2 to 10% by weight of a solvent,
0 to 10,
in particular 0.2 to 5% by weight of a solubilizer,
0 to 10,
in particular 0.5 to 8% by weight of a thickener,
0 to 5,
in particular 0.1 to 2% by weight of corrosion inhibitors and preservatives,
0 to 0.1
% By weight of dye,
0 to 1.0
% By weight of perfume oil and
Balance up to 100% by weight water.

Die erfindungsgemäß eingesetzten wasserlöslichen anionischen Co-Polymerisate werden in bekannter Weise durch Emulsionspolymerisation hergestellt, wie beispielsweise in US 4 795 772 oder EP 184 785 beschrieben. Bei den hierzu verwendeten ungesättigten Carbonsäuren handelt es sich vorzugsweise um Acryl- oder Methacrylsäure.The water-soluble anionic copolymers used according to the invention are prepared in a known manner by emulsion polymerization, as described, for example, in US Pat. No. 4,795,772 or EP 184,785. The unsaturated carboxylic acids used for this purpose are preferably acrylic or methacrylic acid.

Ähnliche Co-Polymerisate, die durch mehrwertige Kationen vernetzt wurden, sind als Beschichtungs- und Konservierungsmittel für Metalloberflächen verwendet worden (vergleiche US 2 754 280, US 2 795 564, EP 14 035, DE 30 24 727 und DE 34 34 668). Wiederum ähnliche Co-Polymerisate sind als Verdickungsmittel für wäßrige Flüssigphasen oder als Flockungsmittel bekannt (DE 38 13 651 und DE 31 30 992). Daraus ließ sich nicht ableiten, daß die erfindungsgemäß eingesetzten Co-Polymerisate weder verdicken noch als Flockungsmittel wirken, sondern durch Steigerung des Emulgiervermögens der Spülflotte zur Reinigungsverstärkung beitragen.Similar copolymers which have been crosslinked by polyvalent cations have been used as coating and preservatives for metal surfaces (compare US 2,754,280, US 2,795,564, EP 14 035, DE 30 24 727 and DE 34 34 668). Similar copolymers are known as thickeners for aqueous liquid phases or as flocculants (DE 38 13 651 and DE 31 30 992). It could not be deduced from this that the copolymers used according to the invention neither thicken nor act as flocculants, but instead contribute to cleaning enhancement by increasing the emulsifying power of the washing liquor.

Die Grenzviskosität wird gemäß der in B. Vollmert: "Grundriß der makromolekularen Chemie", Band III, Seite 55 ff, E. Vollmert Verlag, Karlsruhe, 1988 beschriebenen Methode bestimmt. Bei Co-Polymeren, die ionische Gruppen enthalten, nimmt die spezifische Viskosität bei hohen Konzentrationen proportional mit der Konzentration zu, während bei niedrigen Konzentrationen die Viskosität mit steigender Konzentration abnehmen kann. Die Grenzviskositäten dieser Co-Polymeren werden mit Hilfe von Diagrammen, in denen auf der Abzisse die Konzentration und auf der Ordinate die spezifische Viskosität aufgetragen ist, durch Extrapolation des bei hohen Konzentrationen linear ansteigenden Teils auf die Konzentration 0 ermittelt.The intrinsic viscosity is determined according to the method described in B. Vollmert: "Floor plan of macromolecular chemistry", Volume III, page 55 ff, E. Vollmert Verlag, Karlsruhe, 1988. For copolymers containing ionic groups, the specific viscosity increases proportionally with the concentration at high concentrations, while at low concentrations the viscosity can decrease with increasing concentration. The intrinsic viscosities of these copolymers are determined with the aid of diagrams in which the concentration is plotted on the abscissa and the specific viscosity is plotted on the ordinate by extrapolation of the part which rises linearly at high concentrations to the concentration 0.

Die sulfatierten Anlagerungsprodukte von Ethylenoxid an Alkanole entsprechen der Formel

        R - O - (CH2 - CH2 - O)n - SO3M,

in der R je einen C12- und einen C14-Alkylrest, n = 1 bis 5, vorzugsweise 2 bis 4 und M ein Alkalimetall- oder Ammoniumion bedeuten.The sulfated addition products of ethylene oxide with alkanols correspond to the formula

R - O - (CH 2 - CH 2 - O) n - SO 3 M,

in which R is a C 12 - and a C 14 -alkyl radical, n = 1 to 5, preferably 2 to 4 and M is an alkali metal or ammonium ion.

