EP0763591A1 - Aqueous manual dishwashing composition - Google Patents
Aqueous manual dishwashing composition Download PDFInfo
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- EP0763591A1 EP0763591A1 EP96114276A EP96114276A EP0763591A1 EP 0763591 A1 EP0763591 A1 EP 0763591A1 EP 96114276 A EP96114276 A EP 96114276A EP 96114276 A EP96114276 A EP 96114276A EP 0763591 A1 EP0763591 A1 EP 0763591A1
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- alkyl
- alkenyl
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- alcohol
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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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
- 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
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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
- 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
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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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
- 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
Definitions
- the invention relates to aqueous hand dishwashing detergents with improved emulsifying power, containing defined amounts of low-ethoxylated fatty alcohol ether sulfates in the form of their magnesium salts.
- Hand dishwashing detergents are usually dilute aqueous detergent mixtures which, in addition to anionic surfactants, contain primarily nonionic and amphoteric surfactants. In addition to cleaning the dishes, these agents are required to have a strong and durable foam that does not collapse even when exposed to considerable fat - even if this activation is not directly related to the cleaning performance. However, a particular problem is to emulsify the detached lipophilic skin layer, i.e. to prevent redeposition on the dishes. Products of the state of the art also show deficits here.
- HGSM based on fatty alcohol ether sulfate sodium salts, plane and magnesium ions are proposed.
- HGSM are known from the international patent applications WO 92/06156, WO 94/05769 and WO 94/24241 (Procter & Gamble), the combinations of anionic surfactants and Contain glucamides, ether carboxylic acids or secondary alkyl sulfates with magnesium ions.
- the complex object of the invention was therefore to provide aqueous hand dishwashing detergents which at the same time have good dishwashing power, high base foam, good fat resistance and, in particular, excellent emulsifying power.
- the invention relates to aqueous hand dishwashing detergents containing fatty alcohol ether sulfates of the formula (I), in which R 1 represents an alkyl and / or alkenyl radical having 8 to 18 carbon atoms and n represents numbers from 0.5 to 1.5, in amounts of 40 to 100, preferably 45 to 90 and in particular 45 to 80 parts by weight. % - based on the proportion of detergent active.
- the agents can contain alkyl and / or alkenyl oligoglycosides, betaines and / or fatty alcohol sulfates as further surfactants.
- the fatty alcohol sulfates to be used for the purposes of the invention are substances known per se which, by the addition of very little, namely an average of 0.5 to 1.5, preferably about 1 mol, of ethylene oxide to a technical coconut fatty alcohol containing 8 to 18 and preferably 12 up to 14 carbon atoms, sulfation of the polyglycol ether and neutralization with a basic magnesium salt.
- magnesium salt surfactants is from H.Plate in Parf. Cosm. 76 , 28 (1995) .
- Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (II) in which R 2 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As a representative of the extensive literature, reference is made to steps EP-A1-0 301 298 and WO 90/03977 .
- the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
- the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides .
- the alkyl or alkenyl radical R 2 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capron alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
- the alkyl or alkenyl radical R 2 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as described above, and their technical mixtures. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
- Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds.
- the starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine.
- unsaturated carboxylic acids such as acrylic acid is also possible.
- betaines and "real" amphoteric surfactants reference is made to U.Ploog's article in Soap- Oil -Fat-Waxes, 198 , 373 (1982) . Further overviews on this topic can be found for example by A. O'Lennick et al.
- betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (III) R 3 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 4 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 5 for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X. represents an alkali and / or alkaline earth metal or ammonium.
- Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, Myristyldimethyl-amine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof.
- R 6 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
- m represents numbers from 1 to 3
- R 4 , R 5 , n and X have the meanings given above.
- Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaldic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
- suitable starting materials for the betaines to be used in accordance with the invention are also imidazolines which follow the formula (V) in which R 7 is an alkyl radical having 5 to 21 carbon atoms, R 8 is a hydroxyl group, an OCOR 7 or NHCOR 7 radical and m is 2 or 3.
