EP0652932B1 - Process for producing storable non-ionic tensides - Google Patents

Process for producing storable non-ionic tensides Download PDF

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Publication number
EP0652932B1
EP0652932B1 EP93915972A EP93915972A EP0652932B1 EP 0652932 B1 EP0652932 B1 EP 0652932B1 EP 93915972 A EP93915972 A EP 93915972A EP 93915972 A EP93915972 A EP 93915972A EP 0652932 B1 EP0652932 B1 EP 0652932B1
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EP
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Prior art keywords
alkyl
oligoglycosides
carbon atoms
alkenyl
crystallization
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EP93915972A
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German (de)
French (fr)
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EP0652932A1 (en
Inventor
Manfred Weuthen
Thomas Engels
Hermann Hensen
Holger Tesmann
Dieter Nickel
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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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2072—Aldehydes-ketones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/02—Organic and inorganic agents containing, except water

Definitions

  • the invention relates to a process for the preparation of storage-stable nonionic surfactants with improved crystallization resistance, in which alk (en) yl oligoglycosides are added to selected crystallization moderators.
  • Alk (en) yl oligoglycosides are important non-ionic surfactants which, due to their good detergent properties and high environmental compatibility, are being used increasingly in detergents, dishwashing detergents and cleaning agents.
  • alk (en) yl oligoglycosides available for a certain period of time, for example as aqueous solutions or pastes, until they are finished.
  • aqueous alk (en) yl oligoglycosides show a strong tendency to crystallize, the homogeneity of such preparations decreases over time when they are stored under ambient conditions and form them agglomerates containing water of crystallization, which greatly reduce the pumpability of the products.
  • alk (en) yl oligoglycosides are therefore not stored at room temperature, but at temperatures of at least 40 ° C. In this way, crystallization of the preparations can be largely prevented, but storage at elevated temperature is associated with additional effort and can also severely impair the color quality of the products.
  • EP-A 0 388 810 aqueous compositions which contain alkyl glucosides and short-chain primary alcohols.
  • EP-A 0 487 262 relates to a process for the preparation of storage-stable alkyl glucosides in which fatty alcohol polyglycol ethers are added to the aqueous pastes as stabilizers. Mixtures of alkyl glucosides and ethoxylated fatty alcohols are also mentioned in the documents EP-A 0 377 807 and EP-A 0 405 967 .
  • EP-A 0 408 965 discloses aqueous compositions of alkyl glucosides and polyethylene glycols.
  • mixtures of alkyl glucosides based on linear and branched fatty alcohols are suitable for the production of liquid cleaning agents.
  • the object of the invention was therefore to develop a process by means of which alk (en) yl oligoglucosides can be stored at temperatures below 40 ° C. without impairing the pumpability of the products through the formation of crystalline agglomerates.
  • Alkyl and alkenyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/3977 .
  • the alkyl and / or alkenyl oligoglycosides can differ from aldoses or ketoses with 5 or 6 carbon atoms, preferably derive the glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the alkyl or alkenyl radical R 1 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such 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 1 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, and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
  • the crystallization moderators can be added to the alkyl and / or alkenyl oligoglycosides in amounts of 0.01 to 7, preferably 1 to 3% by weight, based on the alkyl and / or alkenyl oligoglycosides. It has proven advantageous here to use iron (III) ions in amounts of 0.01 to 0.5% by weight in order to reliably prevent discoloration of the products catalyzed by Fe ions.
  • the process according to the invention is used to stabilize aqueous preparations which contain alkyl and / or alkenyl oligoglycosides.
  • the solids content of these preparations can be 1 to 70% by weight, preferably 30 to 60% by weight, the problem of reduced storage stability due to crystallization only becoming more important with products of higher concentration.
  • the aqueous preparations can also contain other ingredients customary for washing, rinsing and cleaning agents, such as: anionic, nonionic, amphoteric or zwitterionic surfactants, oil bodies, builders, hydrotropes, adjusting agents, optical brighteners, graying inhibitors , Defoamers and perfumes.
  • aqueous preparations which can be obtained by the process according to the invention and contain alkyl and / or alkenyl oligoglycosides are color-stable at storage temperatures of about 30 ° C. and show practically no tendency towards crystallization; at the same time the solubility limit is lowered. They are therefore suitable for the production of detergents, dishwashing detergents and cleaning products and products for hair and body care, in which they can be present in amounts of 1 to 50, preferably 10 to 30,% by weight, based on the composition.
  • SET melting end points
  • Tab. 1 shows the melting end points for the hydrates with the highest SET. The results are to be evaluated in such a way that when the coconut alkyl oligoglucoside is stored there is no crystallization above the stated SET and only a greatly delayed crystallization below the SET.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Saccharide Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Storable non-ionic tensides with improved crystallisation resistance are obtained if, to aqueous preparations containing alkyl and/or alkenyl oligoglycosides of formula (I): R1O-[G]p in which R1 is a linear alkyl and/or alkenyl radical with 6 to 22 carbon atoms, G is a sucrose radical with 5 or 6 carbon atoms and p represents numbers from 1 to 10, are added crystallisation moderators selected from the group consisting of a) alkyl oligoglycosides based on short-chained primary alcohols, b) alkyl oligoglycosides based on Guerbet alcohols, c) alkyl oligoglycosides based on polyoles, d) short-chained primary alcohols, e) fatty alcohol polyglycol ethers, f) polyethylene glycols, g) glucose and h) iron-(III)-ions.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft ein Verfahren zur Herstellung von lagerstabilen nichtionischen Tensiden mit verbesserter Kristallisationsbeständigkeit, bei dem man Alk(en)yloligoglykosiden ausgewählte Kristallisationsmoderatoren zusetzt.The invention relates to a process for the preparation of storage-stable nonionic surfactants with improved crystallization resistance, in which alk (en) yl oligoglycosides are added to selected crystallization moderators.

