EP0349906A2 - Detergent mixture containing non-ionic and anionic surfactants, and their use - Google Patents

Detergent mixture containing non-ionic and anionic surfactants, and their use Download PDF

Info

Publication number
EP0349906A2
EP0349906A2 EP89111881A EP89111881A EP0349906A2 EP 0349906 A2 EP0349906 A2 EP 0349906A2 EP 89111881 A EP89111881 A EP 89111881A EP 89111881 A EP89111881 A EP 89111881A EP 0349906 A2 EP0349906 A2 EP 0349906A2
Authority
EP
European Patent Office
Prior art keywords
detergent mixture
iii
alkyl
carbon atoms
hydroxysulfonate
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
EP89111881A
Other languages
German (de)
French (fr)
Other versions
EP0349906A3 (en
EP0349906B1 (en
Inventor
Bernd Dr. Fabry
Brigitte Giesen
Karlheinz Dr. Hill
Martina Dr. Kihn-Botulinski
Robert Dr. Piorr
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
Priority to AT89111881T priority Critical patent/ATE92096T1/en
Publication of EP0349906A2 publication Critical patent/EP0349906A2/en
Publication of EP0349906A3 publication Critical patent/EP0349906A3/en
Application granted granted Critical
Publication of EP0349906B1 publication Critical patent/EP0349906B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the invention relates to detergent mixtures of nonionic surfactants such as alkyl glycosides and anionic surfactants such as hydroxysulfonates, which are used as a component of reduced phosphate detergents or cleaning agents.
  • detergents with reduced phosphate refer to those detergents which contain at most 30% by weight of alkali metal tripolyphosphates, but which can also be phosphate-free.
  • EP 0 075 074A2 describes a detergent mixture of alkyl glycosides and anionic surfactants.
  • EP 0 070 995A2 describes a detergent mixture of alkyl glycosides and nonionic surfactants.
  • EP 0 105 556A1 describes a liquid detergent mixture which does not select anionic surfactants, alkyl glycosides contains ionic surfactants and optionally other additives.
  • Detergents are currently mainly made from petrochemical raw materials.
  • ABS alkylbenzenesulfonates
  • ABS has good wetting and foaming power, but is only partially compatible with the skin, which can lead to allergies. Furthermore, ABS is only partially biodegradable.
  • the present invention has for its object to provide a detergent mixture of a nonionic surfactant, such as an alkyl glycoside, and an anionic surfactant, such as a hydroxysulfonate, which is composed entirely of native, ie renewable, fat-chemical raw materials.
  • This detergent mixture is intended to replace detergents such as ABS, which are made exclusively from petrochemical, i.e. non-renewable raw materials, in phosphate-reduced detergents and cleaning agents.
  • the detergent mixtures according to the invention show a significantly better biodegradability compared to ABS in the closed bottle test and also a significantly better one Skin tolerance in the epidermal swelling test, as can be shown in the examples.
  • phosphate-reduced detergents which contain the detergent mixture according to the invention have better washability than commercially available phosphate-reduced detergents based on ABS.
  • the detergent mixtures according to the invention can be mixed in any ratio to one another, preferably the mixing ratio of alkyl glycoside to hydroxysulfonate is 10 to 90% to 90 to 10%.
  • the products according to the invention remain liquid up to a content of 75% washing active substance (WAS), whereas products based on ABS already form precipitates at a content of 60% WAS and can no longer be pumped.
  • WAS washing active substance
  • Alkyl glycosides suitable for the purposes of this invention are described, for example, in US Pat. Nos. 3,547,828 and 3,839,318.
  • Typical alkyl glycosides are those in which alkyl is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and mixtures thereof.
  • Particularly suitable alkyl glycosides contain a coconut fatty alkyl residue, ie dodecyl and tetradecyl residues.
  • the sugar component comes from the usual aldoses or ketoses, such as glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose.
  • aldoses or ketoses such as glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose.
  • the particularly preferred alkyl glycosides are the alkyl glucosides because of the good reactivity and easy accessibility of the glucose.
