EP0556220A1 - Stabilized surfactant pastes. - Google Patents

Stabilized surfactant pastes.

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Publication number
EP0556220A1
EP0556220A1 EP91918719A EP91918719A EP0556220A1 EP 0556220 A1 EP0556220 A1 EP 0556220A1 EP 91918719 A EP91918719 A EP 91918719A EP 91918719 A EP91918719 A EP 91918719A EP 0556220 A1 EP0556220 A1 EP 0556220A1
Authority
EP
European Patent Office
Prior art keywords
surfactant
paste
product according
ppm
alkaline
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.)
Granted
Application number
EP91918719A
Other languages
German (de)
French (fr)
Other versions
EP0556220B1 (en
Inventor
Paul Schulz
Rainer Eskuchen
Manfred Weuthen
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes

Definitions

  • the invention relates to an aqueous-based surfactant stabilized against microbial attack, the surfactant in particular consisting essentially of a nonionic surfactant of the alkyl glycoside type.
  • the invention further relates to a method for producing this surfactant paste.
  • aqueous surfactant pastes protected against microbial attack can have excellent storage stability even without a content of the usual preservatives, if care is taken in their composition that certain impurities are not present.
  • an aqueous surfactant paste which contains 30 to 70% by weight of a surfactant which is stable in an alkaline environment, in particular a nonionic surfactant of the alkyl glycoside type, and which is characterized in that this paste is essentially free of bleachable color bodies and of such color body precursors which lead to discoloration in the alkaline environment, and is essentially free of by-products and of residues which, during storage due to the consumption of alkalinity, the pH value lower, and that the presence of added alkaline substances means that the paste has a pH of at least 11, in particular 11 to 12.5 and preferably at least 11.5.
  • the product according to the invention is color-stable and free of microbial attack even after storage for several months at 40 to 50 ° C. and therefore does not require any additional chemical preservation.
  • Surfactants which are stable in an alkaline medium include surfactant compounds of the alkoxylated long-chain alcohol type, in particular the fatty alcohol ethoxylates, which also include compounds with closed end groups, surfactants of the alkyl ether carboxylic acid type, the fatty alcohol sulfates and ether sulfates, the alkane sulfonates and in particular such Surfactants, the hydrophilic part of which is derived from carbohydrate compounds, understood.
  • Surfactants of the alkylglycoside type are particularly preferred. This term is understood to mean mixtures of alkyl mono- and alkyl oligoglycosides as obtained in the acid-catalyzed reaction of sugars and alkanols.
  • the particularly preferred alkyl glycosides are non-ionic surfactants such as are known, for example, from US Pat. Nos. 3,547,828 and 3,839,318. Manufacturing processes for particularly light-colored and color-stable alkyl glycosides are described in European patent applications EP 0301 298 AI, EP 0362671 AI and EP 0357969 AI.
  • the alkyl component of the alkyl glycosides generally consists of aliphatic radicals with 8 to 24, in particular 8 to 18, carbon atoms.
  • the corresponding fatty alkyl radicals as are obtainable from fat as a renewable raw material via the fatty alcohols, are particularly preferred.
  • alkyl residues derived from synthetic primary alcohols especially the so-called oxo alcohols useful; however, they are less preferred in the present case.
  • the sugar component in the alkyl glycoside can be from conventional aldoses or ketoses, such as. B. glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose. Because of the raw materials glucose or starch or starch degradation products available in large quantities, glucose is the particularly preferred sugar component.
  • the average degree of oligomerization of the alkyl glycosides, as they are present in the pastes according to the invention, can be arbitrary from the point of view of the paste stability, ie it can be in the usual range from 1.2 to 3.0.
  • This average degree of oligomerization relates to the amount of alkyl mono- and alkyl oligoglycoside surfactant in the alkyl glycoside product.
  • different proportions Cg_ ⁇ o or Ci4_iö can be present.
  • alkyl glycosides are characterized by particularly good surfactant properties. Together with water and the alkaline substances, they form a particularly preferred embodiment of the invention. Further preferred embodiments relate to C-chain cuts centered around C ⁇ / Cio and around C14 / C16. The former have very good solvent-imparting properties, the latter are suitable as wetting agents and emulsifiers.
  • surfactant paste refers to a viscosity range that ranges from flowable to viscous. Accordingly, the viscosities (measured according to Höppler at 40 ° C or according to Brookfield Helipath at 40 ° C and 4 revolutions per minute) are in the range of approximately 1,000 to 100,000.
  • the surfactants present in the aqueous surfactant paste are essentially free from bleachable color bodies, color body precursors, by-products which impair color quality, and residues if these surfactants have been subjected to a bleaching process at the end of their production.
  • This is preferably an oxidative bleaching process, in particular using hydrogen peroxide as the oxidizing agent.
  • This bleaching process will preferably carried out in the presence of magnesium cations, these magnesium cations either in the form of alkaline magnesium compounds such as the oxide, hydroxide, carbonate or an alcoholate for neutralizing the acid catalyst at the end of the production process in the case of the alkylglycosides in the system.
  • the oxidatively bleached products can be post-treated with reducing agents, the pH in the course of the reductive post-treatment not being less than 8.5.
  • the surfactant paste treated in this way obtains the high pH value according to the invention by compensating for the alkali consumption observed during bleaching by adding sodium hydroxide, potassium hydroxide or sodium or potassium carbonates and adjusting the desired pH value.