Auch andere bekannte Alkylethersulfate können als weitere anionische Tenside eingesetzt werden, ebenso wie n-Alkylbenzolsulfonate mit 9 bis 16, vorzugsweise 12 Kohlenstoffatomen im Alkylrest, Alkansulfonate mit 10 bis 20, vorzugsweise 12 bis 18 Kohlenstoffatomen im Alkylrest, Olefinsulfonate mit 12 bis 16, vorzugsweise 12 bis 14 Kohlenstoffatomen im n-Alkylrest und Alkylsulfaten mit 8 bis 18, vorzugsweise 8 bis 14 Kohlenstoffatomen im Alkylrest, einzeln oder als Gemische miteinander oder untereinander.Other known alkyl ether sulfates can also be used as further anionic surfactants, just like n-alkylbenzenesulfonates with 9 to 16, preferably 12 carbon atoms in the alkyl radical, alkanesulfonates with 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical, olefin sulfonates with 12 to 16, preferably 12 up to 14 carbon atoms in the n-alkyl radical and alkyl sulfates with 8 to 18, preferably 8 to 14 carbon atoms in the alkyl radical, individually or as mixtures with one another or with one another.

Als amphotere Tenside können Betain-Verbindungen der Formel

Figure imgb0001
eingesetzt werden, in der R1 einen gegebenenfalls durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 20, vorzugsweise 10 bis 18 Kohlenstoffatomen und R2 und R3 gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten. Bevorzugt werden C10-C18-Alkyl-dimethylcarboxymethylbetain und C11-C17-Alkylamidopropyl-dimethylcarboxymethyl-betain.Betaine compounds of the formula can be used as amphoteric surfactants
Figure imgb0001
 are used in which R 1 is an alkyl radical with 8 to 20, preferably 10 to 18 carbon atoms, which is optionally interrupted by heteroatoms or heteroatom groups, and R 2 and R 3 are identical or different alkyl radicals with 1 to 3 carbon atoms. C 10 -C 18 -Alkyldimethylcarboxymethylbetaine and C 11 -C 17 -Alkylamidopropyldimethylcarboxymethylbetaine are preferred.

Sofern nichtionische Tenside eingesetzt werden, sind Anlagerungsprodukte von 4 bis 20, vorzugsweise von 4- bis 10 Mol Alkylenoxid, vorzugsweise Ethylenoxid an C8-C12-Alkylbenzole, C10-C20-, vorzugsweise C12-C18-Alkanole, C10-C18-, Carbonsäurealkanolamide, aber auch die Anlagerungsprodukte von Ethylenoxid and Polypropylenglykole, die unter dem Namen Pluronics(R) bekannt geworden sind, sowie Anlagerungsprodukte von 1 bis 7 Mol Ethylenoxid an mit 1 bis 5 Mol Propylenoxid umgesetzte C12-C18-Alkanole geeignet. Besonders geeignet sind C8 - C18, vorzugsweise C8 - C12-Alkylpolyglucoside mit 1 bis 10, vorzugsweise 1 bis 2 und insbesondere 1,1 bis 1,4 Glucoseeinheiten im Molekül.If nonionic surfactants are used, adducts are from 4 to 20, preferably from 4 to 10, mol of alkylene oxide, preferably ethylene oxide to C 8 -C 12 alkylbenzenes, C 10 -C 20 -, preferably C 12 -C 18 -alkanols, C 10 -C 18 -, carboxylic acid alkanolamides, but also the addition products of ethylene oxide and polypropylene glycols, which have become known under the name Pluronics (R) , and addition products of 1 to 7 mol of ethylene oxide with C 12 -C 18 reacted with 1 to 5 mol of propylene oxide -Alcanole suitable. C 8 -C 18 , preferably C 8 -C 12 alkyl polyglucosides with 1 to 10, preferably 1 to 2 and in particular 1.1 to 1.4 glucose units in the molecule are particularly suitable.

Bei den bei Bedarf zuzusetzenden Lösungsmitteln handelt es sich um niedermolekulare Alkanole mit 1 bis 4 Kohlenstoffatomen im Molekül, vorzugsweise um Ethanol und Isopropanol.The solvents to be added if necessary are low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol.

Als Lösungsvermittler, etwa für Farbstoffe und Parfümöle können beispielsweise Alkanolamine, Polyole wie Ethylenglykol, Propylenglykol-1,2, Glycerin sowie Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoffatomen im Alkylrest dienen.Solubilizers, for example for dyes and perfume oils, can be used, for example, as alkanolamines, polyols such as ethylene glycol, 1,2-propylene glycol, glycerol and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical.