  • the index number x is any number between 1 and 10, which indicates the degree of oligomerization, ie the distribution of monoglycosides and oligoglycosides.
  • the value x for a specific alkyl glycoside process product is an analytically determined arithmetic parameter, usually one is a fractional number.
  • the alkyl glycosides are represented by the formula RO (G) x , the percentage of fatty alcohol is neglected. In principle, this fatty alcohol portion can largely be controlled by gentle distillative treatment of the alkyl glycoside, ie the excess fatty alcohol resulting from the reaction can be removed from the product except for residual values which are less than 1% total.
  • alkyl glycosides with essentially C12-C22-alkyl or alkenyl radicals belong to the type of nonionic surfactants.
  • the hydrophobic part comes from renewable raw materials if it is derived from fatty alcohols and the hydrophilic part is made up of ethylene oxide units and thus from a petrochemical raw material, the alkyl glycosides as fatty alkyl glycosides can be made entirely from renewable ones Raw materials, namely fat on the one hand and sugars or starches on the other hand, are produced.
  • Alkyl glycosides whose alkyl radical is derived from synthetic primary alcohols, in particular the so-called oxo alcohols, i.e. those primary alkanols, which have a certain percentage, mostly 20 to 40%, of branched isomers, mostly with a 2-methyl residue.
  • oxo alcohols i.e. those primary alkanols, which have a certain percentage, mostly 20 to 40%, of branched isomers, mostly with a 2-methyl residue.
  • surfactants are less preferred if the focus is on the intended use of surfactants with a natural raw material base, including the hydrophobic part.
  • the group R2-CO can be a formyl, acetyl, propionyl or butyryl group; the acetyl group is preferred.
  • the group R 1 is preferably an oleyl group or a fatty alkyl radical consisting predominantly of oleyl groups.
  • Preferred values for the sum (y + z + p) in the compounds (II) and (III) are consequently 12 to 18, preferably 12 to 14.
  • auxiliaries or additives in the sense of this invention are conventional constituents such as Builder substances, bleaching agents, foam stabilizers, complexing agents, optical brighteners, thickeners, dirt suspending agents, graying inhibitors, dyes, perfume oils, enzymes, bactericides, fungicides etc.
  • surfactants can also be added to the mixture, provided that they do not interfere with the synergistic effect of the detergent mixture according to the invention.
  • HOS C18 diolsulfonate Na salt based on Ocenol 90/95 (oleyl alcohol, technical)
  • HOES5 C18 diol ether sulfonate Na salt based on Ocenol 90/95 with an average of 5 mol EO ethoxylated
  • Zeolite NaA product that is used as an undried stabilized suspension that is still moist from manufacture. Enriched in the recipes as an anhydrous substance.
  • the substances used had the chemical composition defined in Application Example 1.
  • HOS HOES5 AG SECTION Remiss. 1) Remiss. 2) % By weight % By weight % By weight % By weight % By weight % By weight % By weight % By weight 100 34.0 41.6 100 0 31.9 41.7 90 10th 32.8 40.8 75 25th 33.7 39.2 50 50 33.0 36.5 25th 75 31.4 32.2 10th 90 28.3 28.6 0 100 25.7 26.7 100 0 31.9 41.7 90 10th 33.1 41.2 75 25th 35.4 42.3 50 50 35.9 41.6 25th 75 36.4 39.8 10th 90 35.4 37.2 0 100 34.3 35.5 Recipe: The specified reflectance measurements refer to the following builder-containing or builder-free recipes: 1) 0.5 g AS / l + 2.0 g sodium sulfate 2) 0.5 g AS / l + 1.5 g NaTPP / zeolite NaA (1: 1)
  • the degradability of surfactants can be assessed based on the biochemical oxygen demand (BOD) in microbial oxidation.
  • BOD biochemical oxygen demand
  • test was carried out over a period of 30 days in a closed system at a test concentration of 2 mg AS / I (for the test method see "Fette Seifen Anstrm.” 65 (1963) 37).
  • a pig epidermis is placed in an aqueous solution of the surfactant to be tested and the swelling compared to pure water.
  • the swelling factors for anionic surfactants and systems containing anionic surfactants found using this method correlate very well with measurements of skin tolerance in vivo (cf. J. Soc. Cosmet. Chem. Jap. 20 (1986) 17).