  • the invention therefore also relates to a process for the preparation of the storage-stable aqueous surfactant paste, in particular the alkyl glycoside paste, as is obtained by the customary production method for alkali-stable surfactants, in particular the alkyl glycosides after the additional bleaching with aqueous H2O2, this bleaching process being used as an oxidative bleaching process with H2O2 in the presence of magnesium compounds in an alkaline medium above pH 9, preferably above pH 10, and this method is characterized in that, after the residual peroxide content has been reduced, the values are at most 50 to 100 ppm H2O2 pH by adding alkalis, in particular those alkaline compounds which do not interfere with the further use of the surfactant paste or whose presence is desired, in particular sodium hydroxide, potassium hydroxide or sodium or potassium carbonates to a pH of at least 11, especially from 11 to 1 2.5 and preferably at least 11.5 and the water content of the pastes is adjusted to be in the range of 30 to 70%.
  • aqueous surfactant pastes according to the invention produced in this way if they are present in the particularly preferred form of the alkyl glucoside pastes, can also be mixed with additional surfactants which have been rendered otherwise alkali stable in order to obtain a product which contains a surfactant mixture in compounded form contains how it is particularly useful for further processing, or by which the viscosity and the flow behavior of the paste are favored during storage.
  • the production stages peroxide bleaching, peroxide degradation, optionally with reductive aftertreatment, and pH adjustment can be carried out continuously or discontinuously.
  • the bleaching stage and the peroxide degradation stage are preferably carried out continuously, in particular choosing stirred tank cascades with suitable temperature and residence time parameters on a production scale.
  • the stage of peroxide bleaching with H2O2 is carried out at 110 ° C with an average residence time of 2 hours, with a residual peroxide value of about 300 to 600 ppm H2O2.
  • the subsequent peroxide degradation stage the mixture is kept at 120 ° C. for a mean residence time of 3 hours and a residual peroxide content of 30 to 70 ppm is thus obtained.
  • the starting point for the preparation of the microbially stable, alkaline version was 100 kg of reaction mixture, prepared by reacting dodecanol with glucose in a molar ratio of 5: 1.
  • the mixture contained approx. 27.5% alkyl glucoside and 0.2% catalyst (paratoluenesulfone - acid).
  • the preparation was carried out as follows:
  • the catalyst was neutralized at 90 ° C. with the addition of 100 g of 50% sodium hydroxide solution.
  • the residue was converted into about 56 kg of aqueous paste by adding demineralized water.
  • the product was thermally treated at 120 ° C. for a further 3 hours.
  • the residual peroxide content dropped to less than 50 ppm without the product color changing significantly.
  • the pH of the paste obtained was 11.5.
  • the product After 4 months of storage it remained stable at 60 ° C.
  • the product showed a maximum of 3 days for bacteria and a maximum of 14 days for fungi over the entire storage period.
  • Bacterial mixture Staphylococcus aureus, Enterococcus faecium, Escherichia coli, Enterobacter aerogenes, Pseudo onas aeruginosa.
  • Fungus mixture Candida albicans, Aspergillus niger, Penicillium rubru, Trichoderma viride).
  • the viscosity of the paste was 1,800 mPa 's at 40 C ⁇ , measured according to DIN 53,015th Example 2:
  • reaction mixture obtained by reacting glucose with fatty alcohol C12 / C14 (75/25%) in a molar ratio of 1: 4.5, with an alkyl glucosid content of 29%, were worked up as follows:
  • the catalyst (0.2% paratoluenesulfonic acid) was neutralized with 110 g of 50% sodium hydroxide solution. 20 g of finely divided MgO were stirred in.
  • the thermal aftertreatment took place at 105 ° C. and lasted 6 hours.
  • the residual peroxide content dropped to less than 50 ppm.
  • the product was degassed in vacuo.
  • the pH was adjusted to 11.8 with the addition of a further 300 g of NaOH (as a 600 g 50% solution).
  • the product was color-stable, the pH remained constant at 11.8 and the microbial stability corresponded to that of the sample from Example 1.
  • Viscosity of the paste 2,000 mPa.s (measurement as in Example 1).

Abstract

Aqueous surfactant pastes, in particular those containing non-ionic surfactants of the alkylglycoside type, are given excellent storage stability against microbial attack when, following an oxidative bleaching procedure to remove alkali-sensitive pigments, the pH is adjusted to a value of at least 11 by the addition of alkaline substances.

Description

Λ Λ
"Stabilisierte Tensidpaste""Stabilized surfactant paste"
Die Erfindung betrifft eine gegen mikrobiellen Befall stabilisierte Ten¬ sidpaste auf wäßriger Basis, wobei das Tensid insbesondere im wesentlichen aus einem nichtionischen Tensid vom Typ der Alkylglykoside besteht. Die Erfindung betrifft ferner ein Verfahren zur Herstellung dieser Tensid¬ paste.The invention relates to an aqueous-based surfactant stabilized against microbial attack, the surfactant in particular consisting essentially of a nonionic surfactant of the alkyl glycoside type. The invention further relates to a method for producing this surfactant paste.