- R 7 is an alkyl radical having 5 to 21 carbon atoms
- R 8 is a hydroxyl group
- an OCOR 7 or NHCOR 7 radical an OCOR 7 or NHCOR 7 radical
- m is 2 or 3.
- These substances are also known substances, for example by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as aminoethylethanolamine (AEEA) or diethylenetriamine can be obtained.
- AEEA aminoethylethanolamine
- diethylenetriamine diethylenetriamine
- Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
- Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (VI) in which R 9 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Z is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucamnonium.
- alkyl sulfates which can be used for the purposes of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arachelyl alcohol, aridyl alcohol, elaidyl alcohol, ela-elyl alcohol, ela-alcohol alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
- the sulfation products can preferably be used in the form of their alkali metal salts, and in particular their sodium salts.
- Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium, ammonium and / or magnesium salts are particularly preferred.
- the percentages relate to the proportion of detergent substance and add up to 100% by weight.
- the preferred ranges are given in brackets.
- the agents have a water content of preferably 75 to 85% by weight
- the agents according to the invention usually have a detergent content in the range from 5 to 40 and preferably 15 to 25% by weight. They are characterized by an excellent dishwashing ability, a high base foam, fat resistance and a particularly advantageous emulsifying ability. Furthermore, they can contain common ingredients of dishwashing detergents such as builders (polycarborylates, EDTA, NTA, citric acid), alkalis, solubilizers (ethanol, propylene glycol, toluenesulfonate, cumene sulfonate), colors and fragrances.
- dishwashing detergents such as builders (polycarborylates, EDTA, NTA, citric acid), alkalis, solubilizers (ethanol, propylene glycol, toluenesulfonate, cumene sulfonate), colors and fragrances.
- fatty alcohol ether sulfate sodium or ammonium salts may also be present.
- sulfosuccinates may also be present.
- monoglyceride sulfates may also be present.
- fatty alcohol polyglycol ethers may also be present.
- protein hydrolysates may also be present.
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Abstract
Description
Die Erfindung betrifft wäßrige Handgeschirrspülmittel mit verbessertem Emulgiervermögen, enthaltend definierte Mengen niedrigethoxylierter Fettalkoholethersulfate in Form ihrer Magnesiumsalze.The invention relates to aqueous hand dishwashing detergents with improved emulsifying power, containing defined amounts of low-ethoxylated fatty alcohol ether sulfates in the form of their magnesium salts.
Handgeschirrspülmittel (HGSM) stellen in der Regel verdünnte wäßrige Detergensmischungen dar, die neben anionischen Tensiden vor allem nichtionische und amphotere Tenside enthalten. Neben der Reinigung des Geschirrs wird an diese Mittel die Anforderung eines starken und beständigen Schaums gestellt, der auch bei erheblicher Fettbelastung nicht zusammenbricht - auch wenn diese Eigenschalt mit der Reinigungsleistung nicht unmittelbar in Zusammenhang steht. Ein besonderes Problem besteht jedoch darin, den abgelösten lipophilen Schinutz zu emulgieren, d.h. eine Wiederablagerung auf dem Spülgut zu verhindern. Hier weisen auch Produkte des Stands der Technik Defizite auf.Hand dishwashing detergents (HGSM) are usually dilute aqueous detergent mixtures which, in addition to anionic surfactants, contain primarily nonionic and amphoteric surfactants. In addition to cleaning the dishes, these agents are required to have a strong and durable foam that does not collapse even when exposed to considerable fat - even if this activation is not directly related to the cleaning performance. However, a particular problem is to emulsify the detached lipophilic skin layer, i.e. to prevent redeposition on the dishes. Products of the state of the art also show deficits here.
