EP0532549A1 - Liquid, free-flowing and pumpable tenside concentrate - Google Patents

Liquid, free-flowing and pumpable tenside concentrate

Info

Publication number
EP0532549A1
EP0532549A1 EP91909996A EP91909996A EP0532549A1 EP 0532549 A1 EP0532549 A1 EP 0532549A1 EP 91909996 A EP91909996 A EP 91909996A EP 91909996 A EP91909996 A EP 91909996A EP 0532549 A1 EP0532549 A1 EP 0532549A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
formula
surfactant mixture
carbon atoms
weight
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.)
Ceased
Application number
EP91909996A
Other languages
German (de)
French (fr)
Inventor
Brigitte Giesen
Andreas Slydath
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0532549A1 publication Critical patent/EP0532549A1/en
Ceased legal-status Critical Current

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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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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

Definitions

  • the present invention relates to concentrated surfactant mixtures of alkyl glycosides, alkyl sulfates and alkanesulfonates as stable, flowable and pumpable liquids and their use as premixes (compounds) for the production of liquid washing and cleaning agents.
  • alkyl glycosides with long-chain alkyl groups belong to the nonionic surfactants.
  • the person skilled in the art also knows, as described, for example, in AM Schwartz, JW Perry, Surface Active Agents, Vol. 1, Interscience Publishers, 1949, page 372, that surfactant mixtures generally have synergistic effects and often have better cleaning properties than would result from the sum of the values of the individual components.
  • Detergents which contain alkyl glycosides in combination with at least one conventional anionic surfactant are described in European patent application EP 070074.
  • Detergents that contain alkyl glycosides and anionic surfactants are also known from European patent application EP 092877.
  • liquid detergents are known from European patent application EP 105556, which contain alkyl glycosides, certain other nonionic surfactants and anionic surfactants. From the international patent application WO 86/02943 alkylglycoside-containing liquid detergents are known which contain conventional anionic surfactants.
  • the individual components are generally used as flowable solutions which each contain a substance or which, as premixes, so-called compounds, consist of several substances which are customary in the finished agents.
  • the components provided for the mixture into the finished agent should have the highest possible active substance content and at the same time be easy to handle, that is to say they should be as flowable and as possible be easy to pump and have the highest possible storage stability.
  • Alkyl glycosides are usually obtained as highly viscous pastes.
  • the object of the present invention was to develop a storage-stable, liquid surfactant mixture from an alkyl glycoside paste.
  • This object is achieved by an aqueous mixture of certain amounts of alkyl glycoside, alkyl sulfate and secondary alkane sulfonate.
  • the compounds according to the invention are aqueous mixtures which consist essentially of an alkyl glycoside and 2 different synthetic anionic surfactants, an alkyl sulfate and an alkane sulfonate, the alkyl glycoside having the formula I
  • R1 is an alkyl radical having 8 to 22 carbon atoms
  • G is a glycose unit and n is a number between 1 and 10
  • the alkyl sulfate has the formula II
  • R2 is an alkyl radical with 8 to 22 C atoms and X is a cation selected from the group comprising hydrogen, alkali and ammonium ions, and the alkanesulfonate has the formula III,
  • R3 and R ⁇ independently of one another are alkyl radicals having 1 to 18 carbon atoms, with the proviso that the total number of carbon atoms in the alkanesulfonate is between 10 and 20, and Y is a cation selected from the group comprising hydrogen, alkali and ammonium ions, and the compounds being 35 to 55% by weight of water, 10 to 30% by weight, preferably 17 to 25% by weight of alkyl glycoside, 10 to 20% by weight, preferably 12 to 18% by weight % Contain alkyl sulfate and 1 to 15 wt .-%, preferably 3 to 10 wt .-% alkanesulfonate.
  • alkyl glycosides suitable for the surfactant mixtures according to the invention and their preparation are described, for example, in European Patent Applications EP 92355, EP 301298, EP 357969 and EP 362671 or in the US Pat. No. 3547828.
  • the glycoside components ((G) n in formula I) of such alkyl glycosides are oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, old rose , Allose, Idose, Ribose, Arabinose, Xylose and Lyxose and mixtures thereof.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
  • the degree of oligomerization (n in formula I) generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the alkyl glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its good availability.
  • the alkyl part (R in formula I) of the alkyl glycosides contained in the surfactant mixtures according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkyl glycosides which can be used .
  • the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • Particularly suitable alkyl glycosides contain a coconut fatty alkyl radical, that is to say mixtures with essentially R - dodecyl and R 1 »tetradecyl.
  • the alkyl glycosides can contain small amounts, for example 1 to 2%, of unconverted long-chain alcohol, which does not have a disadvantageous effect on the properties of the surfactant mixtures produced therewith.
  • the neutralized sulfation products of the above come as alkyl sulfates suitable for use in the surfactant mixtures according to the invention alcohols in question.
  • the derivatives of fatty alcohols with 8 to 22 carbon atoms, in particular with 12 to 16 carbon atoms, are also particularly suitable in this case.
  • the alkyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization, preferably with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases the.
  • the secondary alkanesulfonates used according to the invention are neutralized substances which are obtained by sulfoxidation of hydrocarbons which preferably contain 10 to 20 carbon atoms. This generally results in products with a statistical distribution of the sulfonic acid substituents, which can be separated * in a known manner.
  • the alkanesulfonates having 12 to 17 carbon atoms have proven to be particularly suitable for the mixture according to the invention.
  • Suitable cations are in particular those from the group of alkali ions, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ions.
  • the preparation of the surfactant mixtures according to the invention presents no difficulties. It can be done easily by simply mixing the three individual components, which can be present as such or preferably in aqueous solution.
  • the mixtures according to the invention are notable for their low viscosities, their easy flowability and pumpability and their high storage stability.
  • the viscosity of the compounds is generally between 20,000 Pa.s and 50,000 Pa.s.
  • the compounds of the invention are ⁇ long time, at least 30 days, at temperatures of about 1 ° C to about 45 C storage stable.
  • the coapounds according to the invention can be used, directly or after dilution with water, for technical applications, for example as flotation aids or drilling fluids. However, they are preferably used as premixes for the production of liquid washing and cleaning agents. uses, which include in particular mild detergents, detergents and dishwashing detergents, but also shampoos. Such agents can be produced in a simple manner by diluting the compounds with water to the desired active substance concentration.
  • builder substances such as zeolites and layered silicates, corrosion inhibitors, bleaching agents, bleach activators, optical brighteners, enzymes, graying inhibitors, antimicrobial active ingredients, water-miscible solvents, abrasives, foam stabilizers, preservatives, pH agents Regulators, dyes and fragrances as well as additional surfactants are possible.
  • builder substances such as zeolites and layered silicates, corrosion inhibitors, bleaching agents, bleach activators, optical brighteners, enzymes, graying inhibitors, antimicrobial active ingredients, water-miscible solvents, abrasives, foam stabilizers, preservatives, pH agents Regulators, dyes and fragrances as well as additional surfactants are possible.
  • the surfactant mixtures M1 to M3 according to the invention characterized below in Table 1 by their composition and the compositions VI to V5 used in comparative experiments were prepared.
  • the surfactant mixtures M1 to M3 according to the invention had pH values (10% by weight aqueous solution) of 9.6.
  • Viscosity (20 ° C) 25000 40000 25000 28850 55540 [mPa.s]
  • Mixture V3 was a solid, viscous gel both at room temperature and at 4 ° C., the viscosity of which could not be determined.
  • the mixtures V4 and V5 were inhomogeneous, just flowable pastes at the temperatures indicated.
  • solutions Ml to M3 and VI to V5 were prepared, each containing 0.15 gram of active substance per liter of solution.
  • the cleaning performance of the compounds according to the invention was at least the same as that of the comparative mixtures in all cases.