An die Tenside, wie sie in modernen Waschmitteln und kosmetischen Reini¬ gungsmitteln enthalten sind, werden hohe Anforderungen zu ihrer biologi¬ schen Abbaubarkeit gestellt. Derartige Tenside werden häufig als wäßrige Zubereitungen, die möglichst hochkonzentriert an tensidischem Wirkstoff, aber vorzugsweise noch pump- oder gießbar sind, auf den Markt gebracht. Wegen ihrer guten biologischen Abbaubarkeit werden gerade diese wäßrigen Mischungen leicht durch Mikroben wie Bakterien und Pilze befallen, so daß die Qualität und insbesondere die Lagerstabilität dieser Tensidmischungen beeinträchtigt sein können. Es gibt zwar eine Reihe brauchbarer antimi- krobieller Wirkstoffe, die einen derartigen mikrobiellen Befall verhindern und eine ausreichende Lagerstabilität gewährleisten. Die Verwendung von Konservierungsmittel wie z. B. Glutaraldehyd oder Benzoesäure ist jedoch nicht frei von technischen Bedenken. So ist zu befürchten, daß eine Ver¬ färbung der Tensidpaste während der Lagerung auf die Anwesenheit derar¬ tiger Konservierungsmittel zurückzuführen ist; andererseits wird die An¬ wesenheit von Konservierungsmitteln vom Weiterbenutzer nicht für alle An¬ wendungsgebiete der Tensidpasten akzeptiert.The tensides, as they are contained in modern detergents and cosmetic cleaning agents, are subject to high demands for their biodegradability. Such surfactants are frequently brought onto the market as aqueous preparations which are as highly concentrated as possible in surfactant active ingredient, but are preferably still pumpable or pourable. Because of their good biodegradability, these aqueous mixtures are easily attacked by microbes such as bacteria and fungi, so that the quality and, in particular, the storage stability of these surfactant mixtures can be impaired. There are a number of useful antimicrobial agents that prevent such microbial infestation and ensure adequate storage stability. The use of preservatives such. B. glutaraldehyde or benzoic acid is not free from technical concerns. It is feared that a discoloration of the surfactant paste during storage is due to the presence of such preservatives; on the other hand, the presence of preservatives is not accepted by the user for all areas of application of the surfactant pastes.
Es wurde nun gefunden, daß gegen mikrobiellen Befall geschützte wäßrige Tensidpasten auch ohne einen Gehalt an den üblichen Konservierungsmitteln eine hervorragende Lagerstabilität besitzen können, wenn bei ihrer Zusam¬ mensetzung darauf geachtet wird, daß bestimmte Verunreinigungen nicht vorhanden sind.It has now been found that aqueous surfactant pastes protected against microbial attack can have excellent storage stability even without a content of the usual preservatives, if care is taken in their composition that certain impurities are not present.
Diese Voraussetzungen werden von einer wäßrigen Tensidpaste erfüllt, die 30 bis 70 Gew.-% eines im alkalischen Milieu stabilen Tensids, insbeson¬ dere eines nichtionischen Tensids vom Typ der Alkylglykoside enthält und die dadurch gekennzeichnet ist, daß diese Paste im wesentlichen frei ist von bleichbaren Farbkörpern und solchen Farbkörpervorstufen, die im alka¬ lischen Milieu zur Verfärbung führen, sowie im wesentlichen frei ist von Nebenprodukten und von Rückständen, die bei der Lagerung durch Alkalitätszehrung den pH-Wert senken, und daß die Paste durch das Vorhan¬ densein von hinzugefügten alkalischen Substanzen einen pH-Wert von minde¬ stens 11, insbesondere von 11 bis 12,5 und vorzugsweise von mindestens 11,5 besitzt.These requirements are met by an aqueous surfactant paste which contains 30 to 70% by weight of a surfactant which is stable in an alkaline environment, in particular a nonionic surfactant of the alkyl glycoside type, and which is characterized in that this paste is essentially free of bleachable color bodies and of such color body precursors which lead to discoloration in the alkaline environment, and is essentially free of by-products and of residues which, during storage due to the consumption of alkalinity, the pH value lower, and that the presence of added alkaline substances means that the paste has a pH of at least 11, in particular 11 to 12.5 and preferably at least 11.5.
Es wurde überraschenderweise gefunden, daß das erfindungsgemäße Erzeugnis auch nach mehrmonatiger Lagerung bei 40 bis 50 °C farbstabil und frei von mikrobiellem Befall ist und somit keiner zusätzlichen chemischen Konser¬ vierung bedarf.It has surprisingly been found that the product according to the invention is color-stable and free of microbial attack even after storage for several months at 40 to 50 ° C. and therefore does not require any additional chemical preservation.
Unter Tensiden, die im alkalischen Milieu stabil sind, werden tensidische Verbindungen vom Typ der alkoxylierten langkettigen Alkohole, insbesondere die Fettalkoholethoxylate, wobei auch Verbindungen mit verschlossenen Endgruppen umfaßt sind, Tenside vom Typ der Alkylethercarbonsäuren, der Fettalkoholsulfate und -ethersulfate, der Alkansulfonate und insbesondere solche Tenside, deren hydrophiler Teil sich von Kohlenhydrat-Verbindungen ableitet, verstanden. Besonders bevorzugt sind Tenside vom Typ der Alkyl¬ glykoside. Unter diesem Begriff werden Gemische aus Alkylmono- und Alkyl- oligoglycosiden verstanden, wie man sie bei der säurekatalysierten Umset¬ zung von Zuckern und Alkanolen erhält.Surfactants which are stable in an alkaline medium include surfactant compounds of the alkoxylated long-chain alcohol type, in particular the fatty alcohol ethoxylates, which also include compounds with closed end groups, surfactants of the alkyl ether carboxylic acid type, the fatty alcohol sulfates and ether sulfates, the alkane sulfonates and in particular such Surfactants, the hydrophilic part of which is derived from carbohydrate compounds, understood. Surfactants of the alkylglycoside type are particularly preferred. This term is understood to mean mixtures of alkyl mono- and alkyl oligoglycosides as obtained in the acid-catalyzed reaction of sugars and alkanols.