Abstract

PCT No. PCT/EP89/00732 Sec. 371 Date Mar. 7, 1991 Sec. 102(e) Date Mar. 7, 1991 PCT Filed Jun. 29, 1989 PCT Pub. No. WO90/00592 PCT Pub. Date Jan. 25, 1990.The invention relates to a detergent mixture containing A) at least one alkyl glycoside corresponding to general formula (I) RO(G)x (I) in which R is an aliphatic radical containing at least 8 carbon atoms, preferably a primary alcohol radical and, more preferably, a fatty alkyl or fatty alkenyl radical containing 8 to 22 and preferably 12 to 18 carbon atoms, G is a symbol which stands for a glycose unit, i.e. which derives from a reducing saccharide containing 5 or 6 carbon atoms and X is a number of 1 to 10, B) an anionic surfactant and C) typical auxiliaries and additives, characterized in that the anionic surfactant B) is at least one hydroxysulfonate consisting entirely or predominantly of compounds corresponding to formula (II) or (III) <IMAGE> (II) <IMAGE> (III) in which y and z=0 or numbers of 1 to 18, p=0, 1 or 2 and the sum (y+z+p) is a number of 4 to 18, x=0 or a number of up to 30 and n may be an integer of 2 to 4, or alkali metal, alkaline earth metal and ammonium salts of such compounds, and to its use as a constituent of phosphate-reduced detergents and cleaning preparations.

Description

Die Erfindung betrifft Detergensmischungen aus nichtionischen Tensiden wie Alkylglykosiden und anionischen Tensiden wie Hydroxysulfonaten, die als Bestandteil von phosphatreduzierten Waschmitteln oder Reinigungsmitteln verwendet werden.The invention relates to detergent mixtures of nonionic surfactants such as alkyl glycosides and anionic surfactants such as hydroxysulfonates, which are used as a component of reduced phosphate detergents or cleaning agents.

Mit "phosphatreduziert" werden im folgenden solche Waschmittel bezeichnet, die höchstens 30 Gew.-% Alkalitripolyphosphate enthalten, die aber auch phosphatfrei sein können.In the following, "detergents with reduced phosphate" refer to those detergents which contain at most 30% by weight of alkali metal tripolyphosphates, but which can also be phosphate-free.

Aus der deutschen Patentanmeldung DE 19 61 855 ist bekannt, daß Tensidmischungen von 2 anionischen Tensiden wie Alkylbenzolsul­fonaten und Alkylethersulfaten oder sekundären linearen Alkan­sulfonaten und Alkylethersulfaten synergistische Eigenschaften in bezug auf Schaumbildung und Wascheffekte zeigen.From German patent application DE 19 61 855 it is known that surfactant mixtures of 2 anionic surfactants such as alkylbenzenesulfonates and alkyl ether sulfates or secondary linear alkanesulfonates and alkyl ether sulfates show synergistic properties with regard to foam formation and washing effects.

Die EP 0 075 074A2 beschreibt eine Detergensmischung aus Alkyl­glykosiden und anionischen Tensiden.EP 0 075 074A2 describes a detergent mixture of alkyl glycosides and anionic surfactants.

Die EP 0 070 995A2 beschreibt eine Detergensmischung aus Alkyl­glykosiden und nichtionischen Tensiden.EP 0 070 995A2 describes a detergent mixture of alkyl glycosides and nonionic surfactants.

Die EP 0 105 556A1 beschreibt eine flüssige Detergensmischung, die anionische Tenside, Alkylglykoside, ausgewählte nicht­ ionische Tenside und gegebenenfalls weitere Zusatzstoffe ent­hält.EP 0 105 556A1 describes a liquid detergent mixture which does not select anionic surfactants, alkyl glycosides contains ionic surfactants and optionally other additives.