Aus dem Stand der Technik sind bereits eine Reihe von Handgeschirrspülmitteln bekannt, die unter Mitverwendung von Magnesiumsalzen formuliert werden. So werden beispielsweise in der Europäischen Patentanmeldung EP-A 0 616 028 (Procter & Gamble) HGSM auf Basis von Fettalkoholethersulfat-Natriumsalzen, Eben und Magnesiumionen vorgeschlagen. Aus den Internationalen Patentanmeldungen WO 92/06156, WO 94/05769 und WO 94/24241 (Procter & Gamble) sind HGSM bekannt, die Kombinationen von Aniontensiden und Glucamiden, Ethercarbonsäuren bzw. sekundären Alkylsulfaten mit Magnesiumionen enthalten. Die Internationale Patentanmeldung WO 94/04644 (Unilever) beschreibt flüssige Reinigungsmittel mit einem Gehalt an Fettalkoholsulfaten, nichtionischen Tensiden und Magnesiumionen. Die US-Patentschriften US 5,269,974 und US 5,338,491 (Procter & Gamble) betreffen den Einsatz von Betainen bzw. Glucamiden zusammen mit Magnesiumsalzen in Handgeschirrspülmitteln. Der Einsatz höher ethoxylierter Fettalkoholethersulfat-Magnesiumsalze in HGSM ist schließlich aus der Britischen Patentanmeldung GB-A 20 78 246 (Procter & Gamble) bekannt. Alle diese genannten Schritten halten jedoch für die Verbesserung des Emulgiervermögens von Handgeschirrspülmitteln keine zufriedenstellende Lösung bereit.A number of hand dishwashing detergents are already known from the prior art, which are formulated with the use of magnesium salts. For example, European Patent Application EP-A 0 616 028 (Procter & Gamble) HGSM based on fatty alcohol ether sulfate sodium salts, plane and magnesium ions are proposed. HGSM are known from the international patent applications WO 92/06156, WO 94/05769 and WO 94/24241 (Procter & Gamble), the combinations of anionic surfactants and Contain glucamides, ether carboxylic acids or secondary alkyl sulfates with magnesium ions. The international patent application WO 94/04644 (Unilever) describes liquid cleaning agents containing fatty alcohol sulfates, nonionic surfactants and magnesium ions. US Pat. Nos. 5,269,974 and 5,338,491 (Procter & Gamble) relate to the use of betaines or glucamides together with magnesium salts in hand dishwashing detergents. Finally, the use of higher ethoxylated fatty alcohol ether sulfate magnesium salts in HGSM is known from British patent application GB-A 20 78 246 (Procter & Gamble). However, all of these steps do not provide a satisfactory solution for improving the emulsifying power of hand dishwashing detergents.
Die komplexe Aufgabe der Erfindung hat somit darin bestanden, wäßrige Handgeschirrspülmittel zur Verfügung zu stellen, die gleichzeitig über ein gutes Tellerspülvermögen, einen hohen Basisschaum, gute Fettbelastbarkeit und insbesondere ein ausgezeichnetes Emulgiervermögen verfügen.The complex object of the invention was therefore to provide aqueous hand dishwashing detergents which at the same time have good dishwashing power, high base foam, good fat resistance and, in particular, excellent emulsifying power.
Gegenstand der Erfindung sind wäßrige Handgeschirrspülmittel, enthaltend Fettalkoholethersulfate der Formel (I),
Überraschenderweise wurde gefunden, daß niedrigethoxylierte Fettalkoholethersulfate in Form ihrer Magnesiumsalze nicht nur über ein ausgezeichnetes Tellerspülvermögen und auch bei Fettbelastung über einen hohen Basisschaum verfügen, sondern zudem ein besonders vorteilhaftes Emulgiervermögen verfügen, das es gestattet, eine Wiederablagerung der vom Teller abgelösten lipophilen Anschmutzung auf dem gespülten Gut sicher zu vermeiden. Bedingung ist jedoch, daß der Anteil der oben genannten Magnesiumsalze - bezogen auf den Anteil an waschaktiver, d.h. tensidischer Substanz - oberhalb einer kritischen Grenze liegt. In einer bevorzugten Ausführungsform der Erfindung können die Mittel als weitere Tenside Alkyl- und/oder Alkenyloligoglykoside, Betaine und/oder Fettalkoholsulfate enthalten.Surprisingly, it was found that low-ethoxylated fatty alcohol ether sulfates in the form of their magnesium salts not only have an excellent dishwashing ability and also have a high base foam when loaded with fat, but also have a particularly advantageous emulsifying ability which allows the lipophilic soiling detached from the dish to be redeposited on the washed Good to avoid safely. However, the condition is that the proportion of the above-mentioned magnesium salts - based on the proportion of detergent, ie surfactant - is above a critical limit. In In a preferred embodiment of the invention, the agents can contain alkyl and / or alkenyl oligoglycosides, betaines and / or fatty alcohol sulfates as further surfactants.