Abstract

Des concentrés se composent essentiellement de 35 à 55 % en poids d'eau, de 10 à 30 % en poids d'un alkylglycoside ayant la formule R1-O(G)n, dans laquelle R1 représente un résidu alkyle ayant de 8 à 22 atomes de C, G une unité glucosique et n un nombre entre 1 et 10, de 10 à 30 % en poids d'un sulfate d'alkyle ayant la formule R2-O-SO3X, dans laquelle R2 représente un résidu alkyle ayant de 8 à 22 atomes de C et X représente un ion d'alcali ou d'ammonium, et de 1 à 15 % en poids d'un sulfonate d'alcane ayant la formule (III), dans laquelle R3 et R4 représentent indépendamment l'un de l'autre des résidus alkyles ayant de 1 à 18 atomes de C, à condition que la totalité des atomes de C dans le sulfonate d'alcane soit comprise entre 10 et 20, et qu'Y représente un ion d'alcali ou d'ammonium. Ces concentrés sont utiles comme mélanges mères (compounds) pompables, fluides et supportant le stockage, de préférence pour la fabrication de produits de nettoyage ou détergents.Concentrates consist essentially of 35 to 55 wt% water, 10 to 30 wt% of an alkylglycoside having the formula R1-O (G) n, wherein R1 is an alkyl residue having 8 to 22 atoms of C, G a glucose unit and n a number between 1 and 10, from 10 to 30% by weight of an alkyl sulfate having the formula R2-O-SO3X, in which R2 represents an alkyl residue having 8 at 22 atoms of C and X represents an alkali or ammonium ion, and from 1 to 15% by weight of an alkane sulfonate having the formula (III), wherein R3 and R4 independently represent one on the other, alkyl residues having 1 to 18 C atoms, provided that all of the C atoms in the alkane sulfonate are between 10 and 20, and Y represents an alkali ion or d 'ammonium. These concentrates are useful as pumpable, fluid and storage-supporting masterbatches (compounds), preferably for the manufacture of cleaning products or detergents.

