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EP1382664A1 - Liquid Neutral Cleaning Composition - Google Patents

Liquid Neutral Cleaning Composition Download PDF

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Publication number
EP1382664A1
EP1382664A1 EP03015257A EP03015257A EP1382664A1 EP 1382664 A1 EP1382664 A1 EP 1382664A1 EP 03015257 A EP03015257 A EP 03015257A EP 03015257 A EP03015257 A EP 03015257A EP 1382664 A1 EP1382664 A1 EP 1382664A1
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EP
European Patent Office
Prior art keywords
alkyl
weight
liquid neutral
detergent according
neutral detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03015257A
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German (de)
French (fr)
Inventor
Wilfried Schuler
Wolfgang Walther
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
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Clariant GmbH
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Publication date
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Publication of EP1382664A1 publication Critical patent/EP1382664A1/en
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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
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • 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
    • C11D1/90—Betaines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the invention relates to liquid neutral cleaning agents with excellent homogeneous, creamy appearance containing alkyl glycol ether sulfate, secondary alkane sulfonate, alcohol ethoxylate and amphoteric surfactant.
  • Non-surface-active organic solvents such as ethanol, glycol, polyglycols or solubilizers, for example alkylbenzenesulfonates with short chain lengths, such as, for example, toluene or xylene sulfonate, are usually used for this.
  • Cellulose ethers and derivatives, gelatin, starch, polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylamides, polymethacrylates, etc. are available as thickeners. It is desirable to be able to dispense with those compounds which have little or no washing activity.
  • the alkyl ether sulfates are preferably water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is a C 10 -C 24 alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 alkyl or hydroxyalkyl radical, particularly preferably a C. 12 -C 18 alkyl or hydroxyalkyl.
  • A is an ethoxy or propoxy unit
  • m is a number from 0 to 6, typically between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3
  • M is a hydrogen atom or a cation such as e.g. a metal cation (e.g.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those ammonium cations which are derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
  • alkyl ether sulfates are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 alkyl polyethoxylate ( 3.0) sulfate, C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, the cation being sodium or potassium.
  • Preferred alkanesulfonates are the known (C 9 -C 13 ) -alkylbenzenesulfonates, alpha-olefinsulfonates and alkanesulfonates.
  • Esters of sulfo fatty acids or the disalts of alpha sulfo fatty acids are also suitable.
  • Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterifying 1 mol of monoglycerol with 1 to 3 mols of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Moles of glycerol can be obtained.
  • alkyl alkoxylates preference is given to using ethoxylated alcohols, preferably primary alcohols, preferably having 8 to 22 carbon atoms and preferably 1 to 80 EO units per mole of alcohol, the alcohol radical being methyl or linear or preferably in the 2-position or linear and methyl branched Contains residues in the mixture, as is usually the case in oxo alcohol residues.
  • ethoxylated alcohols preferably primary alcohols, preferably having 8 to 22 carbon atoms and preferably 1 to 80 EO units per mole of alcohol, the alcohol radical being methyl or linear or preferably in the 2-position or linear and methyl branched Contains residues in the mixture, as is usually the case in oxo alcohol residues.
  • the preferred ethoxylated alcohols include, for example, C 11 alcohols with 3, 5, 7, 8 and 11 EO units, (C 12 -C 15 ) alcohols with 3, 6, 7, 8, 10 and 13 EO units , (C 14 -C 15 ) alcohols with 4, 7 or 8 EO units, (C 16 -C 18 ) alcohols with 8, 11, 15, 20, 25, 50 or 80 EO units and mixtures the same.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Fatty alcohol EO / PO adducts can also be used, such as the ®Genapol types 3970, 2909 and 2822 from Clariant GmbH.