Bei den im Sinne der Erfindung einzusetzenden Fettalkoholsulfaten handelt es sich um an sich bekannte Stoffe, die durch Anlagerung von sehr wenig, nämlich durchschnittlich 0,5 bis 1,5, vorzugsweise etwa 1 Mol Ethylenoxid an einen technischen Kokosfettalkohol mit 8 bis 18 und vorzugsweise 12 bis 14 Kohlenstoffatomen, Sulfatierung des Polyglycolethers und Neutralisation mit einem basischen Magnesiumsalz erhalten werden. Eine neuere Übersicht zu Magnesiumsalz-Tensiden ist von H.Plate in Parf. Kosm. 76, 28 (1995) erschienen.The fatty alcohol sulfates to be used for the purposes of the invention are substances known per se which, by the addition of very little, namely an average of 0.5 to 1.5, preferably about 1 mol, of ethylene oxide to a technical coconut fatty alcohol containing 8 to 18 and preferably 12 up to 14 carbon atoms, sulfation of the polyglycol ether and neutralization with a basic magnesium salt. A recent overview of magnesium salt surfactants is from H.Plate in Parf. Cosm. 76 , 28 (1995) .
Alkyl- und Alkenyloligoglykoside stellen bekannte nichtionische Tenside dar, die der Formel (II) folgen,
Die Indexzahl p in der allgemeinen Formel (II) gibt den Oligomerisierungsgrad (DP-Grad), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt.The index number p in the general formula (II) indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6, the value p is one for a certain alkyl oligoglycoside analytically determined arithmetic size, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
Der Alkyl- bzw. Alkenylrest R2 kann sich von primären Alkoholen mit 4 bis 11, vor-zugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capron-alkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3).The alkyl or alkenyl radical R 2 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capron alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C 8 -C 10 (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C 8 -C 18 coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C 12 - Alcohol can be contaminated and alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3).
Der Alkyl- bzw. Alkenylrest R2 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalko-hol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.The alkyl or alkenyl radical R 2 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as described above, and their technical mixtures. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
Betaine stellen bekannte Tenside dar, die überwiegend durch Carboxyalkylierung, vorzugsweise Carboxymethylierung von aminischen Verbindungen hergestellt werden. Vorzugsweise werden die Ausgangsstoffe mit Halogencarbonsäuren oder deren Salzen, insbesondere mit Natriumchloracetat kondensiert, wobei pro Mol Betain ein Mol Salz gebildet wird. Ferner ist auch die Anlagerung von ungesättigten Carbonsäuren wie beispielsweise Acrylsäure möglich. Zur Nomenklatur und insbesondere zur Unterscheidung zwischen Betainen und "echten" Amphotensiden sei auf den Beitrag von U.Ploog in Seifen-Öle-Fette-Wachse, 198, 373 (1982) verwiesen. Weitere Übersichten zu diesem Thema finden sich beispielsweise von A.O'Lennick et al. in HAPPI, Nov. 70 (1986), S.Holzman et al. in Tens. Det. 23, 309 (1986), R.Bibo et al. in Soap Cosm. Chem. Spec. Apr. 46 (1990) und P.Ellis et al. in Euro Cosm. 1, 14 (1994). Außerdem sei auf die Deutsche Patentanmeldung DE-A1 42 34 487 (Henkel) verwiesen, aus der Handgeschirrspülmittel mit einem Gehalt an Alkylglucosiden, Betainen und Fettalkoholpolyglycolethern bekannt sind.Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids such as acrylic acid is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to U.Ploog's article in Soap- Oil -Fat-Waxes, 198 , 373 (1982) . Further overviews on this topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens. Det. 23: 309 (1986), R.Bibo et al. in Soap Cosm. Chem. Spec. Apr. 46 (1990) and P.Ellis et al. in Euro Cosm. 1 , 14 (1994) . In addition, reference is made to the German patent application DE-A1 42 34 487 (Henkel), from which hand dishwashing detergents containing alkyl glucosides, betaines and fatty alcohol polyglycol ethers are known.