Description

"Flüssiges, fließ- und pumpfähiqes Tensidkonzentrat" "Liquid, flowable and pumpable surfactant concentrate"
Die vorliegende Erfindung betrifft konzentrierte Tensidmischungen aus Alkylglykosiden, Alkylsulfaten und Alkansulfonaten als stabile, fließ- und pumpbare Flüssigkeiten sowie deren Verwendung als Vorgemische (Compounds) zur Herstellung von flüssigen Wasch- und Reinigungsmitteln.The present invention relates to concentrated surfactant mixtures of alkyl glycosides, alkyl sulfates and alkanesulfonates as stable, flowable and pumpable liquids and their use as premixes (compounds) for the production of liquid washing and cleaning agents.
Daß Alkylglykoside mit langkettigen Alkylgruppen zu den nichtionischen Tensiden gehören, ist seit langer Zeit bekannt. Ebenso weiß der Fachmann, wie zum Beispiel in A. M. Schwartz, J. W. Perry, Surface Active Agents, Vol. 1, Interscience Publishers, 1949, Seite 372, beschrieben, daß Tensid¬ mischungen in der Regel synergistische Effekte aufweisen und oft bessere Reinigungseigenschaften besitzen, als sich aus der Summe der Werte der Einzelkomponenten ergeben würde.It has long been known that alkyl glycosides with long-chain alkyl groups belong to the nonionic surfactants. The person skilled in the art also knows, as described, for example, in AM Schwartz, JW Perry, Surface Active Agents, Vol. 1, Interscience Publishers, 1949, page 372, that surfactant mixtures generally have synergistic effects and often have better cleaning properties than would result from the sum of the values of the individual components.
Waschmittel, die Alkylglykoside in Kombination mit wenigstens einem übli¬ chen anionischen Tensid enthalten, werden in der europäischen Patentan¬ meldung EP 070074 beschrieben. Waschmittel, die Alkylglykoside und Aniontenside enthalten, sind auch aus der europäischen Patentanmeldung EP 092877 bekannt. Des weiteren sind aus der europäischen Patentanmeldung EP 105556 flüssige Waschmittel bekannt, die Alkylglykoside, bestimmte andere nichtionische Tenside und anionische Tenside enthalten. Aus der internationalen Patentanmeldung WO 86/02943 sind alkylglykosidhaltige Flüssigwaschmittel bekannt, die übliche Aniontenside enthalten.Detergents which contain alkyl glycosides in combination with at least one conventional anionic surfactant are described in European patent application EP 070074. Detergents that contain alkyl glycosides and anionic surfactants are also known from European patent application EP 092877. Furthermore, liquid detergents are known from European patent application EP 105556, which contain alkyl glycosides, certain other nonionic surfactants and anionic surfactants. From the international patent application WO 86/02943 alkylglycoside-containing liquid detergents are known which contain conventional anionic surfactants.
Bei der Herstellung flüssiger Wasch- und Reinigungsmittel werden die ein¬ zelnen Komponenten in der Regel als fließfähige Lösungen eingesetzt, die jeweils einen Stoff enthalten oder die als Vorgemische, sogenannte Com¬ pounds, aus mehreren in den fertigen Mitteln üblichen Stoffen bestehen. Die für die Mischung zum fertigen Mittel vorgesehenen Komponenten sollen einen möglichst hohen Aktivsubstanzgehalt aufweisen und gleichzeitig leicht handhabbar sein, das heißt, sie sollen möglichst fließfähig und leicht pumpbar sein und eine möglichst hohe Lagerstabilität besitzen. Alkylglykoside fallen normalerweise als hochviskose Pasten an.In the production of liquid detergents and cleaning agents, the individual components are generally used as flowable solutions which each contain a substance or which, as premixes, so-called compounds, consist of several substances which are customary in the finished agents. The components provided for the mixture into the finished agent should have the highest possible active substance content and at the same time be easy to handle, that is to say they should be as flowable and as possible be easy to pump and have the highest possible storage stability. Alkyl glycosides are usually obtained as highly viscous pastes.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, aus einer Alkylgly- kosid-Paste ein lagerstabiles, flüssiges Tensidgemisch zu entwickeln.The object of the present invention was to develop a storage-stable, liquid surfactant mixture from an alkyl glycoside paste.