Stand der TechnikState of the art

Alk(en)yloligoglykoside stellen wichtige nichtionische Tenside dar, die infolge ihrer guten Detergenseigenschaften und hohen Umweltverträglichkeit in immer stärkerem Maße Eingang in Wasch-, Spül- und Reinigungsmittel finden.Alk (en) yl oligoglycosides are important non-ionic surfactants which, due to their good detergent properties and high environmental compatibility, are being used increasingly in detergents, dishwashing detergents and cleaning agents.

Für diesen Zweck ist es erforderlich, Alk(en)yloligoglykoside über bestimmte Zeiträume beispielsweise als wäßrige Lösungen oder Pasten zur Verfügung zu halten und zu lagern, bis eine Endverarbeitung stattfindet. Da wäßrige Alk(en)yloligoglykoside jedoch eine starke Neigung zur Kristallisation zeigen, nimmt die Homogenität derartiger Zubereitungen bei Lagerung unter Umgebungsbedingungen im Laufe der Zeit ab und es bilden sich kristallwasserhaltige Agglomerate, die die Pumpfähigkeit der Produkte stark herabsetzen.For this purpose it is necessary to keep alk (en) yl oligoglycosides available for a certain period of time, for example as aqueous solutions or pastes, until they are finished. However, since aqueous alk (en) yl oligoglycosides show a strong tendency to crystallize, the homogeneity of such preparations decreases over time when they are stored under ambient conditions and form them agglomerates containing water of crystallization, which greatly reduce the pumpability of the products.

Üblicherweise erfolgt die Lagerung von Alk(en)yloligoglykosiden daher nicht bei Raumtemperatur, sondern bei Temperaturen von mindestens 40°C. Auf diese Weise kann zwar eine Kristallisation der Zubereitungen weitgehend verhindert werden, die Lagerung bei erhöhter Temperatur ist jedoch mit zusätzlichem Aufwand verbunden und kann zudem die Farbqualität der Produkte stark beeinträchtigen.Usually alk (en) yl oligoglycosides are therefore not stored at room temperature, but at temperatures of at least 40 ° C. In this way, crystallization of the preparations can be largely prevented, but storage at elevated temperature is associated with additional effort and can also severely impair the color quality of the products.