Beispiele für geeignete Betaine stellen die Carboxyalkylierungsprodukte von sekundären und insbesondere tertiären Aminen dar, die der Formel (III) folgen,
Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C12/14-Kokosalkyldimethylamin, Myristyldimethyl-amin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C16/18-Talgalkyldimethylamin sowie deren technische Gemische.Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, Myristyldimethyl-amine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof.
Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (IV) folgen,
Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaldinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C8/18-Kokosfettsäure-N,N-dimethylaminopropylamid mit Natriumchloracetat.Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaldic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
Weiterhin kommen als geeignete Ausgangsstoffe für die im Sinne der Erfindung einzusetzenden Betaine auch Imidazoline in Betracht, die der Formel (V) folgen,
Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C12/14-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden.Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
Unter Alkyl- und/oder Alkenylsulfaten, die auch häufig als Fettalkoholsulfate bezeichnet werden, sind die Sulfatierungsprodukte primärer Alkohole zu verstehen, die der Formel (VI) folgen,
Typische Beispiele für Alkylsulfate, die Sinne der Erfindung Anwendung finden können, sind die Sulfatierungsprodukte von Capronalkohol, Caprylalkohol, Caprinalkohol, 2-Ethylhexylalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technischen Gemischen, die durch Hochdruckhydrierung technischer Methylesterfraktionen oder Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können vorzugsweise in Form ihrer Alkalisalze, und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders bevorzugt sind Alkylsulfate auf Basis von C16/18-Talgfettalkoholen bzw. pflanzlicher Fettalkohole vergleichbarer C-Kettenverteilung in Form ihrer Natrium-, Ammonium- und/oder Magnesiumsalze.Typical examples of alkyl sulfates which can be used for the purposes of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arachelyl alcohol, aridyl alcohol, elaidyl alcohol, ela-elyl alcohol, ela-alcohol alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts, and in particular their sodium salts. Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium, ammonium and / or magnesium salts are particularly preferred.
In einer bevorzugten Ausführungsform der Erfindung enthalten die wäßrigen Handgeschirrspülmittel folgende Inhaltsstoffe:
- 40 bis 100 (45 bis 80) Gew.-% Kokosfettalkohol+1EO-sulfat-Magpesiumsalz,
- 0 bis 35 (20 bis 30) Gew.-% Alkylsulfate (z.B. Laurylsulfat-Ammoniumsalz),
- 0 bis 15 ( 5 bis 15) Gew.-% Alkylglucoside (z.B. Kokosalkyloligoglucosid) und
- 0 bis 15 ( 5 bis 15) Gew.-% Betaine (z.B. Kokosfettsäureamidobetain).
- 40 to 100 (45 to 80)% by weight coconut fatty alcohol + 1EO sulfate magnesium salt,
- 0 to 35 (20 to 30)% by weight alkyl sulfates (e.g. lauryl sulfate ammonium salt),
- 0 to 15 (5 to 15)% by weight alkyl glucosides (e.g. coconut alkyl oligoglucoside) and
- 0 to 15 (5 to 15)% by weight betaines (e.g. coconut fatty acid amido betaine).