Detergenzien werden zur Zeit noch überwiegend aus petrochemi­schen Grundstoffen hergestellt. Das hiervon wirtschaftlich bedeutendste Detergens und auch das in der westlichen Welt am meisten verbrauchte Detergens gehört der Tensidklasse der Al­kylbenzolsulfonate (ABS) an (Verbrauch 1980 USA und Westeuropa: 790 000 t).Detergents are currently mainly made from petrochemical raw materials. The most economically important detergent and also the most widely used detergent in the western world belongs to the surfactant class of alkylbenzenesulfonates (ABS) (consumption 1980 USA and Western Europe: 790,000 t).

ABS besitzt zwar ein gutes Netz- und Schaumbildungsvermögen, ist allerdings nur bedingt hautverträglich, was unter Umständen zu Allergien führen kann. Weiterhin ist ABS nur zum Teil biolo­gisch abbaubar.ABS has good wetting and foaming power, but is only partially compatible with the skin, which can lead to allergies. Furthermore, ABS is only partially biodegradable.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, eine Detergensmischung aus einem nichtionischen Tensid, wie einem Alkylglykosid, und einem anionischen Tensid, wie einem Hydroxy­sulfonat, zu schaffen, die vollständig aus nativen, also nach­wachsenden fettchemischen Grundstoffen zusammengesetzt ist. Diese Detergensmischung soll Detergenzien wie ABS, die aus­schließlich aus petrochemischen, also nicht nachwachsenden Grundstoffen hergestellt werden, in phosphatreduzierten Wasch­mitteln und Reinigungsmitteln substituieren.The present invention has for its object to provide a detergent mixture of a nonionic surfactant, such as an alkyl glycoside, and an anionic surfactant, such as a hydroxysulfonate, which is composed entirely of native, ie renewable, fat-chemical raw materials. This detergent mixture is intended to replace detergents such as ABS, which are made exclusively from petrochemical, i.e. non-renewable raw materials, in phosphate-reduced detergents and cleaning agents.

Die Erfindung betrifft eine Detergensmischung, enthaltend

  • A) mindestens ein Alkylglykosid der allgemeinen Formel (I)
    RO(G)x      (I)
    in der
    R einen aliphatischen Rest mit wenigstens 8 C-Atomen, ins­besondere den Rest eines primären Alkohols und ganz be­sonders einen Fettalkyl- oder Fettalkenyl-Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet,
    G ein Symbol ist, das für eine Glykoseeinheit steht, d.h. das sich von einem reduzierenden Saccharid mit 5 oder 6 C-Atomen ableitet,
    und
    x für eine Zahl zwischen 1 und 10 steht,
  • B) ein anionisches Tensid sowie
  • C) übliche Hilfs- und Zusatzstoffe,
die dadurch gekennzeichnet ist, daß das anionische Tensid B) mindestens ein Hydroxysulfonat, das ganz oder überwiegend aus Verbindungen der Formeln (II) oder (III)
Figure imgb0001
 oder deren Alkali-, Erdalkali- und Ammoniumsalzen zusammenge­setzt ist, wobei y und z = O oder Zahlen von 1 bis 18, p = 0, 1 oder 2 und die Summe (y + z + p) eine Zahl von 4 bis 18, x = 0 oder eine Zahl bis 30 und n eine ganze Zahl von 2 bis 4 sein kann, ist.The invention relates to a detergent mixture containing
  • A) at least one alkyl glycoside of the general formula (I)
    RO (G) x (I)
    in the
    R denotes an aliphatic radical with at least 8 carbon atoms, in particular the radical of a primary alcohol and very particularly a fatty alkyl or fatty alkenyl radical with 8 to 22, preferably 12 to 18, carbon atoms,
    G is a symbol which stands for a glycose unit, ie which is derived from a reducing saccharide with 5 or 6 carbon atoms,
    and
    x represents a number between 1 and 10,
  • B) an anionic surfactant as well
  • C) usual auxiliaries and additives,
which is characterized in that the anionic surfactant B) comprises at least one hydroxysulfonate which is composed entirely or predominantly of compounds of the formulas (II) or (III)
Figure imgb0001
 or their alkali, alkaline earth and ammonium salts are composed, where y and z = O or numbers from 1 to 18, p = 0, 1 or 2 and the sum (y + z + p) a number from 4 to 18, x = 0 or a number up to 30 and n can be an integer from 2 to 4.