Bei den besonders bevorzugten Alkylglykosiden handelt es sich um nicht¬ ionische Tenside wie sie beispielsweise aus den US-Patentschriften 3,547,828 und 3,839,318 bekannt sind. Herstellungsverfahren für besonders hellfarbige und farbstabile Alkylglykoside werden in den europäischen Pa¬ tentanmeldungen EP 0301 298 AI, EP 0362671 AI und EP 0357969 AI be¬ schrieben. Die Alkylkomponente der Alkylglykoside besteht im allgemeinen aus aliphatischen Resten mit 8 bis 24, insbesondere 8 bis 18 C-Atomen. Besonders bevorzugt sind die entsprechenden Fettalkylreste, wie sie aus Fett als nachwachsendem Rohstoff über die Fettalkohole erhältlich sind. Alkylreste, die sich von synthetischen primären Alkoholen, insbesondere den sogenannten Oxoalkoholen ableiten, sind im Prinzip ebenfalls brauchbar; sie sind jedoch im vorliegenden Fall weniger bevorzugt. Die Zuckerkomponente im Alkylglykosid kann von üblichen Aldosen bzw. Ketosen, wie z. B. Glucose, Fructose, Mannose, Galactose, Talose, Gulose, Allose, Altrose, Idose, Arabinose, Xylose, Lyxose und Ribose abstammen. Wegen der in großen Mengen verfügbaren Rohstoffe Glucose bzw. Stärke bzw. Stärkeab¬ bauprodukte ist die Glucose die besonders bevorzugte Zuckerkomponente. Der mittlere Oligomerisierungsgrad der Alkylglykoside, wie sie in den erfindungsgemäßen Pasten vorliegen, kann unter dem Gesichtspunkt der Pa¬ stenstabilität beliebig sein, d. h. er kann in dem üblichen Bereich von 1,2 bis 3,0 liegen. Dieser mittlere Oligomerisierungsgrad bezieht sich auf die Menge an Alkylmono- und Alkyloligoglykosid-Tensid im Alkylglykosid- Produkt. Bevorzugt verwendet werden allerdings solche Alkylglykoside, bei denen der Oligomerisierungsgrad deutlich unterhalb 1,5, insbesondere im Bereich 1,3 bis 1,4 liegt und wobei der zugehörige Fettalkylrest im we¬ sentlichen um C12 liegt. In Abhängigkeit von der Schnittbreite können un¬ terschiedliche Mengenanteile Cg_ιo bzw. Ci4_iö vorliegen. Diese Alkylglykoside zeichnen sich durch besonders gute Tensideigenschaften aus. Sie bilden zusammen mit Wasser und den alkalischen Substanzen eine beson¬ ders bevorzugte Ausführungsform der Erfindung. Weitere bevorzugte Ausfüh¬ rungsformen betreffen um Cβ/Cio sowie um C14/C16 zentrierte C- Kettenschnitte. Erstere besitzen sehr gute lösevermittelnde Eigenschaften, letztere eignen sich als Netzmittel und Emulgatoren.The particularly preferred alkyl glycosides are non-ionic surfactants such as are known, for example, from US Pat. Nos. 3,547,828 and 3,839,318. Manufacturing processes for particularly light-colored and color-stable alkyl glycosides are described in European patent applications EP 0301 298 AI, EP 0362671 AI and EP 0357969 AI. The alkyl component of the alkyl glycosides generally consists of aliphatic radicals with 8 to 24, in particular 8 to 18, carbon atoms. The corresponding fatty alkyl radicals, as are obtainable from fat as a renewable raw material via the fatty alcohols, are particularly preferred. In principle, there are also alkyl residues derived from synthetic primary alcohols, especially the so-called oxo alcohols useful; however, they are less preferred in the present case. The sugar component in the alkyl glycoside can be from conventional aldoses or ketoses, such as. B. glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose. Because of the raw materials glucose or starch or starch degradation products available in large quantities, glucose is the particularly preferred sugar component. The average degree of oligomerization of the alkyl glycosides, as they are present in the pastes according to the invention, can be arbitrary from the point of view of the paste stability, ie it can be in the usual range from 1.2 to 3.0. This average degree of oligomerization relates to the amount of alkyl mono- and alkyl oligoglycoside surfactant in the alkyl glycoside product. However, preference is given to using alkyl glycosides in which the degree of oligomerization is clearly below 1.5, in particular in the range from 1.3 to 1.4, and in which the associated fatty alkyl radical is essentially around C12. Depending on the cutting width, different proportions Cg_ιo or Ci4_iö can be present. These alkyl glycosides are characterized by particularly good surfactant properties. Together with water and the alkaline substances, they form a particularly preferred embodiment of the invention. Further preferred embodiments relate to C-chain cuts centered around Cβ / Cio and around C14 / C16. The former have very good solvent-imparting properties, the latter are suitable as wetting agents and emulsifiers.