Zu den bevorzugten Verdickungsmitteln zählen Harnstoff, Natriumchlorid, Ammoniumchlorid und Magnesiumchlorid, die auch kombiniert eingesetzt werden können.The preferred thickeners include urea, sodium chloride, ammonium chloride and magnesium chloride, which can also be used in combination.

Als Korrosionsinhibitoren und Konservierungsmittel sind beispielsweise Natriumbenzoat, Formaldehyd und Natriumsulfit zu nennen. Die Reinigungsmittel können auch übliche Desinfektionsmittel enthalten.Corrosion inhibitors and preservatives include, for example, sodium benzoate, formaldehyde and sodium sulfite. The cleaning agents can also contain conventional disinfectants.

Die erfindungsgemäßen flüssigen Reinigungsmittel der folgenden Beispiele wurden durch Zusammenrühren der einzelnen Bestandteile in beliebiger Reihenfolge und Stehenlassen des Gemisches bis zur Blasenfreiheit erhalten. Als anionischen Tenside wurden jeweils die Natriumsalze eingesetzt.The liquid cleaning agents according to the invention of the following examples were obtained by stirring the individual constituents in any order and leaving the mixture to stand until there were no bubbles. The sodium salts were used as anionic surfactants.

BeispieleExamples

Herstellung der erfindungsgemäß eingesetzten Co-Polymerisate:Preparation of the copolymers used according to the invention:

Beispiel AExample A

In einem 1 Liter Dreihalskolben mit Rührer, Rückflußkühler, Innenthermometer, Stickstoffeinleitung und Tropftrichter wurden 55 g Ethylacrylat 35 g Methacrylsäure 10 g Acrylsäure 8,3 g C14-Fettalkohol x 10 EO-Sulfonat, Na-Salz, 30 % in H2O 8,3 g Nonylphenol x 9,5 EO-Sulfosuccinat, Na-Salz, 30 % in H2O 0,1 g t-Butylhydroperoxid 378 g destilliertes Wasser gegeben. Unter Rühren wurde das Gemisch durch Evakuieren und Belüften mit Stickstoff von Sauerstoff befreit. Das Gemisch wurde auf 25 °C erwärmt. Bei dieser Temperatur wurden 130 mg Na-Formaldehydsulfoxylat, gelöst in 3 ml H2O, durch den Tropftrichter zugegeben. Die Polymerisation setzte spontan ein. Dabei stieg die Temperatur auf 55 °C an. Man erhielt eine koagulatfreie, feinteilige Emulsion mit 20 Gew.-% Polymergehalt mit einer Grenzviskosität: [n] = 525 ml · g-1, gemessen in THF bei 20 °C.In a 1 liter three-necked flask equipped with a stirrer, reflux condenser, internal thermometer, nitrogen inlet and dropping funnel 55 g Ethyl acrylate 35 g Methacrylic acid 10 g Acrylic acid 8.3 g C 14 fatty alcohol x 10 EO sulfonate, Na salt, 30% in H 2 O 8.3 g Nonylphenol x 9.5 EO sulfosuccinate, Na salt, 30% in H 2 O 0.1 g t-butyl hydroperoxide 378 g distilled water given. With stirring, the mixture was freed from oxygen by evacuating and venting with nitrogen. The mixture was warmed to 25 ° C. At this temperature, 130 mg of Na formaldehyde sulfoxylate, dissolved in 3 ml of H 2 O, were added through the dropping funnel. The polymerization started spontaneously. The temperature rose to 55 ° C. A coagulate-free, finely divided emulsion with a polymer content of 20% by weight and an intrinsic viscosity was obtained: [n] = 525 ml · g −1 , measured in THF at 20 ° C.

Beispiel BExample B

In Analogie zu dem im vorstehend angegebenen Verfahren wurde eine Polymeremulsion aus 55 g Ethylacrylat, 25 g Methacrylsäure, 20 g Acrylsäure und den gleichen Mengen an weiteren Bestandteilen wie in Beispiel A hergestellt. Sie hatte ebenfalls einen Polymergehalt von 20 Gew.-%. Die Grenzviskosität lag bei [n] = 610 ml · g-1.In analogy to that in the method given above, a polymer emulsion was made 55 g Ethyl acrylate, 25 g Methacrylic acid, 20 g Acrylic acid and the same amounts of other ingredients as in Example A. It also had a polymer content of 20% by weight. The intrinsic viscosity was [n] = 610 ml · g -1 .