Die erfindungsgemäßen Detergensmischungen zeigen eine im Ver­gleich zu ABS bedeutend bessere biologische Abbaubarkeit im geschlossenen Flaschentest und ebenso eine deutlich bessere Hautverträglichkeit im Epidermisquelltest, wie in den Bei­spielen gezeigt werden kann.The detergent mixtures according to the invention show a significantly better biodegradability compared to ABS in the closed bottle test and also a significantly better one Skin tolerance in the epidermal swelling test, as can be shown in the examples.

Weiterhin weisen phosphatreduzierte Waschmittel, die die erfin­dungsgemäße Detergensmischung enthalten, ein besseres Waschver­mögen auf als marktübliche phosphatreduzierte Waschmittel auf ABS-Basis.Furthermore, phosphate-reduced detergents which contain the detergent mixture according to the invention have better washability than commercially available phosphate-reduced detergents based on ABS.

Die erfindungsgemäßen Detergensmischungen können in beliebigem Verhältnis zueinander gemischt werden, vorzugsweise beträgt das Mischungsverhältnis Alkylglykosid zu Hydroxysulfonat 10 zu 90 % bis 90 zu 10 %.The detergent mixtures according to the invention can be mixed in any ratio to one another, preferably the mixing ratio of alkyl glycoside to hydroxysulfonate is 10 to 90% to 90 to 10%.

Die erfindungsgemäßen Produkte bleiben bis zu einem Gehalt von 75 % Waschaktivsubstanz (WAS) flüssig, wohingegen Produkte auf Basis ABS bereits bei einem Gehalt von 60 % WAS Ausfällungen bilden und nicht mehr pumpbar sind.The products according to the invention remain liquid up to a content of 75% washing active substance (WAS), whereas products based on ABS already form precipitates at a content of 60% WAS and can no longer be pumped.

Im Sinne dieser Erfindung geeignete Alkylglykoside werden bei­spielsweise in den US-Patentschriften 3,547,828 und 3,839,318 beschrieben. Besonders bevorzugt verwendete Alkylglykoside sind die in der deutschen Patentanmeldung P 37 23 826.4 beschriebe­nen Verfahrensprodukte, die einen Alkylmonoglykosidanteil von über 70 Gew.-% (bezogen auf die Gesamtmenge aus Alkylmono- und Alkyloligoglykosiden) und einem mittleren Oligomerisierungsgrad von weniger als x = 1,5 aufweisen.Alkyl glycosides suitable for the purposes of this invention are described, for example, in US Pat. Nos. 3,547,828 and 3,839,318. Alkyl glycosides used with particular preference are the process products described in German patent application P 37 23 826.4, which have an alkyl monoglycoside content of more than 70% by weight (based on the total amount of alkyl mono- and alkyl oligoglycosides) and an average degree of oligomerization of less than x = 1.5 exhibit.

Typische Alkylglykoside sind solche, in denen Alkyl für Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Penta­decyl, Hexadecyl, Heptadecyl, Octadecyl und Mischungen daraus steht. Besonders geeignete Alkylglykoside enthalten einen Kokosfettalkylrest, d.h. Dodecyl- und Tetradecylreste.Typical alkyl glycosides are those in which alkyl is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and mixtures thereof. Particularly suitable alkyl glycosides contain a coconut fatty alkyl residue, ie dodecyl and tetradecyl residues.