Der Begriff der "Tensidpaste" bezieht sich auf einen Viskositätsbereich, der von fließfähig bis zähviskos reicht. Dementsprechend liegen die Viskositäten (gemessen nach Höppler bei 40 °C bzw. nach Brookfield Helipath bei 40 °C und 4 Umdrehungen pro Minute) im Bereich von etwa 1 000 bis 100000.The term "surfactant paste" refers to a viscosity range that ranges from flowable to viscous. Accordingly, the viscosities (measured according to Höppler at 40 ° C or according to Brookfield Helipath at 40 ° C and 4 revolutions per minute) are in the range of approximately 1,000 to 100,000.
Die in der wäßrigen Tensidpaste vorliegenden Tenside, insbesondere die Alkylglykoside, sind im wesentlichen frei von bleichbaren Farbkörpern, Farbkörpervorstufen, die Farbqualität beeinträchtigenden Nebenprodukten und Rückständen, wenn diese Tenside am Ende ihrer Herstellung einem Bleichprozeß unterworfen worden sind. Vorzugsweise handelt es sich dabei um einen oxidativen Bleichprozeß, insbesondere unter Verwendung von Was¬ serstoffperoxid als Oxidationsmittel. Dieser Bleichprozeß wird vorzugsweise in Gegenwart von Magnesiumkationen durchgeführt, wobei diese Magnesiumkationen entweder in Form von alkalischen Magnesiumverbindungen wie dem Oxid, Hydroxid, Carbonat oder einem Alkoholat bereits zur Neutra¬ lisation des sauren Katalysators am Ende des Herstellungsprozesses im Falle der Alkylglykoside in das System gelangen können. Es ist aber auch ausreichend, wenn am Ende des Tensidherstellungsverfahrens mit üblichen Alkalien, insbesondere alkalischen Natriumverbindungen, neutralisiert wird und dann zusätzlich wasserlösliche oder unlösliche Magnesiumverbindungen, z. B. die obengenannten, in einer solchen Menge hinzugesetzt werden, daß die nachfolgende Bleiche in Gegenwart von 100 bis 1 000 ppm Magnesium stattfindet. Wenn man bei dem Bleichprozeß dafür sorgt, daß ein hoher pH- Wert von mindestens 9, vorzugsweise mindestens 10, beibehalten wird, läßt sich als letzte Stufe des Bleichprozesses durch thermische Behandlung der Paste bei 80 bis 150 °C der Restperoxidgehalt auf Werte von höchstens 50 bis 100 ppm H2O2 abbauen. Die oxidativ gebleichten Produkte können mit Reduktionsmitteln nachbehandelt werden, wobei der pH-Wert im Verlauf der reduktiven Nachbehandlung den Wert 8,5 nicht unterschreiten darf. Die so behandelte Tensidpaste erhält den erfindungsgemäß hohen pH-Wert dadurch, daß die während der Bleiche beobachtete Alkalizehrung durch Zugabe von Natriumhydroxid, Kaliumhydroxid bzw. Natrium- oder Kaliumcarbonaten kom¬ pensiert und der gewünschte pH-Wert eingestellt wird.The surfactants present in the aqueous surfactant paste, in particular the alkyl glycosides, are essentially free from bleachable color bodies, color body precursors, by-products which impair color quality, and residues if these surfactants have been subjected to a bleaching process at the end of their production. This is preferably an oxidative bleaching process, in particular using hydrogen peroxide as the oxidizing agent. This bleaching process will preferably carried out in the presence of magnesium cations, these magnesium cations either in the form of alkaline magnesium compounds such as the oxide, hydroxide, carbonate or an alcoholate for neutralizing the acid catalyst at the end of the production process in the case of the alkylglycosides in the system. However, it is also sufficient if, at the end of the surfactant production process, neutralization is carried out using conventional alkalis, in particular alkaline sodium compounds, and then additionally water-soluble or insoluble magnesium compounds, e.g. B. the above, are added in such an amount that the subsequent bleaching takes place in the presence of 100 to 1000 ppm magnesium. If the bleaching process ensures that a high pH of at least 9, preferably at least 10, is maintained, the last stage of the bleaching process can be by thermal treatment of the paste at 80 to 150 ° C., the residual peroxide content to a value of at most 50 Reduce up to 100 ppm H2O2. The oxidatively bleached products can be post-treated with reducing agents, the pH in the course of the reductive post-treatment not being less than 8.5. The surfactant paste treated in this way obtains the high pH value according to the invention by compensating for the alkali consumption observed during bleaching by adding sodium hydroxide, potassium hydroxide or sodium or potassium carbonates and adjusting the desired pH value.