Die Prozentangaben beziehen sich auf den Anteil an waschaktiver Substanz und ergänzen sich zu 100 Gew.-%. In Klammern angegeben sind die bevorzugten Bereiche. Die Mittel weisen einen Wassergehalt von vorzugsweise 75 bis 85 Gew.-% aufThe percentages relate to the proportion of detergent substance and add up to 100% by weight. The preferred ranges are given in brackets. The agents have a water content of preferably 75 to 85% by weight
Die erfindungsgemäßen Mittel besitzen üblicherweise einen Anteil an waschaktiver Substanz im Bereich von 5 bis 40 und vorzugsweise 15 bis 25 Gew.-%. Sie zeichnen sich durch ein ausgezeichnetes Tellerspülvermögen, einen hohen Basisschaum, Fettbelastbarkeit und ein besonders vorteilhaftes Emulgiervermögen aus. Des weiteren können sie übliche Bestandteile von Geschirrspülmitteln wie beispielsweise Builder (Polycarborylate, EDTA, NTA, Citronensäure), Alkalien, Lösungsvermittler (Ethanol, Propylenglycol, Toluolsulfonat, Cumolsulfonat), Farb- und Duftstoffe enthalten. Neben den genannten Tensiden können zudem noch Fettalkoholethersulfate-Natrium- bzw. Ammoniumsalze, Sulfosuccinate, Monoglyceridsulfate, Fettalkoholpolyglycolether, Fettsäure-N-alkylglucamide, Proteinhydrolysate, Proteinfettsäurekondensate und/oder Aminoxide enthalten sein.The agents according to the invention usually have a detergent content in the range from 5 to 40 and preferably 15 to 25% by weight. They are characterized by an excellent dishwashing ability, a high base foam, fat resistance and a particularly advantageous emulsifying ability. Furthermore, they can contain common ingredients of dishwashing detergents such as builders (polycarborylates, EDTA, NTA, citric acid), alkalis, solubilizers (ethanol, propylene glycol, toluenesulfonate, cumene sulfonate), colors and fragrances. In addition to the surfactants mentioned, fatty alcohol ether sulfate sodium or ammonium salts, sulfosuccinates, monoglyceride sulfates, fatty alcohol polyglycol ethers, fatty acid N-alkylglucamides, protein hydrolysates, protein fatty acid condensates and / or amine oxides may also be present.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung erläutern ohne ihn darauf einzuschränken.The following examples are intended to explain the subject matter of the invention without restricting it.
Die Testrezepturen R1 bis R10 stellen Mischungen verschiedener anionischer Tenside (Fettalkoholethersulfate bzw. Fettalkoholsulfate), nichtionischer und amphoterer Tenside dar, die als weitere Bestandteile Polycarbonsäuresalze, Natriumhydroxid und Ethanol enthalten. Der Gehalt an waschaktiver Substanz betrug in allen Fallen 19 Gew.-%. Die Rezepturen R1 bis R3 sind erfindungsgemäß, die Rezepturen R4 bis R10 dienen zum Vergleich. Die Zusammensetzung der Rezepturen ist in Tabelle 1 zusammengefaßt; alle Angaben verstehen sich als Gew.-% bezogen auf 100 Gew.-% Aktivsubstanz. Im Rahmen der Untersuchungen wurden folgende anwendungstechnischen Eigenschalten geprüft (zu den Ergebnissen vgl. ebenfalls Tabelle 1):
- Die Ermittlung des Tellerspülvermögens wurde mit Hilfe des Tellertestes [Fette, Seifen, Anstrichmitt., 74, 163 (1972)] durchgeführt. Hierzu wurden Teller mit einem Durchmesser von 14 cm mit je 2 g Rindertalg ("RiTa", Säurezahl 9-10) bzw. einer Mischanschmutzung angeschmutzt und 24 h bei Raumtemperatur gelagert. Anschließend wurden die Teller bei 50°C bzw. 45°C mit 5 l Leitungswasser der Härte 16°d gespült. Die Prüfmischung wurde mit einer Dosierung von 0,5 g/l Aktivsubstanz/l eingesetzt. Der Spülversuch wurde abgebrochen, sobald der Schaum an der Oberfläche völlig verschwunden war.
- Die Ermittlung des Schaumvermögens erfolgte gemäß DIN 53 902, Teil 2 gemäß dem Ross-Miles Test. Die Testtemperatur betrug 20°C, die Wasserhärte 16°d und die Aktivsubstanzmenge 25 g/l. Bestimmt wurde der Basisschaum in mi mit und ohne Fettbelastung (Olivenöl).