Die Zuckerkomponente stammt von den üblichen Aldosen bzw. Ketosen, wie z.B. Glucose, Fructose, Mannose, Galactose, Talose, Gulose, Allose, Altrose, Idose, Arabinose, Xylose, Lyxose und Ribose. Die besonders bevorzugten Alkylglykoside sind wegen der guten Reaktionsfähigkeit und leichten Zugäng­lichkeit der Glucose die Alkylglucoside. Die Indexzahl x ist eine beliebige Zahl zwischen 1 und 10, womit der sogenannte Oligomerisierungsgrad, d.h. die Verteilung von Monoglykosiden und Oligoglykosiden angegeben wird. Während x in einer gegebe­nen Verbindung immer eine ganze Zahl sein muß, und hier vor allem die Zahlen x = 1, 2, 3, 4 infrage kommen, ist der Wert x für ein spezielles Alkylglykosid-Verfahrensprodukt eine analy­tisch ermittelte rechnerische Größe, die meistens eine ge­brochene Zahl ist. Bei der Wiedergabe der Alkylglykoside durch die Formel RO(G)x wird der Fettalkoholanteil vernachlässigt. Dieser Fettalkoholanteil kann prinzipiell weitgehend durch schonende destillative Behandlung des Alkylglykosids gesteuert werden, d.h. der aus der Reaktion stammende Fettalkoholüber­schuß kann bis auf Restwerte, die unter 1 % Gesamtanteil lie­gen, aus dem Produkt entfernt werden.The sugar component comes from the usual aldoses or ketoses, such as glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose. The particularly preferred alkyl glycosides are the alkyl glucosides because of the good reactivity and easy accessibility of the glucose. The index number x is any number between 1 and 10, which indicates the degree of oligomerization, ie the distribution of monoglycosides and oligoglycosides. While x must always be an integer in a given compound, and especially the numbers x = 1, 2, 3, 4 come into question, the value x for a specific alkyl glycoside process product is an analytically determined arithmetic parameter, usually one is a fractional number. When the alkyl glycosides are represented by the formula RO (G) x , the percentage of fatty alcohol is neglected. In principle, this fatty alcohol portion can largely be controlled by gentle distillative treatment of the alkyl glycoside, ie the excess fatty alcohol resulting from the reaction can be removed from the product except for residual values which are less than 1% total.

Die Alkylglykoside mit im wesentlichen C₁₂-C₂₂-Alkyl- bzw. Alkenyl-Resten gehören zum Typ der nichtionischen Tenside.The alkyl glycosides with essentially C₁₂-C₂₂-alkyl or alkenyl radicals belong to the type of nonionic surfactants.

Während aber bei den üblichen nichtionischen Tensiden vom Typ der Alkylpolyglykolether allenfalls der hydrophobe Teil von nachwachsenden Rohstoffen stammt, wenn er sich von Fettalko­holen ableitet, und der hydrophile Teil aus Ethylenoxidein­heiten und damit aus einem petrochemischen Rohstoff aufgebaut ist, können die Alkylglykoside als Fettalkylglykoside vollstän­dig aus nachwachsenden Rohstoffen, nämlich Fett einerseits und Zuckern bzw. Stärken andererseits, hergestellt werden.However, while with the usual nonionic surfactants of the alkyl polyglycol ether type, the hydrophobic part comes from renewable raw materials if it is derived from fatty alcohols and the hydrophilic part is made up of ethylene oxide units and thus from a petrochemical raw material, the alkyl glycosides as fatty alkyl glycosides can be made entirely from renewable ones Raw materials, namely fat on the one hand and sugars or starches on the other hand, are produced.

Zwar können im Sinne der Erfindung auch solche Alkylglykoside verwendet werden, deren Alkylrest sich von synthetischen pri­mären Alkoholen, insbesondere den sogenannten Oxoalkoholen, d.h. solchen primären Alkanolen, die einen gewissen Prozent­satz, meist 20 bis 40 %, an verzweigten Isomeren, meist mit einem 2-Methyl-Rest, aufweisen, ableitet. Jedoch sind derartige Tenside dann weniger bevorzugt, wenn der Schwerpunkt beim ge­wollten Einsatz von Tensiden mit natürlicher Rohstoffbasis auch des hydrophoben Teils liegt.Alkyl glycosides whose alkyl radical is derived from synthetic primary alcohols, in particular the so-called oxo alcohols, i.e. those primary alkanols, which have a certain percentage, mostly 20 to 40%, of branched isomers, mostly with a 2-methyl residue. However, such surfactants are less preferred if the focus is on the intended use of surfactants with a natural raw material base, including the hydrophobic part.