Die Erfindung betrifft deshalb auch ein Verfahren zur Herstellung der la¬ gerstabilen wäßrigen Tensidpaste, insbesondere der Alkylglykosidpaste, wie man sie nach den üblichen Herstellungsmethodeπ für alkalistabile Tenside, insbesondere die Alkylglykoside nach der zusätzlichen Bleiche mit wäßrigem H2O2 erhält, wobei man diesen Bleichprozeß als oxidativen Bleichprozeß mit H2O2 in Gegenwart von Magnesiumverbindungen im alkalischen Milieu oberhalb pH 9, vorzugsweise oberhalb pH 10, durchführt, und wobei dieses Verfahren dadurch gekennzeichnet ist, daß man im Anschluß an den Abbau des Restper- oxidgehaltes auf Werte von höchstens 50 bis 100 ppm H2O2, den pH-Wert durch Zugabe von Alkalien, insbesondere solchen alkalischen Verbindungen, die bei der Weiterverwendung der Tensidpaste nicht stören bzw. deren An¬ wesenheit erwünscht ist, insbesondere Natriumhydroxid, Kaliumhydroxid, bzw. Natrium- oder Kaliumcarbonate auf einen pH-Wert von mindestens 11, insbesondere von 11 bis 12,5 und vorzugsweise von mindestens 11,5 einstellt, und wobei der Wassergehalt der Pasten so eingestellt wird, daß er im Bereich von 30 bis 70 % liegt.The invention therefore also relates to a process for the preparation of the storage-stable aqueous surfactant paste, in particular the alkyl glycoside paste, as is obtained by the customary production method for alkali-stable surfactants, in particular the alkyl glycosides after the additional bleaching with aqueous H2O2, this bleaching process being used as an oxidative bleaching process with H2O2 in the presence of magnesium compounds in an alkaline medium above pH 9, preferably above pH 10, and this method is characterized in that, after the residual peroxide content has been reduced, the values are at most 50 to 100 ppm H2O2 pH by adding alkalis, in particular those alkaline compounds which do not interfere with the further use of the surfactant paste or whose presence is desired, in particular sodium hydroxide, potassium hydroxide or sodium or potassium carbonates to a pH of at least 11, especially from 11 to 1 2.5 and preferably at least 11.5 and the water content of the pastes is adjusted to be in the range of 30 to 70%.
Die so hergestellten erfindungsgemäßen wäßrigen Tensidpasten können, wenn sie in der besonders bevorzugten Form der Alkylglucosid-Pasten vorliegen, noch mit zusätzlichen, anderweitig alkalistabil gemachten Tensiden ver¬ mischt werden, um so zu einem Erzeugnis zu gelangen, das eine Tensidmi- schung in compoundierter Form enthält, wie sie für die Weiterverarbeitung besonders zweckmäßig ist, bzw. wodurch die Viskosität und das Fließver¬ halten der Paste während der Lagerung begünstigt werden.The aqueous surfactant pastes according to the invention produced in this way, if they are present in the particularly preferred form of the alkyl glucoside pastes, can also be mixed with additional surfactants which have been rendered otherwise alkali stable in order to obtain a product which contains a surfactant mixture in compounded form contains how it is particularly useful for further processing, or by which the viscosity and the flow behavior of the paste are favored during storage.
Zur Herstellung der erfindungsgemäßen stabilisierten Paste können die Herstellungsstufen Peroxidbleiche, Peroxidabbau, gegebenenfalls mit reduktiver Nachbehandlung, und pH-Werteinstellung kontinuierlich oder aber diskontinuierlich durchgeführt werden. Vorzugsweise werden die Bleichstufe und die Peroxidabbau-Stufe kontinuierlich durchgeführt, wobei man im Pro¬ duktionsmaßstab insbesondere Rührkesselkaskaden mit geeigneten Temperatur¬ bzw. Verweilzeitparametern wählt. So wird beispielsweise die Stufe der Peroxidbleiche mit H2O2 bei 110 °C mit einer mittleren Verweilzeit von 2 Stunden durchgeführt, wobei man zu einem Restperoxidwert von etwa 300 bis 600 ppm H2O2 kommt. In der anschließenden Peroxidabbau-Stufe hält man das Gemisch auf 120 °C während einer mittleren Verweilzeit von 3 Stunden und kommt so zu einem Restperoxidgehalt von 30 bis 70 ppm. To produce the stabilized paste according to the invention, the production stages peroxide bleaching, peroxide degradation, optionally with reductive aftertreatment, and pH adjustment can be carried out continuously or discontinuously. The bleaching stage and the peroxide degradation stage are preferably carried out continuously, in particular choosing stirred tank cascades with suitable temperature and residence time parameters on a production scale. For example, the stage of peroxide bleaching with H2O2 is carried out at 110 ° C with an average residence time of 2 hours, with a residual peroxide value of about 300 to 600 ppm H2O2. In the subsequent peroxide degradation stage, the mixture is kept at 120 ° C. for a mean residence time of 3 hours and a residual peroxide content of 30 to 70 ppm is thus obtained.
B E I S P I E L EB E I S P I E L E
Beispiel 1:Example 1:
Ausgangspunkt für die Herstellung der mikrobiell stabilen, alkalischen Version waren 100 kg Reaktionsgemisch, hergestellt durch Umsetzung von Dodecanol mit Glucose im molaren Verhältnis von 5 : 1. Das Gemisch ent¬ hielt ca. 27,5 % Alkylglucosid und 0,2 % Katalysator (Paratoluolsulfon- säure). Die Aufbereitung wurde wie folgt durchgeführt:The starting point for the preparation of the microbially stable, alkaline version was 100 kg of reaction mixture, prepared by reacting dodecanol with glucose in a molar ratio of 5: 1. The mixture contained approx. 27.5% alkyl glucoside and 0.2% catalyst (paratoluenesulfone - acid). The preparation was carried out as follows:
Der Katalysator wurde unter Zugabe von 100 g 50%iger Natronlauge bei 90 °C neutralisiert.The catalyst was neutralized at 90 ° C. with the addition of 100 g of 50% sodium hydroxide solution.
15 g feinverteiltes Magnesiumoxid wurden anschließend eingerührt. Das Gemisch wurde im Dünnschichtverdampfer bei 1 mbar und 200 °C Wär¬ meträgertemperatur auf 1 % Restfettalkohol eingedampft. Es resultier¬ ten ca. 28 kg Destillationsrückstand.15 g of finely divided magnesium oxide were then stirred in. The mixture was evaporated to 1% residual fatty alcohol in a thin film evaporator at 1 mbar and 200 ° C. heat transfer medium temperature. This resulted in about 28 kg of distillation residue.