Diese Aufgabe wird durch eine wäßrige Mischung aus bestimmten Mengen an Alkylglykosid, Alkylsulfat und sekundärem Alkansulfonat gelöst.This object is achieved by an aqueous mixture of certain amounts of alkyl glycoside, alkyl sulfate and secondary alkane sulfonate.
Die erfindungsgemäßen Compounds sind wäßrige Mischungen, die im wesent¬ lichen aus einem Alkylglykosid und 2 verschiedenartigen synthetischen anionischen Tensiden, einem Alkylsulfat und einem Alkansulfonat, bestehen, wobei das Alkylglykosid die Formel I aufweist,The compounds according to the invention are aqueous mixtures which consist essentially of an alkyl glycoside and 2 different synthetic anionic surfactants, an alkyl sulfate and an alkane sulfonate, the alkyl glycoside having the formula I
Rx-0(G)n ' (I)R x -0 (G) n ' (I)
in der Rl einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl zwischen 1 und 10 bedeuten, das Alkylsulfat die Formel II auf¬ weist,in which R1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10, the alkyl sulfate has the formula II,
in der R2 einen Alkylrest mit 8 bis 22 C-Atomen und X ein Kation, ausge¬ wählt aus der Gruppe umfassend Wasserstoff-, Alkali- und Ammoniumionen, bedeuten, und das Alkansulfonat die Formel III aufweist,in which R2 is an alkyl radical with 8 to 22 C atoms and X is a cation selected from the group comprising hydrogen, alkali and ammonium ions, and the alkanesulfonate has the formula III,
R3-CH-S03Y (III)R3-CH-S0 3 Y (III)
R4R4
in der R3 und R^ unabhängig voneinander Alkylreste mit 1 bis 18 C-Atomen mit der Maßgabe, daß die Gesamtzahl der C-Atome im Alkansulfonat zwischen 10 und 20 liegt, und Y ein Kation, ausgewählt aus der Gruppe umfassend Wasserstoff-, Alkali- und Ammoniumionen bedeuten, und wobei die Compounds 35 bis 55 Gew.-% Wasser, 10 bis 30 Gew.-%, vorzugsweise 17 bis 25 Gew.-% Alkylglykosid, 10 bis 20 Gew.-%, vorzugsweise 12 bis 18 Gew.-% Alkylsulfat und 1 bis 15 Gew.-%, vorzugsweise 3 bis 10 Gew.-% Alkansulfonat enthalten. Die für die erfindungsgemäßen Tensidmischungen geeigneten Alkylglykoside und ihre Herstellung werden zum Beispiel in den europäischen Patentanmel¬ dungen EP 92355, EP 301298, EP 357969 und EP 362671 oder der US-ameri¬ kanischen Patentschrift US 3547828 beschrieben. Bei den Glykosidkompo- nenten ((G)n in Formel I) derartiger Alkylglykoside handelt es sich um Oligo- oder Polymere aus natürlich vorkommenden Aldose- oder Ketose- Monomeren, zu denen insbesondere Glucose, Mannose, Fruktose, Galaktose, Talose, Gulose, Altrose, AIlose, Idose, Ribose, Arabinose, Xylose und Lyxose sowie deren Gemische gehören. Die aus derartigen glykosidisch ver¬ knüpften Monomeren bestehenden Oligo ere werden außer durch die Art der in ihnen enthaltenen Zucker durch deren Anzahl, den sogenannten Oligomeri- sierungsgrad, charakterisiert. Der Oligomerisierungsgrad (n in Formel I) nimmt als analytisch zu ermittelnde Größe im allgemeinen gebrochene Zahlenwerte an; er liegt bei Werten zwischen 1 und 10, bei den vorzugswei¬ se eingesetzten Alkylglykosiden unter einem Wert von 1,5, insbesondere zwischen 1,2 und 1,4. Bevorzugter Monomer-Baustein ist wegen der guten Verfügbarkeit Glucose.in which R3 and R ^ independently of one another are alkyl radicals having 1 to 18 carbon atoms, with the proviso that the total number of carbon atoms in the alkanesulfonate is between 10 and 20, and Y is a cation selected from the group comprising hydrogen, alkali and ammonium ions, and the compounds being 35 to 55% by weight of water, 10 to 30% by weight, preferably 17 to 25% by weight of alkyl glycoside, 10 to 20% by weight, preferably 12 to 18% by weight % Contain alkyl sulfate and 1 to 15 wt .-%, preferably 3 to 10 wt .-% alkanesulfonate. The alkyl glycosides suitable for the surfactant mixtures according to the invention and their preparation are described, for example, in European Patent Applications EP 92355, EP 301298, EP 357969 and EP 362671 or in the US Pat. No. 3547828. The glycoside components ((G) n in formula I) of such alkyl glycosides are oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, old rose , Allose, Idose, Ribose, Arabinose, Xylose and Lyxose and mixtures thereof. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization (n in formula I) generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the alkyl glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability.