  • condensation products of alcohols which contain an alkyl chain of 10 to 20 carbons with 2 to 18 mol of ethylene oxide per mol of alcohol are particularly preferred.
  • the alcohol ethoxylates can have a narrow homolog distribution of the ethylene oxide ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates").
  • nonionic surfactants of this type are Tergitol TM 15-S-9 (condensation product of a C 11 -C 15 linear secondary alcohol with 9 mol of ethylene oxide), Tergitol TM 24-L-NMW (condensation product of a C 12 -C 14 linear primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution).
  • the alcohol ethoxylates obtainable under the trade name Genapol TM from Clariant GmbH are particularly preferred.
  • Suitable betaines and amine oxides are, in particular, those of the following formulas: where R is an alkyl, hydroxyalkyl or alkylphenyl group with 8 to 22 carbon atoms, each radical R 1 independently of one another is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms or a polyethylene oxide group with 1 to 3 ethylene oxide units or two R 1 groups via a - O or -NH group are connected to form a ring, R 2 is an alkylene group having 2 to 3 carbon atoms or mixtures thereof, and x is a number from 0 to 10.
  • Particularly preferred amine oxides are C 10 -C 18 -alkyldimethylamine oxides and C 8 -C 12 -alkoxyethyl-dihydroxyethylamine oxides and C 10 -C 18 -acylamidopropyldimethylamine oxides.
  • the neutral detergents according to the invention can contain further specific auxiliaries Additives, for example, salts, bleaches, bleach activators, optical Brighteners, graying inhibitors, solubilizers, thickeners, Preservatives, fragrances and dyes, pearlescent agents, foam inhibitors, Sequestrant included.
  • these neutral cleaning agents Contain acids or alkali to adjust the pH to a range from 6.7 to 7.3, preferably adjusted to pH 7.
  • the agents according to the invention can be used as foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica.
  • foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica.
  • foam inhibitors can also be used advantageously, e.g. those made of silicone oil, paraffin oil or waxes.
  • the desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners.
  • organic solvents all monohydric or polyhydric alcohols come into consideration as organic solvents.
  • Alcohols with 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used.
  • Further preferred alcohols are polyethylene glycols with a relative molecular weight below 2000.
  • polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred.
  • An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, it being possible for the neutral cleaning agents according to the invention to contain 8 to 12% by weight of such a mixture.
  • suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
  • Hardened castor oil, salts of long chain fatty acids preferably in amounts of 0 to 5 wt .-% and especially in amounts of 0.5 to 2% by weight, for example sodium.
  • Potassium-, Aluminum, magnesium and titanium stearates or the sodium and / or potassium salts behenic acid, and polysaccharides, in particular xanthan gum, guar guar, Agar, alginates and tyloses, carboxymethyl cellulose and Hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP Diethylenetriaminepentamethylenephosphonic acid
  • Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, pentanediol or sorbic acid.
  • pearlescent agents examples include glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters into consideration.
  • salts or adjusting agents are sodium chloride, sodium sulfate, Sodium carbonate or sodium silicate (water glass) are used.
  • Typical examples for other additives are sodium borate, starch, Sucrose, polydextrose, stilbene compounds, methyl cellulose, toluenesulfonate, Cumene sulfonate, soaps and silicones.
  • the neutral cleaning agents according to the invention are notable for their light weight Solubility and dilutability in water, good skin friendliness with high Cleanability and good storage stability. They can be harder to treat Surfaces such as Facades, windows and floors from a wide variety Materials, e.g. Metals, glass, ceramics, plastics, textiles etc., are used become.
  • Hostapur® SAS 60 secondary sodium alkanesulfonate (approx. 60% WAS)
  • Genapol® LRO C 12 -C 14 sodium alkyl diglycol ether sulfate (30% WAS)
  • Genagen® CAB 818 Cocoamidopropyl betaine (approx.