Beispiel CExample C

In Analogie zu Beispiel A wurde eine 20 Gew.-%ige Polymeremulsion mit den Monomeranteilen

Figure imgb0002
Figure imgb0003
 hergestellt. Ihre Grenzviskosität lag bei [n] = 650 ml/g-1.In analogy to Example A, a 20 wt .-% polymer emulsion with the monomer was
Figure imgb0002
Figure imgb0003
 manufactured. Their intrinsic viscosity was [n] = 650 ml / g -1 .

Die in den nachfolgenden Tabellen verwendeten Abkürzungen haben folgende Bedeutung:

E0:
Ethylenoxid
AS:
Aktivsubstanz
FAEOS:
C12/14-Fettalkoholethersulfat mit ca. 2 EO, Na-Salz
FAEO:
C12/14-Fettalkoholethoxylat mit ca. 4 EO
Betain:
C8 - C18-Alkylamidopropyldimethyl-ammoniumbetain
APG® 600 :
C12 - C14-Alkylglucosid mit 1,4 Glucoseeinheiten im Molekül
Polyox R WSR 105:
Polyethylenglykol MG 600 000 (UCC)
The abbreviations used in the following tables have the following meanings:
E0:
Ethylene oxide
AS:
Active substance
FAEOS:
C 12/14 fatty alcohol ether sulfate with approx. 2 EO, Na salt
FAEO:
C 12/14 fatty alcohol ethoxylate with approx. 4 EO
Betaine:
C 8 -C 18 alkylamidopropyldimethylammonium betaine
APG® 600:
C 12 - C 14 alkyl glucoside with 1.4 glucose units in the molecule
Polyox R WSR 105:
Polyethylene glycol MG 600 000 (UCC)

Beispiel 1example 1

An einer handelsüblichen Spülmittelrezeptur (I) wurde bei Zusatz der erfindungsgemäßen Verbindungen der Einfluß auf das sogenannte Fett-Emulgiervermögen nach der sogenannten Rührmethode geprüft. Hiernach wurde die Emulsionsstabilität von Olivenöl in den Reinigungsmittel-Lösungen ermittelt. Hierzu wurden 50 g Prüflösungen (10 g Spülmittel / 40 g Wasser) mit Stadtwasser von 16 °d in einem 400 ml-Becherglas hergestellt, bei Raumtemperatur (20 bis 30 °C) mit 50 g 0livenöl (Olio Dante R) überschichtet und mit einem Propellerrührer (Flügellänge 50 mm aus V2A-Stahl) mit einer Drehzahl von 1200 Umdrehungen pro Minute genau 2 Minuten gerührt. Der Rührflügel befand sich dabei etwa an der Grenze der beiden Phasen. Anschließend wurde die Emulsion in einem 250 ml-Meßzylinder mit einem Durchmesser von 3,6 cm (2 ml-Graduierung, Industrienorm) gegossen und die sich abscheidende wäßrige Phase nach 1 Stunde und nach 4 Stunden ermittelt. Je weniger Wasser in der Zeiteinheit abgeschieden wurde, desto stabiler war die Emulsion und somit das Öl-/Fetttragevermögen der Reinigungsmittellösung, was eine wesentliche Reinigungsverstärkung bedeutet.

Figure imgb0004
The influence on the so-called fat emulsifying ability was tested on a commercially available dishwashing detergent formulation (I) when the compounds according to the invention were added, using the so-called stirring method. The emulsion stability of olive oil in the detergent solutions was then determined. For this purpose, 50 g test solutions (10 g dishwashing liquid / 40 g water) with city water of 16 ° d were prepared in a 400 ml beaker, covered with 50 g olive oil (Olio Dante R ) at room temperature (20 to 30 ° C) and coated with a Propeller stirrer (blade length 50 mm made of V2A steel) with a speed of 1200 revolutions per minute stirred exactly 2 minutes. The impeller was roughly at the border of the two phases. The emulsion was then poured into a 250 ml measuring cylinder with a diameter of 3.6 cm (2 ml graduation, industrial standard) and the aqueous phase which separated out was determined after 1 hour and after 4 hours. The less water was separated in the unit of time, the more stable the emulsion and thus the oil / fat carrying capacity of the cleaning agent solution, which means a significant cleaning boost.
Figure imgb0004

Die Angaben beziehen auf Gew.-% des reinen Wirkstoffs (AS).The data relate to% by weight of the pure active ingredient (AS).