Der Alkylteil (R in Formel I) der in den erfindungsgemäßen Tensid¬ mischungen enthaltenen Alkylglykoside stammt bevorzugt ebenfalls aus leicht zugänglichen Derivaten nachwachsender Rohstoffe, insbesondere aus Fettalkoholen, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Alkylglykoside ein¬ gesetzt werden können. Brauchbar sind demgemäß insbesondere die primären Alkohole mit linearen Octyl-, Decyl-, Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Besonders geeignete Alkylgly¬ koside enthalten einen Kokosfettalkylrest, das heißt Mischungen mit im wesentlichen R-***Dodecyl und R1»Tetradecyl.The alkyl part (R in formula I) of the alkyl glycosides contained in the surfactant mixtures according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkyl glycosides which can be used . Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly suitable alkyl glycosides contain a coconut fatty alkyl radical, that is to say mixtures with essentially R - dodecyl and R 1 »tetradecyl.
Die Alkylglykoside können herstellungsbedingt geringe Mengen, beispiels¬ weise 1 bis 2 %, an nicht umgesetztem langkettigem Alkohol enthalten, was sich nicht nachteilig auf die Eigenschaften der damit hergestellten Ten¬ sidmischungen auswirkt.The alkyl glycosides can contain small amounts, for example 1 to 2%, of unconverted long-chain alcohol, which does not have a disadvantageous effect on the properties of the surfactant mixtures produced therewith.
Als für den Einsatz in den erfindungsgemäßen Tensidmischungen geeignete Alkylsulfate kommen die neutralisierten Sulfatierungsprodukte der oben genannten Alkohole in Frage. Besonders geeignet sind auch in diesem Fall die Derivate der Fettalkohole mit 8 bis 22 C-Atomen, insbesondere mit 12 bis 16 C-Atomen. Die Alkylsulfate können in bekannter Weise durch Reaktion der entsprechenden Alkoholkomponente mit einem üblichen Sulfatierungsrea- genz, insbesondere Schwefeltrioxid oder Chlorsulfonsäure, und anschlie¬ ßende Neutralisation, vorzugsweise mit Alkali-, Ammonium- oder Alkyl- be¬ ziehungsweise Hydroxyalkyl-substituierten Ammoniumbasen, hergestellt wer¬ den.The neutralized sulfation products of the above come as alkyl sulfates suitable for use in the surfactant mixtures according to the invention alcohols in question. The derivatives of fatty alcohols with 8 to 22 carbon atoms, in particular with 12 to 16 carbon atoms, are also particularly suitable in this case. The alkyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization, preferably with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases the.
Bei den erfindungsgemäß eingesetzten sekundären Alkansulfonaten handelt es sich um neutralisierte Substanzen, die durch Sulfoxidation von Kohlen¬ wasserstoffen, die vorzugsweise 10 bis 20 C-Atome enthalten, gewonnen werden. Dabei entstehen in der Regel Produkte mit statistischer Verteilung der Sulfonsäure-Substituenten, die in bekannter Weise* getrennt, werden können. Für die erfindungsgemäße Mischung haben sich die Alkansulfonate mit 12 bis 17 C-Atomen als besonders geeignet erwiesen. Als Kationen kom¬ men insbesondere solche aus der Gruppe der Alkaliionen, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituierten Ammoniumionen in Be¬ tracht.The secondary alkanesulfonates used according to the invention are neutralized substances which are obtained by sulfoxidation of hydrocarbons which preferably contain 10 to 20 carbon atoms. This generally results in products with a statistical distribution of the sulfonic acid substituents, which can be separated * in a known manner. The alkanesulfonates having 12 to 17 carbon atoms have proven to be particularly suitable for the mixture according to the invention. Suitable cations are in particular those from the group of alkali ions, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ions.