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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)

Abstract

A liquid, neutral cleansing agent comprises by weight: alkylether sulfate (6-16 %); alkane sulfonate (5-7 %); alkyl alkoxylate (4-8 %); amphoteric surfactant and water (2-4 %).

Description

Die Erfindung betrifft flüssige Neutralreinigungsmittel mit ausgezeichnetem homogenen, cremigen Erscheinungsbild enthaltend Alkylglykolethersulfat, sekundäres Alkansulfonat, Alkoholethoxylat und amphoteres Tensid.The invention relates to liquid neutral cleaning agents with excellent homogeneous, creamy appearance containing alkyl glycol ether sulfate, secondary alkane sulfonate, alcohol ethoxylate and amphoteric surfactant.

An moderne Haushaltsreinigungsmittel und Geschirrspülmittel werden hohe Ansprüche gestellt: Sie müssen ein gutes und rasches Reinigungsvermögen gegenüber Schmutz und Fett haben, sehr gut hautverträglich, aber auch umweltverträglich sein.
Zur Minimierung von Transport-, Lager- und Verpackungskosten, sowie zur Verbesserung der Handhabung für den Verbraucher kommen moderne Reinigungsund Geschirrspülmittel mit hohen Konzentrationen an Waschaktivsubstanzen und höheren Viskositäten in den Handel. Hochkonzentrierte Zubereitungen erfordern entweder den Einsatz von Lösungsmitteln und/oder Hydrotropen, die die unterschiedlichen Bestandteile in Lösung bringen oder aber Verdicker um eine klare und homogene Formulierung mit geeigneten Viskositäten zu erhalten und Gelbildung bei der Herstellung oder Lagerung der Mittel zu vermeiden. Üblicherweise werden hierfür nichtoberflächenaktive organische Lösungsmittel, wie Ethanol, Glykol, Polyglykole oder Lösungsvermittler, beispielsweise Alkylbenzolsulfonate mit niedrigen Kettenlängen, wie zum Beispiel Toluol- oder Xylensulfonat eingesetzt. An Verdickern stehen Celluloseether und -derivate, Gelatine, Stärke, Polymere, beispielsweise Polyvinylalkohole, Polyvinylpyrrolidone, Polyacrylamide, Polymethacrylate etc zur Verfügung. Wünschenswert ist, auf solche Verbindungen verzichten zu können, die kein oder wenig Waschaktivvermögen zeigen.High demands are placed on modern household cleaning agents and dishwashing detergents: they must have a good and quick cleaning ability against dirt and grease, be very well tolerated by the skin, but also environmentally friendly.
To minimize transport, storage and packaging costs, and to improve handling for consumers, modern cleaning and dishwashing detergents with high concentrations of detergent substances and higher viscosities are on the market. Highly concentrated preparations either require the use of solvents and / or hydrotropes, which bring the different components into solution, or thickeners in order to obtain a clear and homogeneous formulation with suitable viscosities and to avoid gel formation during the preparation or storage of the agents. Non-surface-active organic solvents, such as ethanol, glycol, polyglycols or solubilizers, for example alkylbenzenesulfonates with short chain lengths, such as, for example, toluene or xylene sulfonate, are usually used for this. Cellulose ethers and derivatives, gelatin, starch, polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylamides, polymethacrylates, etc. are available as thickeners. It is desirable to be able to dispense with those compounds which have little or no washing activity.

Gegenstand der Erfindung sind flüssige Neutralreinigungsmittel enthaltend im wesentlichen

  • a) 6 bis 16 Gew.-%, bevorzugt 5 bis 13 Gew.-%, Alkylethersulfat,
  • b) 5 bis 7 Gew.-%, bevorzugt 6 Gew.-% Alkansulfonat
  • c) 4 bis 8 Gew.-%, bevorzugt 5 bis 7 Gew.-% Alkylalkoxylat und
  • d) 2 bis 4 Gew.-%, bevorzugt 3 Gew.-% amphoteres Tensid sowie Wasser.
    • The invention relates essentially to liquid neutral cleaning agents
  • a) 6 to 16% by weight, preferably 5 to 13% by weight, alkyl ether sulfate,
  • b) 5 to 7 wt .-%, preferably 6 wt .-% alkanesulfonate
  • c) 4 to 8 wt .-%, preferably 5 to 7 wt .-% alkyl alkoxylate and
  • d) 2 to 4 wt .-%, preferably 3 wt .-% amphoteric surfactant and water.

    • Die Alkylethersulfate sind vorzugsweise wasserlösliche Salze oder Säuren der Formel RO(A)mSO3M, worin R einen C10-C24-Alkyl- oder Hydroxyalkylrest, bevorzugt einen C12-C20-Alkyl- oder Hydroxyalkylrest, besonders bevorzugt einen C12-C18-Alkyloder Hydroxyalkylrest darstellt. A ist eine Ethoxy- oder Propoxyeinheit, m ist eine Zahl von 0 bis 6, typischerweise zwischen ca. 0,5 und ca. 6, besonders bevorzugt zwischen ca. 0,5 und ca. 3 und M ist ein Wasserstoffatom oder ein Kation wie z.B. ein Metallkation (z.B. Natrium, Kalium, Lithium, Calcium, Magnesium, etc.), Ammonium oder ein substituiertes Ammoniumkation. Beispiele für substituierte Ammoniumkationen sind Methyl-, Dimethyl-, Trimethylammonium- und quaternäre Ammoniumkationen wie Tetramethylammonium und Dimethylpiperidiniumkationen, sowie solche Ammoniumkationen, die von Alkylaminen, wie Ethylamin, Diethylamin, Triethylamin oder Mischungen davon abgeleitet sind. Als Beispiele für Alkylethersulfate seien genannt C12-C18-Alkyl-polyethoxylat-(1,0)-sulfat, C12-C18-Alkyl-polyethoxylat (2,25)sulfat, C12-C18-Alkyl-polyethoxylat (3,0)sulfat, C12-C18-Alkylpolyethoxylat (4,0)sulfat, wobei das Kation Natrium oder Kalium ist.The alkyl ether sulfates are preferably water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is a C 10 -C 24 alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 alkyl or hydroxyalkyl radical, particularly preferably a C. 12 -C 18 alkyl or hydroxyalkyl. A is an ethoxy or propoxy unit, m is a number from 0 to 6, typically between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as e.g. a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those ammonium cations which are derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples of alkyl ether sulfates are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 alkyl polyethoxylate ( 3.0) sulfate, C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, the cation being sodium or potassium.