- Das Emulgiervermögen wurde schließlich bei einer Temperatur von 25°C bei einer Wasserhärte von 16°d bestimmt. Hierzu wurden Emulsionen aus jeweils 10 g der Rezepturen R1 bis R10, 40 ml Wasser und 50 g Olivenöl hergestellt. Angegeben ist die Menge des aus der Emulsion abgeschiedenen Wassers nach 1 bzw. 4 h in %.
- The determination of the dishwashing power was determined using the plate test [Fette, Seifen, Anstrichmittel Mitt., 74, 163 (1972)] is performed. For this purpose, plates with a diameter of 14 cm were soiled with 2 g of beef tallow ("RiTa", acid number 9-10) or mixed soiling and stored for 24 hours at room temperature. The plates were then rinsed at 50 ° C or 45 ° C with 5 l tap water with a hardness of 16 ° d. The test mixture was used at a dosage of 0.5 g / l active substance / l. The rinsing attempt was stopped as soon as the foam on the surface had completely disappeared.
- The foaming power was determined in accordance with DIN 53 902, part 2 in accordance with the Ross-Miles test. The test temperature was 20 ° C, the water hardness 16 ° d and the amount of active substance 25 g / l. The base foam was determined in mi with and without fat (olive oil).
- The emulsifying power was finally determined at a temperature of 25 ° C and a water hardness of 16 ° d. For this purpose, emulsions were prepared from 10 g of the formulations R1 to R10, 40 ml of water and 50 g of olive oil. The amount of water separated from the emulsion is given in% after 1 or 4 hours.
Diskussion der Ergebnisse. Die Beispiele und Vergleichsbeispiele zeigen, daß ein optimales Emulgiervermögen bei hohem Tellerspülvermögen und zufriedenstellendem Basisschaum nur dann erreicht wird, weg als anionisches Tensid ein Kokosfettalkohol+1EO-sulfat-Magnesiumsalz in einer Konzentration von 50 Gew.-% und mehr bezogen auf den Gehalt an waschaktiver Substanz im Mittel vorhanden ist. Oberhalb der kritischen Grenze verträgt die Rezeptur die Mitverwendung von weiteren, ansonsten nicht unbedingt vorteilhaften anionischen Tensiden, wird der Gehalt jedoch unterschritten, tritt sofort eine signifikante Verschlechterung des Emulgiervermögens auf. Discussion of the results. The examples and comparative examples show that optimal emulsifying power with high dishwashing power and satisfactory base foam is only achieved as a anionic surfactant, a coconut oil alcohol + 1EO sulfate magnesium salt in a concentration of 50% by weight and more based on the content of detergent Substance is present on average. Above the critical limit, the recipe tolerates the use of other, otherwise not necessarily advantageous, anionic surfactants, but if the content falls below this level, the emulsifying capacity immediately deteriorates significantly.
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DE19534369A DE19534369C2 (en) | 1995-09-15 | 1995-09-15 | Aqueous hand dishwashing liquid |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999010463A1 (en) * | 1997-08-25 | 1999-03-04 | Cognis Deutschland Gmbh | Aqueous agents for washing dishes by hand |
FR2826017A1 (en) * | 2001-06-15 | 2002-12-20 | Cognis France Sa | Surfactant mixtures useful in cosmetics, body care products, shower gels or shower baths and baby care products comprises oligoglycosides, betaines and alkyl ether sulfates |
WO2009007166A1 (en) * | 2007-07-09 | 2009-01-15 | Henkel Ag & Co. Kgaa | Washing or cleaning composition comprising surfactants based on renewable raw materials |
WO2009024747A2 (en) * | 2007-08-17 | 2009-02-26 | Reckitt Benckiser Inc. | Environmentally acceptable hard surface treatment compositions |
WO2015178902A1 (en) * | 2014-05-21 | 2015-11-26 | Colgate-Palmolive Company | Aqueous liquid dishwashing composition |