Die für die Zwecke der Erfindung als zweite Komponente verwen­deten Hydroxysulfonate sind ausführlich in der älteren deut­schen Patentanmeldung P 37 25 030.2 beschrieben. Sie werden beispielsweise erhalten, indem man einen ungesättigten Fett­alkyl- oder Fettalkylpolyoxyalkylester der allgemeinen Formel (IV)

R¹-O-(CnH2nO)x-

Figure imgb0002
-R²      (IV)
in welcher
R¹ eine lineare Alkenylgruppe mit 16 bis 22 C-Atomen oder eine überwiegend aus Oleyl-, Palmitoleyl-, Linoleyl-, Gadoleyl- und/oder Erucylgruppen bestehende Fettalkyl­gruppen,
n eine ganze Zahl von 2 bis 4,
x = 0 oder eine Zahl bis 30 und
R²CO eine Acylgruppe mit 1 bis 4 C-Atomen darstellt,
mit Schwefeltrioxid umsetzt, das Umsetzungsprodukt in eine wäßrige Lösung von 1 bis 2,5 Mol Alkali-, Erdalkali- oder Am­ moniumhydroxid pro Mol angelagertes SO₃ einträgt und die Lösung bis zur Hydrolyse der enthaltenen Ester- und Sultongruppen erwärmt.The hydroxysulfonates used as the second component for the purposes of the invention are described in detail in the earlier German patent application P 37 25 030.2. They are obtained, for example, by using an unsaturated fatty alkyl or fatty alkyl polyoxyalkyl ester of the general formula (IV)

R¹-O- (C n H 2n O) x -
Figure imgb0002
-R² (IV)
in which
R¹ is a linear alkenyl group with 16 to 22 C atoms or a fatty alkyl group consisting predominantly of oleyl, palmitoleyl, linoleyl, gadoleyl and / or erucyl groups,
n is an integer from 2 to 4,
x = 0 or a number up to 30 and
R²CO represents an acyl group with 1 to 4 carbon atoms,
reacted with sulfur trioxide, the reaction product in an aqueous solution of 1 to 2.5 mol of alkali metal, alkaline earth metal or Am enters monium hydroxide per mole of attached SO₃ and the solution is heated until the hydrolysis of the ester and sulton groups contained.

Bevorzugte Hydroxysulfonate als Komponente in der erfindungsge­mäßen Detergensmischung werden erhalten, wenn zur Sulfonierung ein ungesättigter C₁₂ bis C₁₈-, vorzugsweise C₁₆ bis C₁₈-Fett­alkohol- oder Fettalkylpolyoxyalkylester der Formel (IV), in der n = 2 und x = 0 oder eine Zahl bis 20, vorzugsweise 1 bis 10 ist, d.h. ein Ester eines ungesättigten Fettalkohols und eines Anlagerungsproduktes von bis zu 20 Mol Ethylenoxid, vorzugsweise bis zu 10 Mol Ethylenoxid, an einem ungesättigten Fettalkohol eingesetzt wird. Die Gruppe R²-CO kann eine For­myl-, Acetyl-, Propionyl oder Butyrylgruppe sein; bevorzugt ist die Acetylgruppe. Die Gruppe R¹ ist bevorzugt eine Oleylgruppe oder ein vorwiegend aus Oleylgruppen bestehender Fettalkylrest.Preferred hydroxysulfonates as a component in the detergent mixture according to the invention are obtained if an unsaturated C₁₂ to C₁₈, preferably C₁₆ to C₁₈ fatty alcohol or fatty alkyl polyoxyalkyl ester of the formula (IV) in which n = 2 and x = 0 or a number to 20 for sulfonation , preferably 1 to 10, ie an ester of an unsaturated fatty alcohol and an adduct of up to 20 moles of ethylene oxide, preferably up to 10 moles of ethylene oxide, is used on an unsaturated fatty alcohol. The group R²-CO can be a formyl, acetyl, propionyl or butyryl group; the acetyl group is preferred. The group R 1 is preferably an oleyl group or a fatty alkyl radical consisting predominantly of oleyl groups.

Bevorzugte Werte für die Summe (y + z + p) in den Verbindungen (II) und (III) sind folglich 12 bis 18, vorzugsweise 12 bis 14.Preferred values for the sum (y + z + p) in the compounds (II) and (III) are consequently 12 to 18, preferably 12 to 14.