    Als Alkansulfonate kommen vorzugsweise die bekannten (C9-C13)-Alkylbenzolsulfonate, alpha-Olefinsulfonate und Alkansulfonate in Betracht. Geeignet sind auch Ester von Sulfofettsäuren bzw. die Disalze der alpha-Sulfofettsäuren. Weitere geeignete anionische Tenside sind sulfierte Fettsäureglycerinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung von 1 Mol Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden.Preferred alkanesulfonates are the known (C 9 -C 13 ) -alkylbenzenesulfonates, alpha-olefinsulfonates and alkanesulfonates. Esters of sulfo fatty acids or the disalts of alpha sulfo fatty acids are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterifying 1 mol of monoglycerol with 1 to 3 mols of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Moles of glycerol can be obtained.

    Unter den Alkylalkoxylaten werden bevorzugt ethoxylierte Alkohole, bevorzugt primäre Alkohole, mit bevorzugt 8 bis 22 C-Atomen und bevorzugt 1 bis 80 EO-Einheiten pro Mol Alkohol, eingesetzt, wobei der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt ist oder lineare und methylverzweigte Reste im Gemisch enthält, so wie dies üblicherweise in Oxoalkoholresten der Fall ist. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C11-Alkohole mit 3, 5, 7, 8 und 11 EO-Einheiten, (C12-C15)-Alkohole mit 3, 6, 7, 8, 10 bzw. 13 EO-Einheiten, (C14-C15)-Alkohole mit 4, 7 bzw. 8 EO-Einheiten, (C16-C18)-Alkohole mit 8, 11, 15, 20, 25, 50 bzw. 80 EO-Einheiten und Mischungen derselben. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Es können auch Fettalkohol-EO/PO-Addukte eingesetzt werden, wie z.B. die ®Genapol-Typen 3970, 2909 und 2822 der Fa. Clariant GmbH.
    Besonders bevorzugt sind die Kondensationsprodukte von Alkoholen, die eine Alkylkette von 10 bis 20 Kohlenstoffen enthalten, mit 2 bis 18 mol Ethylenoxid pro mol Alkohol. Ebenso können die Alkoholethoxylate eine enge Homologenverteilung des Ethylenoxides ("Narrow Range Ethoxylates") oder eine breite Homologenverteilung des Ethylenoxides ("Broad Range Ethoxylates") aufweisen. Beispiele von kommerziell erhältlichen nichtionischen Tensiden dieses Types sind Tergitol™ 15-S-9 (Kondensationsprodukt eines C11-C15 linearen sekundären Alkohols mit 9 mol Ethylenoxid), Tergitol™ 24-L-NMW (Kondensationsprodukt eines C12-C14-linearen primären Alkohols mit 6 mol Ethylenoxid mit enger Molgewichtsverteilung). Besonders bevorzugt sind die unter dem Handelsnamen Genapol™ der Clariant GmbH erhältlichen Alkoholethoxylate.    Among the alkyl alkoxylates, preference is given to using ethoxylated alcohols, preferably primary alcohols, preferably having 8 to 22 carbon atoms and preferably 1 to 80 EO units per mole of alcohol, the alcohol radical being methyl or linear or preferably in the 2-position or linear and methyl branched Contains residues in the mixture, as is usually the case in oxo alcohol residues. The preferred ethoxylated alcohols include, for example, C 11 alcohols with 3, 5, 7, 8 and 11 EO units, (C 12 -C 15 ) alcohols with 3, 6, 7, 8, 10 and 13 EO units , (C 14 -C 15 ) alcohols with 4, 7 or 8 EO units, (C 16 -C 18 ) alcohols with 8, 11, 15, 20, 25, 50 or 80 EO units and mixtures the same. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Fatty alcohol EO / PO adducts can also be used, such as the ®Genapol types 3970, 2909 and 2822 from Clariant GmbH.
    The condensation products of alcohols which contain an alkyl chain of 10 to 20 carbons with 2 to 18 mol of ethylene oxide per mol of alcohol are particularly preferred. Likewise, the alcohol ethoxylates can have a narrow homolog distribution of the ethylene oxide ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates"). Examples of commercially available nonionic surfactants of this type are Tergitol ™ 15-S-9 (condensation product of a C 11 -C 15 linear secondary alcohol with 9 mol of ethylene oxide), Tergitol ™ 24-L-NMW (condensation product of a C 12 -C 14 linear primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution). The alcohol ethoxylates obtainable under the trade name Genapol ™ from Clariant GmbH are particularly preferred.