Die Herstellung der erfindungsgemäßen Tensidmischungen bereitet keinerlei Schwierigkeiten. Sie kann problemlos durch einfaches Mischen der drei Einzelkomponenten, die als solche oder vorzugsweise in wäßriger Lösung vorliegen können, erfolgen.The preparation of the surfactant mixtures according to the invention presents no difficulties. It can be done easily by simply mixing the three individual components, which can be present as such or preferably in aqueous solution.
Die erfindungsgemäßen Mischungen zeichnen sich durch ihre niedrigen Vis¬ kositäten, ihre leichte Fließfähigkeit und Pumpbarkeit und ihre hohe La¬ gerstabilität aus. Die Viskosität der Compounds liegt im allgemeinen bei 20000 Pa.s bis 50 000 Pa.s. Die erfindungsgemäßen Compounds sind über längere Zeit, mindestens 30 Tage, bei Temperaturen von etwa 1°C bis etwa 45βC lagerstabil.The mixtures according to the invention are notable for their low viscosities, their easy flowability and pumpability and their high storage stability. The viscosity of the compounds is generally between 20,000 Pa.s and 50,000 Pa.s. The compounds of the invention are β long time, at least 30 days, at temperatures of about 1 ° C to about 45 C storage stable.
Die erfindungsgemäBen Coapounds können, direkt oder nach Verdünnen mit Wasser, für technische Anwendungen, zum Beispiel als Flotationshilfsβittel oder Bohrspülungen, eingesetzt werden. Vorzugsweise werden sie jedoch als Vorgemische zur Herstellung flüssiger Wasch- und Reinigungsaittel ver- wendet, zu denen insbesondere Feinwaschmittel, Wo!1Waschmittel und Ge¬ schirrspülmittel, aber auch Shampoos gehören. Derartige Mittel können in einfacher Weise durch Verdünnen der Compounds mit Wasser auf die ge¬ wünschte Aktivsubstanzkonzentration hergestellt werden. Die Zugabe anderer in derartigen Mitteln üblicher Bestandteile, zu denen insbesondere Buil- dersubstanzen, wie Zeolithe und Schichtsilikate, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, optische Aufheller, Enzyme, Vergrauungs- inhibitoren, antimikrobielle Wirkstoffe, wassermischbare Lösungsmittel, Abrasivmittel, Schaumstabilisatoren, Konservierungsmittel, pH-Regulatoren, Färb- und Duftstoffe sowie zusätzliche Tenside gehören, ist möglich.The coapounds according to the invention can be used, directly or after dilution with water, for technical applications, for example as flotation aids or drilling fluids. However, they are preferably used as premixes for the production of liquid washing and cleaning agents. uses, which include in particular mild detergents, detergents and dishwashing detergents, but also shampoos. Such agents can be produced in a simple manner by diluting the compounds with water to the desired active substance concentration. The addition of other constituents customary in such agents, to which in particular builder substances, such as zeolites and layered silicates, corrosion inhibitors, bleaching agents, bleach activators, optical brighteners, enzymes, graying inhibitors, antimicrobial active ingredients, water-miscible solvents, abrasives, foam stabilizers, preservatives, pH agents Regulators, dyes and fragrances as well as additional surfactants are possible.
BeispieleExamples
Beispiel 1example 1
Durch einfaches Mischen der Komponenten, die als wäßrige Lösungen vor¬ lagen, wurden die nachfolgend in Tabelle 1 durch ihre Zusammensetzung charakterisierten erfindungsgemäßen Tensidmischungen Ml bis M3 sowie die in Vergleichsversuchen verwendeten Mittel VI bis V5 hergestellt.By simply mixing the components which were in the form of aqueous solutions, the surfactant mixtures M1 to M3 according to the invention characterized below in Table 1 by their composition and the compositions VI to V5 used in comparative experiments were prepared.
Tabelle 1 : Zusammensetzung der Tensidmischungen [Gew.-%]Table 1: Composition of the surfactant mixtures [% by weight]
Hl M2 M3 VI V2 V3 V4 V5Hl M2 M3 VI V2 V3 V4 V5
A 21,8 24,0 23,0 50,0 24,0 21,8 16,3 30,5A 21.8 24.0 23.0 50.0 24.0 21.8 16.3 30.5
B 14,5 16,1 15,4 - 16,1 14,5 10,8 - C 9,0 3,6 6,0 - - - - 19,8B 14.5 16.1 15.4 - 16.1 14.5 10.8 - C 9.0 3.6 6.0 - - - - 19.8
Ethersulfat9) 9,1 - -Ether sulfate 9 ) 9.1 - -