Aus der EP-A 0 388 810 sind wäßrige Zusammensetzungen bekannt, die Alkylglucoside und kurzkettige primäre Alkohole enthalten. Gegenstand der EP-A 0 487 262 ist ein Verfahren zur Herstellung von lagerstabilen Alkylglucosiden, bei dem man den wäßrigen Pasten Fettalkoholpolyglycolether als Stabilisatoren zusetzt. Mischungen aus Alkylglucosiden und ethoxylierten Fettalkoholen werden auch in den Schriften EP-A 0 377 807 und EP-A 0 405 967 genannt. Die EP-A 0 408 965 offenbart wäßrige Zusammensetzungen von Alkylglucosiden und Polyethylenglycolen. Gemäß der Lehre der EP-A 0 444 262 eignen sich schließlich Mischungen von Alkylglucosiden auf Basis von linearen und verzweigten Fettalkoholen zur Herstellung von flüssigen Reinigungsmitteln.From EP-A 0 388 810 aqueous compositions are known which contain alkyl glucosides and short-chain primary alcohols. EP-A 0 487 262 relates to a process for the preparation of storage-stable alkyl glucosides in which fatty alcohol polyglycol ethers are added to the aqueous pastes as stabilizers. Mixtures of alkyl glucosides and ethoxylated fatty alcohols are also mentioned in the documents EP-A 0 377 807 and EP-A 0 405 967 . EP-A 0 408 965 discloses aqueous compositions of alkyl glucosides and polyethylene glycols. Finally, according to the teaching of EP-A 0 444 262 , mixtures of alkyl glucosides based on linear and branched fatty alcohols are suitable for the production of liquid cleaning agents.

Die Aufgabe der Erfindung bestand somit darin, ein Verfahren zu entwickeln, mit dessen Hilfe eine Lagerung von Alk(en)yloligoglucosiden bei Temperaturen unterhalb von 40°C möglich ist, ohne daß die Pumpfähigkeit der Produkte durch Bildung von kristallinen Agglomeraten beeinträchtigt wird.The object of the invention was therefore to develop a process by means of which alk (en) yl oligoglucosides can be stored at temperatures below 40 ° C. without impairing the pumpability of the products through the formation of crystalline agglomerates.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung ist ein Verfahren zur Herstellung von lagerstabilen nichtionischen Tensiden, bei dem man wäßrigen Zubereitungen enthaltend Alkyl- und/oder Alkenyloligoglykosiden der Formel (I)

        R 1 O-[G] p    (I)

in der R1 für einen linearen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht, Kristallisationsmoderatoren zusetzt, die ausgewählt sind aus der Gruppe, die von

  • a) Alkyloligoglykosiden auf Basis von kurzkettigen primären Alkoholen mit 1 bis 4 Kohlenstoffatomen
  • b) Alkyloligoglykosiden auf Basis von Polyolen,
  • c) Glucose und
  • d) Eisen-(III)-ionen
gebildet wird.The invention relates to a process for the preparation of storage-stable nonionic surfactants, in which aqueous preparations containing alkyl and / or alkenyl oligoglycosides of the formula (I)

R 1 O- [G] p (I)

in which R 1 is a linear alkyl and / or alkenyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10, Add crystallization moderators selected from the group consisting of
  • a) Alkyl oligoglycosides based on short-chain primary alcohols with 1 to 4 carbon atoms
  • b) alkyl oligoglycosides based on polyols,
  • c) glucose and
  • d) iron (III) ions
is formed.