    Als Betaine und Aminoxide kommen insbesondere solche der folgenden Formeln in Frage:

    Figure 00030001
    wobei R eine Alkyl-, Hydroxyalkyl- oder Alkylphenylgruppe mit 8 bis 22 Kohlenstoffatomen, jeder Rest R1 unabhängig voneinander eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit 1 bis 3 Ethylenoxideinheiten bedeuten oder zwei R1-Gruppen über eine -O- oder -NH-Gruppe unter Ringbildung miteinander verbunden sind, R2 eine Alkylengruppe mit 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon, und x eine Zahl von 0 bis 10 bedeuten.Suitable betaines and amine oxides are, in particular, those of the following formulas:
    Figure 00030001
    where R is an alkyl, hydroxyalkyl or alkylphenyl group with 8 to 22 carbon atoms, each radical R 1 independently of one another is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms or a polyethylene oxide group with 1 to 3 ethylene oxide units or two R 1 groups via a - O or -NH group are connected to form a ring, R 2 is an alkylene group having 2 to 3 carbon atoms or mixtures thereof, and x is a number from 0 to 10.

    Als Aminoxide sind besonders bevorzugt C10-C18-Alkyldimethylaminoxide und C8-C12-Alkoxyethyl-Dihydroxyethylaminoxide und C10-C18-Acylamidopropyldimethylaminoxide.Particularly preferred amine oxides are C 10 -C 18 -alkyldimethylamine oxides and C 8 -C 12 -alkoxyethyl-dihydroxyethylamine oxides and C 10 -C 18 -acylamidopropyldimethylamine oxides.

    Die erfindungsgemäßen Neutralreinigungsmittel können weitere spezifische Hilfsund Zusatzstoffe beispielsweise, Salze, Bleichmittel, Bleichaktivatoren, optische Aufheller, Vergrauungsinhibitoren, Lösungsvermittler, Verdickungsmittel, Konservierungsmittel, Duft- und Farbstoffe, Perlglanzmittel, Schauminhibitoren, Sequestriermittel enthalten. Insbesondere können diese Neutralreinigungsmittel Säuren oder Alkali enthalten, um den pH-Wert auf einen Bereich von 6,7 bis 7,3, vorzugsweise auf pH 7, einzustellen.The neutral detergents according to the invention can contain further specific auxiliaries Additives, for example, salts, bleaches, bleach activators, optical Brighteners, graying inhibitors, solubilizers, thickeners, Preservatives, fragrances and dyes, pearlescent agents, foam inhibitors, Sequestrant included. In particular, these neutral cleaning agents Contain acids or alkali to adjust the pH to a range from 6.7 to 7.3, preferably adjusted to pH 7.

    Die erfindungsgemäßen Mittel können als Schauminhibitoren Fettsäurealkylesteralkoxylate, Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure, enthalten. Mit Vorteil können auch Gemische verschiedener Schauminhibitoren verwendet werden, z.B. solche aus Silikonöl, Paraffinöl oder Wachsen. Vorzugsweise sind Schauminhibitoren an eine granulare, in Wasser lösliche oder dispergierbare Trägersubstanz gebunden.The agents according to the invention can be used as foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica. With Mixtures of different foam inhibitors can also be used advantageously, e.g. those made of silicone oil, paraffin oil or waxes. Are preferred Foam inhibitors on a granular, water soluble or dispersible Carrier substance bound.

    Die gewünschte Viskosität der Mittel kann durch Zugabe von Wasser und/oder organischen Lösungsmitteln oder durch Zugabe einer Kombination aus organischen Lösungsmitteln und Verdickungsmitteln eingestellt werden.
    Prinzipiell kommen als organische Lösungsmittel alle ein- oder mehrwertigen Alkohole in Betracht. Bevorzugt werden Alkohole mit 1 bis 4 Kohlenstoffatomen wie Methanol, Ethanol, Propanol, Isopropanol, geradkettiges und verzweigtes Butanol, Glycerin und Mischungen aus den genannten Alkoholen eingesetzt. Weitere bevorzugte Alkohole sind Polyethylenglykole mit einer relativen Molekülmasse unter 2000. Insbesondere ist ein Einsatz von Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 600 und in Mengen bis zu 45 Gew.-% und von Polyethylenglykol mit einer relativen Molekülmasse zwischen 400 und 600 in Mengen von 5 bis 25 Gew.-% bevorzugt. Eine vorteilhafte Mischung aus Lösungsmitteln besteht aus monomerem Alkohol, beispielsweise Ethanol und Polyethylenglykol im Verhältnis 0,5 : 1 bis 1,2 : 1, wobei die erfindungsgemäßen Neutralreinigungsmittel 8 bis 12 Gew.-% einer solchen Mischung enthalten können. Weitere geeignete Lösungsmittel sind beispielsweise Triacetin (Glycerintriacetat) und 1-Methoxy-2-propanol.    The desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners.
    In principle, all monohydric or polyhydric alcohols come into consideration as organic solvents. Alcohols with 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used. Further preferred alcohols are polyethylene glycols with a relative molecular weight below 2000. In particular, use of polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred. An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, it being possible for the neutral cleaning agents according to the invention to contain 8 to 12% by weight of such a mixture. Other suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.