Arylsulfonat0) - - - 18,0 -Aryl sulfonate 0 ) - - - 18.0 -
Wasser ad 100Water ad 100
a):,Texapon(R) N 70 (Hersteller Henkel); b): Na-Alkylbenzolsulfonat (Mara- nil(R) A 55, Hersteller Henkel) a ):, Texapon ( R ) N 70 (manufacturer Henkel); b ): Na-alkylbenzenesulfonate (Maranil (R) A 55, manufacturer Henkel)
A: Ci2/14-Alkylglukosid, Oligo erisierungsgrad 1,4A: Ci2 / 14-alkyl glucoside, degree of oligomerization 1.4
B: Na-Kokosalkoholsulfat (Texapon(R) LS 35, Hersteller Henkel)B: Na coconut alcohol sulfate (Texapon ( R ) LS 35, manufacturer Henkel)
C: Na-Cχ4/i6-Alkansulfonat (Hostapur(R) SAS 60 S, Hersteller Hoechst) Die erfindungsgemäßen Tensidmischungen Ml bis M3 besaßen pH-Werte (10 Gew.-prozentige wäßrige Lösung) von 9,6.C: Na-Cχ4 / i6 alkanesulfonate (Hostapur ( R ) SAS 60 S, manufacturer Hoechst) The surfactant mixtures M1 to M3 according to the invention had pH values (10% by weight aqueous solution) of 9.6.
Tabelle 2 : Viskositäten (20 °C, Kugelfallviskosimeter nach Höppler)Table 2: Viscosities (20 ° C, falling ball viscometer according to Höppler)
Ml M2 M3 VI V2Ml M2 M3 VI V2
Viskosität (20°C) 25000 40000 25000 28850 55540 [mPa.s]Viscosity (20 ° C) 25000 40000 25000 28850 55540 [mPa.s]
Optische Erschei¬ klar klar klar klar trüb nung (Raumtempe¬ fl. fl. fl. fl. fl. ratur)Optical appearance clear clear clear turbidity (room temperature fl. Fl. Fl. Fl. Rature)
Optische Erschei¬ klar klar klar feste feste' nung (+4°C) fl. fl. fl. Masse MasseOptical evidence clear clear firm solid ' (+ 4 ° C) fl. Fl. Fl. Mass mass
fl. = flüssigfl. = liquid
Mischung V3 war sowohl bei Raumtemperatur als auch bei 4°C ein festes, zähes Gel, dessen Viskosität nicht bestimmt werden konnte. Die Mischungen V4 und V5 waren bei den angegebenen Temperaturen inhomogene, gerade noch fließfähige Pasten.Mixture V3 was a solid, viscous gel both at room temperature and at 4 ° C., the viscosity of which could not be determined. The mixtures V4 and V5 were inhomogeneous, just flowable pastes at the temperatures indicated.
Proben der erfindungsgemäßen Mischungen Ml, M2 und M3 wurden 60 Tage bei 4 °C, 10 °C oder 40 °C gelagert, ohne daß eine Veränderung ihrer Konsi¬ stenz festgestellt wurde. Die Compounds konnten 30 Tage auf Temperaturen von 1 °C abgekühlt werden, ohne daß nach Erwärmen auf Raumtemperatur Vis¬ kositätsänderungen gegenüber den frisch hergestellten Mischungen beob¬ achtet wurden. Beispiel 2: ReinigungsleistungSamples of the mixtures M1, M2 and M3 according to the invention were stored at 4 ° C., 10 ° C. or 40 ° C. for 60 days without a change in their consistency being found. The compounds could be cooled to temperatures of 1 ° C. for 30 days without any changes in viscosity after heating to room temperature compared to the freshly prepared mixtures. Example 2: Cleaning performance
Durch Verdünnen mit Wasser wurden aus den Mischungen Ml bis M3 und VI bis V5 Lösungen hergestellt, die jeweils 0,15 Gramm Aktivsubstanz pro Liter Lösung enthielten. Zur Demonstration der Reinigungsleistung wurde der von H.-J. Lehmann in "Fette, Seifen, Anstrichmittel", 74 (1972), 163, be¬ schriebene Tellertest durchgeführt. Es wurde mit Wasserhärten von 3°d (30mg CaO/Liter) und 16°d (160 mg CaO/Liter) bei 50 °C und mit Rindertalg (2g/Teller) gearbeitet; die angeschmutzten Teller wurden nach 24 Stunden Lagerung bei Raumtemperatur mittels einer rotierenden Spülbürste gespült. Dabei war die Reinigungsleistung der erfindungsgemäßen Compounds derje¬ nigen der Vergleichsmischungen in allen Fällen zumindest gleich. By dilution with water, solutions Ml to M3 and VI to V5 were prepared, each containing 0.15 gram of active substance per liter of solution. To demonstrate the cleaning performance, the one by H.-J. Lehmann in "Fette, Seifen, Anstrichmittel", 74 (1972), 163, described plate test. It worked with water hardness of 3 ° d (30 mg CaO / liter) and 16 ° d (160 mg CaO / liter) at 50 ° C and with beef tallow (2 g / plate); the soiled plates were rinsed after 24 hours of storage at room temperature using a rotating dish brush. The cleaning performance of the compounds according to the invention was at least the same as that of the comparative mixtures in all cases.