Durch Zugabe von vollentsalztem Wasser wurde der Rückstand in ca. 56 kg wäßrige Paste übergeführt.The residue was converted into about 56 kg of aqueous paste by adding demineralized water.
Unter Zugabe von 300 g H2O2 (1000 g 30%ige Lösung) und 420 g NaOH (840 g 50%ige Lösung) wurde bei 110 °C im Druckreaktor 1 Stunde ge¬ bleicht. Nach Vakuumentgasung resultierte ein hellgelbes Produkt mit ca. 350 ppm Restgehalt an Wasserstoffperoxid.With the addition of 300 g of H2O2 (1000 g of 30% solution) and 420 g of NaOH (840 g of 50% solution), bleaching was carried out at 110 ° C. in the pressure reactor for 1 hour. After vacuum degassing, a light yellow product resulted with a residual hydrogen peroxide content of about 350 ppm.
Das Produkt wurde bei 120 °C weitere 3 Stunden thermisch nachbehan¬ delt. Der Restperoxidgehalt sank auf kleiner als 50 ppm ab, ohne daß die Produktfarbe sich wesentlich änderte. Der pH-Wert der erhaltenen Paste lag bei 11,5. Er blieb nach 4monatiger Lagerung bei 60 °C stabil. Das Produkt ergab im mikrobiellen Belastungs¬ test mit 106 Bakterien und 10*-* Pilzen/g Abtδtungszeiten von maximal 3 Ta¬ gen für Bakterien und maximal 14 Tagen für Pilze über die gesamte Lager¬ zeit. (Bakterienmischung: Staphylococcus aureus, Enterococcus faecium, Escherichia coli, Enterobacter aerogenes, Pseudo onas aeruginosa. Pilzmi¬ schung: Candida albicans, Aspergillus niger, Penicillium rubru , Tricho- derma viride).The product was thermally treated at 120 ° C. for a further 3 hours. The residual peroxide content dropped to less than 50 ppm without the product color changing significantly. The pH of the paste obtained was 11.5. After 4 months of storage it remained stable at 60 ° C. In the microbial load test with 10 6 bacteria and 10 * - * fungi / g, the product showed a maximum of 3 days for bacteria and a maximum of 14 days for fungi over the entire storage period. (Bacterial mixture: Staphylococcus aureus, Enterococcus faecium, Escherichia coli, Enterobacter aerogenes, Pseudo onas aeruginosa. Fungus mixture: Candida albicans, Aspergillus niger, Penicillium rubru, Trichoderma viride).
Die Viskosität der Paste betrug 1800 mPa«s bei 40 βC, gemessen nach DIN 53015. Beispiel 2:The viscosity of the paste was 1,800 mPa 's at 40 C β, measured according to DIN 53,015th Example 2:
100 kg Reaktionsgemisch, erhalten durch Umsetzung von Glucose mit Fettal¬ kohol C12/C14 (75/25 %) im Molverhältnis 1 : 4,5, mit einem Alkylgluco- sid-Gehalt von 29 %, wurde wie folgt aufgearbeitet:100 kg of reaction mixture, obtained by reacting glucose with fatty alcohol C12 / C14 (75/25%) in a molar ratio of 1: 4.5, with an alkyl glucosid content of 29%, were worked up as follows:
Der Katalysator (0,2 % Paratoluolsulfonsäure) wurde mit 110 g 50%iger Natronlauge neutralisiert. 20 g feinverteiltes MgO wurden eingerührt.The catalyst (0.2% paratoluenesulfonic acid) was neutralized with 110 g of 50% sodium hydroxide solution. 20 g of finely divided MgO were stirred in.
Die Destillation erfolgte wie in Beispiel 1 und ergab ca. 30 kg APG- Rückstand.The distillation was carried out as in Example 1 and gave about 30 kg of APG residue.
Nach Herstellung einer 50%igen wäßrigen Paste wurde unter Zugabe von 400 g H2O2 (1330 g 30%ige Lösung) und 300 g NaOH (600 g 50%ige Lösung) bei 105 °C 2 Stunden gebleicht.After a 50% strength aqueous paste had been prepared, 400 g of H2O2 (1330 g of 30% strength solution) and 300 g of NaOH (600 g of 50% strength solution) were bleached at 105 ° C. for 2 hours.
Die thermische Nachbehandlung erfolgte bei 105 °C und dauerte 6 Stun¬ den. Der Restperoxidgehalt sank auf kleiner als 50 ppm ab. Das Produkt wurde im Vakuum entgast. Unter Zugabe weiterer 300 g NaOH (als 600 g 50%ige Lösung) wurde der pH-Wert auf 11.8 eingestellt. Das Produkt war nach 4 Monaten Lagerung farbstabil, der pH-Wert blieb konstant bei 11,8 und die mikrobielle Stabilität entsprach jener des Mu¬ sters aus Beispiel 1. Viskosität der Paste: 2 000 mPa-s (Messung wie in Beispiel 1). The thermal aftertreatment took place at 105 ° C. and lasted 6 hours. The residual peroxide content dropped to less than 50 ppm. The product was degassed in vacuo. The pH was adjusted to 11.8 with the addition of a further 300 g of NaOH (as a 600 g 50% solution). After 4 months of storage, the product was color-stable, the pH remained constant at 11.8 and the microbial stability corresponded to that of the sample from Example 1. Viscosity of the paste: 2,000 mPa.s (measurement as in Example 1).