    Als Verdickungsmittel werden bevorzugt gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-. Kalium-, Aluminium-, Magnesium- und Titan-Stearate oder die Natrium und/oder KaliumSalze der Behensäure, sowie Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethylcellulose, ferner höhermolekulare Polyethylenglycolmono- und diester von Fettsäuren, Polyacrylate, Polyvinylalkohol und Polyvinylpyrrolidon eingesetzt.Hardened castor oil, salts of long chain fatty acids, preferably in amounts of 0 to 5 wt .-% and especially in amounts of 0.5 to 2% by weight, for example sodium. Potassium-, Aluminum, magnesium and titanium stearates or the sodium and / or potassium salts behenic acid, and polysaccharides, in particular xanthan gum, guar guar, Agar, alginates and tyloses, carboxymethyl cellulose and Hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone.

    Um Spuren von Schwermetallen zu binden, können die Salze von Polyphosphonsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und Diethylentriaminpentamethylenphosphonsäure (DTPMP) eingesetzt werden.In order to bind traces of heavy metals, the salts of Polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and Diethylenetriaminepentamethylenephosphonic acid (DTPMP) can be used.

    Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Pentandiol oder Sorbinsäure.Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, pentanediol or sorbic acid.

    Als Perlglanzmittel kommen beispielsweise Glycoldistearinsäureester wie Ethylenglycoldistearat, aber auch Fettsäuremonoglykolester in Betracht.Examples of pearlescent agents are glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters into consideration.

    Als Salze bzw. Stellmittel kommen beispielsweise Natriumchlorid, Natriumsulfat, Natriumcarbonat oder Natriumsilikat (Wasserglas) zum Einsatz. Examples of salts or adjusting agents are sodium chloride, sodium sulfate, Sodium carbonate or sodium silicate (water glass) are used.

    Als typische Einzelbeispiele für weitere Zusatzstoffe sind Natriumborat, Stärke, Saccharose, Polydextrose, Stilbenverbindungen, Methylcellulose, Toluolsulfonat, Cumolsulfonat, Seifen und Silicone zu nennen.Typical examples for other additives are sodium borate, starch, Sucrose, polydextrose, stilbene compounds, methyl cellulose, toluenesulfonate, Cumene sulfonate, soaps and silicones.

    Die erfindungsgemäßen Neutralreinigungsmittel zeichnen sich aus durch eine leichte Löslichkeit und Verdünnbarkeit in Wasser, gute Hautfreundlichkeit bei hohem Reinigungsvermögen und gute Lagerstabilität. Sie können zur Behandlung harter Oberflächen wie z.B. Fassaden, Fenster und Fußboden aus den verschiedensten Materialien, z.B. Metallen, Glas, Keramiken, Kunststoffen, Textilien etc., eingesetzt werden.The neutral cleaning agents according to the invention are notable for their light weight Solubility and dilutability in water, good skin friendliness with high Cleanability and good storage stability. They can be harder to treat Surfaces such as Facades, windows and floors from a wide variety Materials, e.g. Metals, glass, ceramics, plastics, textiles etc., are used become.

    Nachfolgende Beispiele sollen die Erfindung näher erläutern ohne sie darauf einzuschränken.The following examples are intended to explain the invention in more detail without referring to it limit.

    BeispieleExamples

    Alle Prozentangaben sind Gewichtsprozente. Die Gewichtsprozente der Waschaktivgehalte sind in Klammern angegeben.All percentages are percentages by weight. The weight percent of Active detergent contents are given in brackets.

    Neutralreinigungsmittel 1Neutral detergent 1

    Gesamttensidgehalt: 29 Gew.-%Total surfactant content: 29% by weight

    Zusammensetzung:Composition:

    AA 42,8 %42.8% (12 %)(12%) ®Genapol LRO flüssig®Genapol LRO liquid 10 %10% (6)(6) ®Hostapur SAS 60®Hostapur SAS 60 5 %5% (5)(5) ®Genapol OA 070®Genapol OA 070 3 %3% (3)(3) ®Genapol TSM®Genapol TSM BB 10 %10% (3)(3) ® Genagen CAB 818® Genagen CAB 818 28,5 %28.5% Wasserwater q.s.q.s. Farbstoff, Konservierungsmittel, ParfümDye, preservative, perfume CC 0,7 %0.7% Natriumchloridsodium chloride