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EP0125854A2 (en) * | 1983-05-14 | 1984-11-21 | The Procter & Gamble Company | Liquid detergent compositions |
EP0157443A1 (en) * | 1984-03-19 | 1985-10-09 | THE PROCTER & GAMBLE COMPANY | Detergent composition containing semi-polar nonionic detergent, alkaline earth metal anionic detergent, and amidoalkylbetaine detergent |
WO1991011506A1 (en) * | 1990-02-02 | 1991-08-08 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous liquid cleaning agent |
US5338491A (en) * | 1992-03-26 | 1994-08-16 | The Proctor & Gamble Co. | Cleaning compositions with glycerol amides |
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US4316824A (en) * | 1980-06-26 | 1982-02-23 | The Procter & Gamble Company | Liquid detergent composition containing alkyl sulfate and alkyl ethoxylated sulfate |
DE69408532D1 (en) * | 1993-04-08 | 1998-03-19 | Procter & Gamble | CLEANING AGENTS CONTAINING MAGNESIUM IN STABLE LIQUID, GEL-SHAPED OR OTHER FORMS WITH SECONDARY (2,3) ALKYL SULFATE TENSIDES |
-
1995
- 1995-09-15 DE DE19534369A patent/DE19534369C2/en not_active Expired - Fee Related
-
1996
- 1996-09-06 ES ES96114276T patent/ES2153925T3/en not_active Expired - Lifetime
- 1996-09-06 EP EP96114276A patent/EP0763591B1/en not_active Expired - Lifetime
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Publication number | Priority date | Publication date | Assignee | Title |
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EP0125854A2 (en) * | 1983-05-14 | 1984-11-21 | The Procter & Gamble Company | Liquid detergent compositions |
EP0157443A1 (en) * | 1984-03-19 | 1985-10-09 | THE PROCTER & GAMBLE COMPANY | Detergent composition containing semi-polar nonionic detergent, alkaline earth metal anionic detergent, and amidoalkylbetaine detergent |
WO1991011506A1 (en) * | 1990-02-02 | 1991-08-08 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous liquid cleaning agent |
US5338491A (en) * | 1992-03-26 | 1994-08-16 | The Proctor & Gamble Co. | Cleaning compositions with glycerol amides |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999010463A1 (en) * | 1997-08-25 | 1999-03-04 | Cognis Deutschland Gmbh | Aqueous agents for washing dishes by hand |
FR2826017A1 (en) * | 2001-06-15 | 2002-12-20 | Cognis France Sa | Surfactant mixtures useful in cosmetics, body care products, shower gels or shower baths and baby care products comprises oligoglycosides, betaines and alkyl ether sulfates |
WO2002102949A1 (en) * | 2001-06-15 | 2002-12-27 | Cognis France S.A. | Surfactant mixtures |
US7279456B2 (en) | 2001-06-15 | 2007-10-09 | Gognis France S.A. | Surfactant mixtures |
WO2009007166A1 (en) * | 2007-07-09 | 2009-01-15 | Henkel Ag & Co. Kgaa | Washing or cleaning composition comprising surfactants based on renewable raw materials |
WO2009024747A2 (en) * | 2007-08-17 | 2009-02-26 | Reckitt Benckiser Inc. | Environmentally acceptable hard surface treatment compositions |
WO2009024747A3 (en) * | 2007-08-17 | 2009-04-09 | Reckitt Benckiser Inc | Environmentally acceptable hard surface treatment compositions |
WO2015178902A1 (en) * | 2014-05-21 | 2015-11-26 | Colgate-Palmolive Company | Aqueous liquid dishwashing composition |
US20170121652A1 (en) * | 2014-05-21 | 2017-05-04 | Colgate-Palmolive Company | Aqueous Liquid Dishwashing Composition |
US10329521B2 (en) * | 2014-05-21 | 2019-06-25 | Colgate-Palmolive Company | Aqueous liquid dishwashing composition comprising an ammonium alkyl ether sulfate and alkylamidopropyl betaine |
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DE59606206D1 (en) | 2001-01-18 |
ES2153925T3 (en) | 2001-03-16 |
DE19534369C2 (en) | 2000-06-15 |
DE19534369A1 (en) | 1997-03-20 |
EP0763591B1 (en) | 2000-12-13 |
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