Überraschenderweise wurde gefunden, daß man die Kristallisationsneigung der Alk(en)yloligoglucoside stark herabsetzen kann, wenn man ihnen kleine Mengen ausgesuchter Moderatoren zusetzt. Auf diese Weise werden wäßrige Zubereitungen erhalten, die bei Temperaturen um 30°C über Monate lager- und farbstabil sind und praktisch keine Tendenzen zur Kristallisation zeigen.Surprisingly, it was found that the tendency of the alk (en) yl oligoglucosides to crystallize can be greatly reduced if small amounts of selected moderators are added to them. In this way, aqueous preparations are obtained which are stable in storage and color at temperatures around 30 ° C. for months and show practically no tendencies towards crystallization.

Alkyl- und Alkenyloligoglykoside stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP-A1-0 301 298 und WO 90/3977 verwiesen.Alkyl and alkenyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/3977 .

Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside.The alkyl and / or alkenyl oligoglycosides can differ from aldoses or ketoses with 5 or 6 carbon atoms, preferably derive the glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.

Die Indexzahl p in der allgemeinen Formel (I) 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 (I) 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 in particular, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, 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, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

Der Alkyl- bzw. Alkenylrest R1 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, 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 anfallen. 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 1 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such 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 as well Alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3).

Der Alkyl- bzw. Alkenylrest R1 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, Behenylalkohol, Erucylalkohol, 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 1 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, and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Als Kristallisationsmoderatoren kommen folgende Substanzklassen in Betracht:

  • a) Alkyloligoglykoside auf Basis von kurzkettigen primären Alkoholen. Hierunter sind Methyl- und Butylglucoside zu verstehen.
  • b) Alkyloligoglykoside auf Basis von Polyolen. Hierunter sind Alkyloligoglykoside zu verstehen, die durch säurekatalysierte Acetalisierung von Glykosen, insbesondere Glucose mit Polyolen erhalten werden und der Formel (II) folgen,

            HO-(CH 2 CH 2 O) n -[G] p    (II)

    in der n für Zahlen von 1 bis 10 steht und G und p die oben angegebenen Bedeutungen besitzen. Typische Beispiele sind Alkyloligoglucoside mit einem DP-Grad von 1,3 bis 1,6 auf Basis von Ethylenglycol, Diethylenglycol oder Triethylenglycol.
  • c) Glucose;
  • d) Eisen-(III)-ionen, die beispielsweise in Form von Eisen(III)-salzen wie etwa FeCl3 zudosiert werden können.
The following classes of substances are suitable as crystallization moderators:
  • a) Alkyl oligoglycosides based on short-chain primary alcohols. This includes methyl and butyl glucosides.
  • b) alkyl oligoglycosides based on polyols. These are understood to mean alkyl oligoglycosides which are obtained by acid-catalyzed acetalization of glycoses, in particular glucose with polyols, and which follow the formula (II),

    HO- (CH 2 CH 2 O) n - [G] p (II)

    in which n stands for numbers from 1 to 10 and G and p have the meanings given above. Typical examples are alkyl oligoglucosides with a DP degree of 1.3 to 1.6 based on ethylene glycol, diethylene glycol or triethylene glycol.
  • c) glucose;
  • d) iron (III) ions, which can be metered in, for example, in the form of iron (III) salts such as FeCl 3 .

Die Kristallisationsmoderatoren können den Alkyl- und/oder Alkenyloligoglykosiden in Mengen von 0,01 bis 7, vorzugsweise 1 bis 3 Gew.-% - bezogen auf die Alkyl- und/oder Alkenyloligoglykoside - zugesetzt werden. Hierbei hat es sich als vorteilhaft erwiesen, Eisen-(III)-ionen in Mengen von 0,01 bis 0,5 Gew.-% einzusetzen, um einer durch Fe-ionen katalysierten Verfärbung der Produkte zuverlässig vorzubeugen.The crystallization moderators can be added to the alkyl and / or alkenyl oligoglycosides in amounts of 0.01 to 7, preferably 1 to 3% by weight, based on the alkyl and / or alkenyl oligoglycosides. It has proven advantageous here to use iron (III) ions in amounts of 0.01 to 0.5% by weight in order to reliably prevent discoloration of the products catalyzed by Fe ions.