    Herstellung:production:

  • I Die Komponenten von A wurden gemischtI The components of A were mixed
  • II Zugabe der Komponenten BII addition of components B
  • III Anschließend wurde mit C die Viskosität eingestellt und gut homogenisiertIII Then the viscosity was adjusted with C and homogenized well

    • Neutralreinigungsmittel 2Neutral detergent 2

    Gesamttensidgehalt: 30,1 Gew.-%Total surfactant content: 30.1% by weight

    Zusammensetzung:Composition:

    AA 3 %3% tri-Natriumcitrat x 2H2Otri sodium citrate x 2H 2 O 2 %2% ®Dequest 2066®Dequest 2066 BB 34.5 %34.5% Wasserwater Parfüm, Farbstoff, KonservierungsmittelPerfume, dye, preservative CC 25 % (7)25% (7) ®Genapol LRO flüssig®Genapol LRO liquid 10 % (6)10% (6) ®Hostapur SAS 60®Hostapur SAS 60 7 % (7)7% (7) ®Genapol OA 40®Genapol OA 40 7 % (7)7% (7) ®Genapol OA 70®Genapol OA 70 10 % (3.1)10% (3.1) ®Genaminox LA®Genaminox LA DD 1,0 %1.0% Natriumchloridsodium chloride 0,5 %0.5% ®Kelzan RD   (Kelco)®Kelzan RD (Kelco)

    Herstellung:production:

  • I Die Komponenten A wurden in B gelöst,I Components A were dissolved in B,
  • II Zugabe der Komponenten C,II addition of components C,
  • III Zugabe der Komponenten D, anschließend HomogenisierungIII addition of components D, then homogenization

    • Chemische Beschreibung der eingesetzten HandelsprodukteChemical description of the commercial products used

    Hostapur® SAS 60Hostapur® SAS 60 sekundäres Natriumalkansulfonat (ca. 60 % WAS)secondary sodium alkanesulfonate (approx. 60% WAS) Genapol® LROGenapol® LRO C12-C14-Natriumalkyldiglycolethersulfat (30 %WAS)C 12 -C 14 sodium alkyl diglycol ether sulfate (30% WAS) Genagen® CAB 818Genagen® CAB 818 Cocoamidopropylbetain (ca. 30 % WAS)Cocoamidopropyl betaine (approx. 30% WAS) Genapol® OA 040Genapol® OA 040 C12-C14-Oxalkoholpolyglykolether mit 4 EO C 12 -C 14 oxalcohol polyglycol ether with 4 EO Genapol® OA 070Genapol® OA 070 C12-C14-Oxalkoholpolyglykolether mit 7 EOC 12 -C 14 oxalcohol polyglycol ether with 7 EO Genapol® TSMGenapol® TSM Mischung aus PEG-3 Distearat und NatriumlaurethsulfatMixture of PEG-3 distearate and sodium laureth sulfate Genaminox® LAGenaminox® LA Lauryldimethylaminoxidlauryl dimethyl ®Dequest 2006®Dequest 2006 Phosphonat (Monsanto)Phosphonate (Monsanto) ®Kelzan RD®Kelzan RD Xanthan Gum (Kelco)Xanthan Gum (Kelco)

    Claims (6)