Beispiel 2Example 2

In Analogie zu Beispiel 1 wurde der Einfluß der erfindungsgemäß eingesetzten Co-Polymeren auf das Emulgiervermögen einer weiteren handelsüblichen Rezeptur (Mengen in Gew.-% AS) für manuelle Geschirrspülmittel II gezeigt:

Figure imgb0005
In analogy to Example 1, the influence of the copolymers used according to the invention on the emulsifying power of a further commercial formulation (amounts in% by weight AS) for manual dishwashing agents II was shown:
Figure imgb0005

Die Beispiele zeigten, daß das Emulgiervermögen der Formulierungen bei zunehmender Einsatzkonzentration der erfindungsgemäßen Verbindungen zunimmt.The examples showed that the emulsifying power of the formulations increases with increasing use concentration of the compounds according to the invention.

Claims (5)

  1. A liquid dishwashing detergent bades on an aqueous solution of anionic surfactants, optionally together with nonionic and/or amhoteric surfactants, solvents, solubilizers, corrosion inhibitors, preservatives, thickeners and also dyes and fragrances, characterized in that it additionally cotains 0.001 to 1.0% by weight of a detergency-boosting practically uncrosslinked copolymer of
    a) esters of acrylic and/or methacrylic acid containing 1 to 4 carbon atoms in the alcohol component and b) unsaturated aliphatic carboxylic acids containing 3 to 5 carbon atoms with an intrinsic viscosity [η] of ≥ 400 ml·g-1, as measured in tetrahydrofuran at 20°C.
  2. A detergent as claimed in claim 1, characterized in that it contains a copolymer of 80 to 20% by weight and preferably 60 to 40% by weight of a) and 20 to 80% by weight and preferably 40 to 60% by weight of b).
  3. A detergent as claimed in claims 1 and 2, characterized in that the alcohol component of the esters a) contains 1 to 2 carbon atoms.
  4. A detergent as claimed in claims 1 to 3, characterized in that the unsaturated aliphatic carboxylic acid components of the copolymers emanate from acrylic or methacrylic acid.
  5. A detergent as claimed in claims 1 to 4, characterized in that it consists of an aqueous solution of 5 to 65% by weight and more particularly 10 to 40% by weight of a mixture consisting of at least two of the following surfactants:
    0 to 40% by weight and preferably 5 to 20% by weight of a mixture of 50 parts by weight of a sulfated adduct of 1 to 5 and preferably 2 to 4 moles of ethylene oxide with an n C12 alkanol and of a corresponding adduct with an n C14 alkanol,
    0 to 40% by weight and preferably 5 to 20% by weight of one or more anionic surfactants,
    0 to 20% by weight and preferably 1 to 5% by weight of an amphoteric surfactant,
    0 to 20% by weight and preferably 0 to 5% by weight of a nonionic surfactant,
    0.005 to 0.5% by weight of a detergency-boosting water-soluble anionic copolymer of a) around 80 to 20% by weight and preferably around 60 to 40% by weight of esters of acrylic and/or methacrylic acid containing 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms and more particularly 1 to 2 carbon atoms in the alcohol component and b) around 20 to 80% by weight and preferably around 40 to 60% by weight of unsaturated aliphatic carboxylic acids containing 3 to 5, carbon atoms in the acyl component with an intrinsic viscosity [η] of ≥ 400 ml·g-1, as measured in THF at 20°C,
    0 to 20% by weight and preferably 2 to 10% by weight of a solvent,
    0 to 10% by weight and preferably 0.2 to 5% by weight of a solubilizer,
    0 to 10% by weight and preferably 0.5 to 8% by weight of a thickener,
    0 to 5% by weight and preferably 0.1 to 2% by weight of corrosion inhibitors and preservatives,
    0 to 0.1% by weight of dye,
    0 to 1.0% by weight of perfume oil and
    balance to 100% by weight water.
EP93906556A 1992-03-27 1993-03-18 Liquid cleaning products Expired - Lifetime EP0632824B1 (en)

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DE19817833A1 (en) * 1997-11-26 1999-10-28 Henkel Kgaa Dishwashing liquid with a specific viscosity profile
DE19814768A1 (en) 1998-04-02 1999-10-07 Viessmann Werke Kg Blue burner
US7063895B2 (en) * 2001-08-01 2006-06-20 National Starch And Chemical Investment Holding Corporation Hydrophobically modified solution polymers and their use in surface protecting formulations
FR2865401B1 (en) * 2004-01-27 2006-04-28 Oreal COMPOSITION FOR CLEANING THE SKIN
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US4529773A (en) * 1982-03-17 1985-07-16 David Witiak Alkali-soluble emulsion polymers in acidic surfactant compositions
DE3445549A1 (en) * 1984-12-14 1986-06-19 Henkel KGaA, 4000 Düsseldorf ACRYLATE DISPERSION AND THEIR USE FOR THICKENING HYDROGEN PEROXIDE PREPARATIONS
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