Naturgemäß findet das erfindungsgemäße Verfahren zur Stabilisierung wäßriger Zubereitungen Verwendung, die Alkyl- und/ oder Alkenyloligoglykoside enthalten. Der Feststoffgehalt dieser Zubereitungen kann 1 bis 70, vorzugsweise 30 bis 60 Gew.-% betragen, wobei das Problem der durch Kristallisation bedingten verminderten Lagerstabilität verstärkt erst bei höher konzentrierten Produkten an Bedeutung gewinnt. Im Sinne des erfindungsgemäßen Verfahrens können die wäßrigen Zubereitungen auch weitere für Wasch-, Spül- und Reinigungsmittel übliche Inhaltsstoffe enthalten, als da beispielsweise sind: anionische, nichtionische, amphotere bzw. zwitterionische Tenside, Ölkörper, Builder, Hydrotrope, Stellmittel, Optische Aufheller, Vergrauungsinhibitoren, Entschäumer und Parfumstoffe.Naturally, the process according to the invention is used to stabilize aqueous preparations which contain alkyl and / or alkenyl oligoglycosides. The solids content of these preparations can be 1 to 70% by weight, preferably 30 to 60% by weight, the problem of reduced storage stability due to crystallization only becoming more important with products of higher concentration. In the sense of the process according to the invention, the aqueous preparations can also contain other ingredients customary for washing, rinsing and cleaning agents, such as: anionic, nonionic, amphoteric or zwitterionic surfactants, oil bodies, builders, hydrotropes, adjusting agents, optical brighteners, graying inhibitors , Defoamers and perfumes.

Gewerbliche AnwendbarkeitIndustrial applicability

Die nach dem erfindungsgemäßen Verfahren erhältlichen wäßrigen Zubereitungen enthaltend Alkyl- und/oder Alkenyloligoglykoside sind bei Lagertemperaturen von ca. 30°C farbstabil und zeigen praktisch keine Tendenz zur Kristallisation; gleichzeitig wird die Löslichkeitsgrenze herabgesenkt. Sie eignen sich daher zur Herstellung von Wasch-, Spül- und Reinigungsmitteln sowie Produkten zur Haar- und Körperpflege, in denen sie in Mengen von 1 bis 50, vorzugsweise 10 bis 30 Gew.-% - bezogen auf die Mittel - enthalten sein können.The aqueous preparations which can be obtained by the process according to the invention and contain alkyl and / or alkenyl oligoglycosides are color-stable at storage temperatures of about 30 ° C. and show practically no tendency towards crystallization; at the same time the solubility limit is lowered. They are therefore suitable for the production of detergents, dishwashing detergents and cleaning products and products for hair and body care, in which they can be present in amounts of 1 to 50, preferably 10 to 30,% by weight, based on the composition.

Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken.The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

BeispieleExamples I. Eingesetzte Stoffe I. Substances used

  • A) C12/14-Kokosalkyloligoglucosid (DP = 1,3) Plantaren(R) APG 600, Fa.Henkel KGaA, Düsseldorf/FRG.A) C 12/14 coconut alkyl oligoglucoside (DP = 1.3) Plantaren (R) APG 600, from Henkel KGaA, Düsseldorf / FRG.
  • B1) GlucoseB1) glucose
  • B2) Fe-(III)-ionen, eingesetzt als FeCl3 B2) Fe (III) ions used as FeCl 3
II. Vorbereitung der Proben II. Preparation of the samples