Claims

ßP A T E N T A N S P R Ü C H E ßP ATENT CLAIMS
1. Wäßrige Tensidpaste, enthaltend 30 bis 70 Gew.-% eines im alkalischen Milieu stabilen Tensids, insbesondere eines nichtionischen Tensids vom Typ der- Alkylglykoside, dadurch gekennzeichnet, daß diese Paste im wesentlichen frei ist von bleichbaren Farbkörpern und solchen Farb¬ körpervorstufen, die im alkalischen Milieu zur Verfärbung führen, so¬ wie im wesentlichen frei ist von Nebenprodukten und von Rückständen, die bei der Lagerung durch Alkalitätszehrung den pH-Wert senken, und daß die Paste durch das Vorhandensein von hinzugefügten alkalischen Substanzen einen pH-Wert von mindestens 11, insbesondere von 11 bis 12,5 und vorzugsweise von mindestens 11,5 besitzt.1. Aqueous surfactant paste containing 30 to 70% by weight of a surfactant which is stable in an alkaline medium, in particular a nonionic surfactant of the alkyl glycoside type, characterized in that this paste is essentially free of bleachable color bodies and color body precursors which lead to discoloration in an alkaline environment, as is essentially free of by-products and of residues which reduce the pH during storage due to the consumption of alkalinity, and that the paste has a pH of at least 11 due to the presence of added alkaline substances , in particular from 11 to 12.5 and preferably from at least 11.5.
2. Erzeugnis nach Anspruch 1, dadurch gekennzeichnet, daß die Paste aus einem oxidativen Bleichprozeß hervorgegangen und gegebenenfalls mit Reduktionsmitteln nachbehandelt worden ist.2. Product according to claim 1, characterized in that the paste has arisen from an oxidative bleaching process and, if appropriate, has been aftertreated with reducing agents.
3. Erzeugnis nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß die Paste 100 bis 1 000 ppm Magnesium, bezogen auf das Tensid als Ak¬ tivsubstanz, enthält und der Restperoxidgehalt bei höchstens 50 bis 100 ppm H2O2 liegt.3. Product according to claims 1 or 2, characterized in that the paste contains 100 to 1,000 ppm magnesium, based on the surfactant as active substance, and the residual peroxide content is at most 50 to 100 ppm H2O2.
4. Erzeugnis nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Tensidpaste im wesentlichen aus einem nichtionischen Tensid vom Typ der Alkylglykoside mit insbesondere C8- bis Cjβ-Eettalkyl- resten und einem Oligomerisierungsgrad von 1,2 bis 3, vorzugsweise von 1,3 bis 1,4, und Wasser sowie den alkalischen Substanzen besteht.4. Product according to any one of claims 1 to 3, characterized in that the surfactant paste consists essentially of a nonionic surfactant of the alkyl glycoside type with in particular C8- to Cj β -etalkyl residues and a degree of oligomerization of 1.2 to 3, preferably of 1.3 to 1.4, and water and the alkaline substances.
5. Erzeugnis nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Tensidpaste neben einem Alkylglykosid noch wenigstens ein an¬ deres, bei pH-Werten von oberhalb 11 stabiles Tensid in compoundierter Form enthält.5. Product according to one of claims 1 to 4, characterized in that the surfactant paste contains in addition to an alkyl glycoside at least one other, at pH values above 11 stable surfactant in compounded form.
6. Verfahren zur Herstellung der wäßrigen Tensidpasten nach den Ansprü¬ chen 1 bis 5, dadurch gekennzeichnet, daß man im Anschluß an den Abbau des Restperoxidgehaltes auf Werte von höchstens 50 bis 100 ppm H2O2, den pH-Wert durch Zugabe von Alkalien, insbesondere solchen alkali¬ schen Verbindungen, die bei der Weiterverwendung der Tensidpaste nicht stören bzw. deren Anwesenheit erwünscht ist, insbesondere Natrium¬ hydroxid, Kaliumhydroxid, bzw. Natrium- oder Kaliumcarbonate auf einen pH-Wert von mindestens 11, insbesondere von 11 bis 12,5 und vorzugs¬ weise von mindestens 11,5 einstellt, und wobei der Wassergehalt der Pasten so eingestellt wird, daß er im Bereich von 30 bis 70 % liegt. 6. Process for the preparation of the aqueous surfactant pastes according to claims 1 to 5, characterized in that after the degradation the residual peroxide content to values of at most 50 to 100 ppm H2O2, the pH by adding alkalis, in particular those alkali compounds which do not interfere with the further use of the surfactant paste or whose presence is desired, in particular sodium hydroxide, potassium hydroxide, or sodium or potassium carbonates to a pH of at least 11, in particular from 11 to 12.5 and preferably at least 11.5, and wherein the water content of the pastes is adjusted so that it is in the range from 30 to 70% lies.
EP91918719A 1990-11-09 1991-11-04 Method for producing aqueous stabilized surfactant pastes Expired - Lifetime EP0556220B1 (en)

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DE4035722A DE4035722A1 (en) 1990-11-09 1990-11-09 STABILIZED SURFACTANT PASTE
PCT/EP1991/002073 WO1992008781A1 (en) 1990-11-09 1991-11-04 Stabilized surfactant pastes

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