Claims

_ _Patentansprüche _ _Patent claims
1. Wäßrige, fließfähige und pumpbare Tensidmischung, enthaltend ein Alkylglykosid und 2 verschiedenartige synthetische anionische Tenside, dadurch gekennzeichnet, daß sie im wesentlichen besteht aus1. Aqueous, flowable and pumpable surfactant mixture containing an alkyl glycoside and 2 different types of synthetic anionic surfactants, characterized in that it consists essentially of
35 bis 55 Gew.-% Wasser,35 to 55% by weight of water,
10 bis 30 Gew.-% eines Alkylglykosids der Formel I,10 to 30% by weight of an alkyl glycoside of the formula I,
R KGJn (I)R KGJn (I)
in der Rl einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykose-Ein- heit und n eine Zahl zwischen 1 und 10 bedeuten, 10 bis 20 Gew.-% eines Alkylsulfats der Formel II,in which R1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10, 10 to 20% by weight of an alkyl sulfate of the formula II,
in der R2 einen Alkylrest mit 8 bis 22 C-Atomen und X ein Alkali- oderin R2 an alkyl radical with 8 to 22 C atoms and X an alkali or
Ammoniumion bedeuten, undMean ammonium ion, and
1 bis 15 Gew.-% eines Alkansulfonats der Formel III,1 to 15% by weight of an alkanesulfonate of the formula III,
in der R3 und R^ unabhängig voneinander Alkylreste mit 1 bis 18 C- Atomen mit der Maßgabe, daß die Gesamtzahl der C-Atome im Alkansul¬ fonat zwischen 10 und 20 liegt, und Y ein Alkali- oder Ammoniumion bedeuten.in which R3 and R ^ independently of one another are alkyl radicals having 1 to 18 carbon atoms with the proviso that the total number of carbon atoms in the alkanesulfonate is between 10 and 20 and Y is an alkali metal or ammonium ion.
2. Tensidmischung nach Anspruch 1, dadurch gekennzeichnet, daß sie 17 bis 25 Gew.-% Alkylglykosid, 12 bis 18 Gew.-% Alkylsulfat und 3 bis 10 Gew.-% Alkansulfonat enthält.2. Surfactant mixture according to claim 1, characterized in that it contains 17 to 25 wt .-% alkyl glycoside, 12 to 18 wt .-% alkyl sulfate and 3 to 10 wt .-% alkane sulfonate.
3. Tensidmischung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Alkylglykosid der Forael (I) einen Oligomerisierungsgrad n unter 1,5, vorzugsweise von 1,2 bis 1,4, besitzt. _ _3. surfactant mixture according to claim 1 or 2, characterized in that the alkyl glycoside of Forael (I) has a degree of oligomerization n below 1.5, preferably from 1.2 to 1.4. _ _
4. Tensidmischung nach einem der Ansprüche 1 bis 3, dadurch gekennzeich¬ net, daß das Alkylglykosid der Formel (I) ein Alkylglucosid ist.4. surfactant mixture according to one of claims 1 to 3, characterized gekennzeich¬ net that the alkyl glycoside of formula (I) is an alkyl glucoside.
5. Tensidmischung nach einem der Ansprüche 1 bis 4, dadurch gekennzeich¬ net, daß das Alkylsulfat der Formel (II) einen Alkylrest R2 mit 12 bis 16 C-Atomen besitzt.5. surfactant mixture according to one of claims 1 to 4, characterized gekennzeich¬ net that the alkyl sulfate of formula (II) has an alkyl radical R2 having 12 to 16 carbon atoms.
6. Tensidmischung nach einem der Ansprüche 1 bis 5, dadurch gekennzeich¬ net, daß das Alkansulfonat der Formel (III) insgesamt 12 bis 17 C-Atome aufweist.6. surfactant mixture according to one of claims 1 to 5, characterized gekennzeich¬ net that the alkanesulfonate of formula (III) has a total of 12 to 17 carbon atoms.
7. Verwendung der Tensidmischung nach einem der Ansprüche 1 bis 6 als la¬ gerstabiles, fließfähiges, pumpbares Vorgemisch für die Herstellung von Wasch- oder Reinigungsmitteln. 7. Use of the surfactant mixture according to one of claims 1 to 6 as a storage stable, flowable, pumpable premix for the production of detergents or cleaning agents.
EP91909996A 1990-06-05 1991-05-27 Liquid, free-flowing and pumpable tenside concentrate Ceased EP0532549A1 (en)

Applications Claiming Priority (2)

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DE4017922A DE4017922A1 (en) 1990-06-05 1990-06-05 LIQUID ALKYL GLYCOSIDE-CONTAINING SURFACTANT
DE4017922 1990-06-05

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DE4017922A1 (en) 1991-12-12
JPH05509111A (en) 1993-12-16
CA2084655A1 (en) 1991-12-06
KR930700632A (en) 1993-03-15

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