Eine Paste von 500 g C12/14-Kokosalkyloligoglucosid A (Festtoffgehalt 52 Gew.-%) wurde mit bzw. ohne Kristallisationsmoderatoren solange erwärmt, bis eine klare Lösung vorlag. Diese wurden zunächst über einen Zeitraum von 7 Tagen bei 6°C und anschließend über 6 Wochen bei Raumtemperatur gelagert. Mit Hilfe der Differential-Thermoanalyse wurden in Abhängigkeit der Lagerzeit die Schmelzendpunkte (SET) für Hydrate des Kokosalkyloligoglucosids mit 1 bis 4 Mol Kristallwasser ermittelt, die nacheinander durchlaufen werden.A paste of 500 g of C 12/14 coconut alkyl oligoglucoside A (solids content 52% by weight) was heated with or without crystallization moderators until a clear solution was obtained. These were initially stored at 6 ° C. for 7 days and then at room temperature for 6 weeks. With the help of differential thermal analysis, the melting end points (SET) for hydrates of coconut alkyl oligoglucoside with 1 to 4 moles of water of crystallization were determined, depending on the storage time, which are run through in succession.

In Tab.1 sind die Schmelzendpunkte für die Hydrate mit dem jeweils höchsten SET angegeben. Die Ergebnisse sind so zu werten, daß bei Lagerung des Kokosalkyloligoglucosids oberhalb der angegebenen SET keine, und unterhalb der SET nur eine stark verzögerte Kristallisation eintritt. Tab.1: DSC-Untersuchungen Bsp. KM c(KM) % SET °C 1 B1 1,00 29 2 B2 0,01 30 V1 - - >40 Legende: KM = Kristallisationsmoderator
   c(KM) = Konzentration Kristallisationsmoderator Tab. 1 shows the melting end points for the hydrates with the highest SET. The results are to be evaluated in such a way that when the coconut alkyl oligoglucoside is stored there is no crystallization above the stated SET and only a greatly delayed crystallization below the SET. Tab. 1: DSC examinations E.g. KM c (KM) % SET ° C 1 B1 1.00 29 2nd B2 0.01 30th V1 - - > 40 Legend: KM = crystallization moderator
c (KM) = concentration of crystallization moderator

Claims (4)

  1. A process for the production of storable nonionic surfactants, in which crystallization moderators are added to aqueous formulations containing alkyl and/or alkenyl oligoglycosides corresponding to formula (I):

            R 1 O-[G] p    (I)

    in which R1 is a linear alkyl and/or alkenyl radical containing 6 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number of 1 to 10, characterized in that the moderators are selected from the group consisting of
    (a) alkyl oligoglycosides based on short-chain primary alcohols containing 1 to 4 carbon atoms,
    (b) alkyl oligoglycosides based on polyols,
    (c) glucose and
    (d) iron(III) ions.
  2. A process as claimed in claim 1, characterized in that butyl glucosides are used as component (a).
  3. A process as claimed in claims 1 and 2, characterized in that alkyl oligoglycosides based on polyols corresponding to formula (II):

            HO-(CH 2 CH 2 O) n -[G] p    (II)

    in which n is a number of 1 to 10 and G and p are as defined above,
    are used as component (b).
  4. A process as claimed in claims 1 to 3, characterized in that the crystallization moderators are used in quantities of 0.01 to 7% by weight, based on the alkyl and/or alkenyl oligoglycosides.
EP93915972A 1992-07-30 1993-07-21 Process for producing storable non-ionic tensides Expired - Lifetime EP0652932B1 (en)

Applications Claiming Priority (3)

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DE4225224 1992-07-30
DE4225224A DE4225224A1 (en) 1992-07-30 1992-07-30 Process for the production of storage-stable nonionic surfactants
PCT/EP1993/001939 WO1994003569A1 (en) 1992-07-30 1993-07-21 Process for producing storable non-ionic tensides

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EP0652932B1 true EP0652932B1 (en) 1997-05-14

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EP (1) EP0652932B1 (en)
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WO (1) WO1994003569A1 (en)

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WO1994003569A1 (en) 1994-02-17
US5556573A (en) 1996-09-17
JPH07509515A (en) 1995-10-19
DE4225224A1 (en) 1994-02-03
ES2102044T3 (en) 1997-07-16
DE59306461D1 (en) 1997-06-19
EP0652932A1 (en) 1995-05-17

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