    Flüssige Neutralreinigungsmittel enthaltend im wesentlichen a) 6 bis 16 Gew.-% Alkylethersulfat, b) 5 bis 7 Gew.-% Alkansulfonat c) 4 bis 8 Gew.-% Alkylalkoxylat d) 2 bis 4 Gew.-% amphoteres Tensid und Wasser. Essentially containing liquid neutral detergents a) 6 to 16% by weight of alkyl ether sulfate, b) 5 to 7 wt .-% alkanesulfonate c) 4 to 8 wt .-% alkyl alkoxylate d) 2 to 4% by weight of amphoteric surfactant and water. Flüssige Neutralreinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, dass sie
    5 bis 13 Gew.-% Alkylethersulfat,
    5 bis 7 Gew.-% Alkansulfonat
    5 bis 7 Gew.-% Alkylalkoxylat und
    3 Gew.-% amphoteres Tensid enthalten.    Liquid neutral detergent according to claim 1, characterized in that it
    5 to 13% by weight of alkyl ether sulfate,
    5 to 7% by weight alkanesulfonate
    5 to 7 wt .-% alkyl alkoxylate and
    3% by weight of amphoteric surfactant.         Flüssige Neutralreinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, dass sie als Alkylethersulfat eine Verbindung der Formel RO(A)mSO3M enthalten, worin R C10-C24-Alkyl oder Hydroxyalkyl, A eine Ethoxy- oder Propoxyeinheit, m eine Zahl von 0 bis 6 und M ein Proton oder ein Metallkation bedeutet.Liquid neutral detergent according to claim 1, characterized in that it is a compound of the formula as alkyl ether sulfate RO (A) m SO 3 M contain, wherein RC 10 -C 24 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is a number from 0 to 6 and M is a proton or a metal cation. Flüssige Neutralreinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, dass sie als Alkylalkoxylate mit 1 bis 80 Ethylenoxideinheiten oxethylierte C8-C22-Alkohole enthalten.Liquid neutral detergent according to claim 1, characterized in that they contain as alkyl alkoxylates with 1 to 80 ethylene oxide units oxyethylated C 8 -C 22 alcohols. Flüssige Neutralreinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, dass sie als amphotere Tenside Verbindungen der folgenden Formeln enthalten
    Figure 00100001
    wobei R eine Alkyl-, Hydroxyalkyl- oder Alkylphenylgruppe mit 8 bis 22 Kohlenstoffatomen, jeder Rest R1 unabhängig voneinander eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit 1 bis 3 Ethylenoxideinheiten bedeuten oder zwei R1-Gruppen über eine -O- oder - NH-Gruppe unter Ringbildung miteinander verbunden sind, R2 eine Alkylengruppe mit 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon, und x eine Zahl von 0 bis 10 bedeuten.    Liquid neutral detergent according to claim 1, characterized in that they contain compounds of the following formulas as amphoteric surfactants
    Figure 00100001
    where R is an alkyl, hydroxyalkyl or alkylphenyl group with 8 to 22 carbon atoms, each radical R 1 independently of one another is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms or a polyethylene oxide group with 1 to 3 ethylene oxide units or two R 1 groups via a - O or NH groups are linked to form a ring, R 2 is an alkylene group having 2 to 3 carbon atoms or mixtures thereof, and x is a number from 0 to 10.         Verwendung der flüssigen Neutralreinigungsmittel nach Anspruch 1 zum Reinigen harter Oberflächen.Use of the liquid neutral detergent according to claim 1 for Cleaning hard surfaces.
    EP03015257A 2002-07-13 2003-07-07 Liquid Neutral Cleaning Composition Withdrawn EP1382664A1 (en)

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    Application Number Priority Date Filing Date Title
    DE10231741A DE10231741A1 (en) 2002-07-13 2002-07-13 Liquid neutral detergent
    DE10231741 2002-07-13

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    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2007003302A1 (en) * 2005-07-01 2007-01-11 Henkel Kommanditgesellschaft Auf Aktien Viscosity adjustment in detergents for washing-up by hand
    EP1875891A1 (en) * 2006-07-06 2008-01-09 Clariant International Ltd. Cosmetic or dermatologic cleaning agents containing secondary alkane sulphonates

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    Publication number Priority date Publication date Assignee Title
    US3928249A (en) * 1972-02-07 1975-12-23 Procter & Gamble Liquid detergent composition
    WO1999003968A1 (en) * 1997-07-17 1999-01-28 Colgate-Palmolive Company Microemulsion light duty liquid cleaning compositions
    US5952278A (en) * 1993-09-14 1999-09-14 The Procter & Gamble Company Light duty liquid or gel dishwashing detergent compositions containing protease
    US6013611A (en) * 1996-08-26 2000-01-11 Colgate Palmolive Company Light duty liquid cleaning compositions
    DE10045289A1 (en) * 2000-09-13 2002-03-28 Henkel Kgaa Fast-drying detergent and cleaning agent, especially hand dishwashing liquid

    Patent Citations (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3928249A (en) * 1972-02-07 1975-12-23 Procter & Gamble Liquid detergent composition
    US5952278A (en) * 1993-09-14 1999-09-14 The Procter & Gamble Company Light duty liquid or gel dishwashing detergent compositions containing protease
    US6013611A (en) * 1996-08-26 2000-01-11 Colgate Palmolive Company Light duty liquid cleaning compositions
    WO1999003968A1 (en) * 1997-07-17 1999-01-28 Colgate-Palmolive Company Microemulsion light duty liquid cleaning compositions
    DE10045289A1 (en) * 2000-09-13 2002-03-28 Henkel Kgaa Fast-drying detergent and cleaning agent, especially hand dishwashing liquid

    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2007003302A1 (en) * 2005-07-01 2007-01-11 Henkel Kommanditgesellschaft Auf Aktien Viscosity adjustment in detergents for washing-up by hand
    EP1875891A1 (en) * 2006-07-06 2008-01-09 Clariant International Ltd. Cosmetic or dermatologic cleaning agents containing secondary alkane sulphonates

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