Geeignete Hilfs- oder Zusatzstoffe im Sinne dieser Erfindung sind übliche Bestandteile wie z.B. Buildersubstanzen, Bleich­mittel, Schaumstabilisatoren, Komplexierungsmittel, optische Aufheller, Verdickungsmittel, Schmutzsuspendiermittel, Ver­grauungsinhibitoren, Farbstoffe, Parfümöle, Enzyme, Bakteri­zide, Fungizide usw.Suitable auxiliaries or additives in the sense of this invention are conventional constituents such as Builder substances, bleaching agents, foam stabilizers, complexing agents, optical brighteners, thickeners, dirt suspending agents, graying inhibitors, dyes, perfume oils, enzymes, bactericides, fungicides etc.

Auch andere Tenside können der Mischung hinzugefügt werden, sofern sie die synergistische Wirkung der erfindungsgemäßen Detergensmischung nicht störend beeinflussen.Other surfactants can also be added to the mixture, provided that they do not interfere with the synergistic effect of the detergent mixture according to the invention.

Die Erfindung wird durch die nachfolgenden Beispiele und An­wendungsbeispiele erläutert:The invention is illustrated by the following examples and application examples:

Anwendungsbeispiel 1:Application example 1: Waschvermögen von Mischungen aus Hydroxysulfonaten (Diol­(ether)sulfonaten) und Alkylglucosiden in einer phosphatfreien EinfachrezepturWashability of mixtures of hydroxysulfonates (diol (ether) sulfonates) and alkyl glucosides in a phosphate-free single formulation Eingesetzte Substanzen:Substances used:

HOS = C₁₈-Diolsulfonat-Na-Salz auf Basis von Ocenol 90/95 (Oleylalkohol, technisch)
HOES5 = C₁₈-Diolethersulfonat-Na-Salz auf Basis Ocenol 90/95 mit durchschnittlich 5 mol EO ethoxyliert
HOES10 = C₁₈-Diolethersulfonat-Na-Salz auf Basis Ocenol 90/95 mit durchschnittlich 10 mol EO ethoxyliert
AG = C12/14-Glucosid (Oligomerisierungsgrad 1,3)
Zeolith NaA = Produkt, das als ungetrocknete, von der Herstel­lung her noch feuchte, stabilisierte Suspension zum Einsatz kommt. In den Rezepturen als wasserfreie Sub­stanz bereichnet. Calciumbindevermögen 165 mg CaO/g, gemäß DE 24 12 837A1 bestimmt.
SokalanR CP5 = Copolymerisat aus Acrylsäure und Maleinsäure. ABS = Dodecylbenzolsulfonat-Na-Salz. Rezepturen (Gew.-%): A) 3,0 Wasserglas B) 3,0 Wasserglas 1,5 Kokosfettsäure, Natriumsalz 1,5 Kokosfettsäure, Natriumsalz 20,0 Zeolith NaA 20,0 Zeolith NaA 3,5 Sokalan CP5 3,5 Sokalan CP5 7,0 Soda 7,0 Soda 41,0 Natriumsulfat 41,0 Natriumsulfat 13,5 ABS 7,5 Alkylglucosid 1,5 C16/18-Fettalkohol mit durchschnittlich 8 mol EO ethoxyliert 7,5 HOS C) 3,0 Wasserglas D) 3,0 Wasserglas 1,5 Kokosfettsäure, Natriumsalz 1,5 Kokosfettsäure, Natriumsalz 20,0 Zeolith NaA 20,0 Zeolith NaA 3,5 Sokalan CP5 3,5 Sokalan CP5 7,0 Soda 7,0 Soda 41,0 Natriumsulfat 41,0 Natriumsulfat 7,5 Alkylglucosid 7,5 Alkylglucosid 7,5 HOES5 7,5 HOES10 Rezeptur Remiss.1. 1) Remiss.2. 2) Remiss.3. 3) % % % A (Vergleich) 44,5 33,5 43,5 B 55,0 33,0 47,0 C 57,5 35,0 48,5 D 56,0 36,0 49,0 Test-Anschmutzungen: 1) Fett-Pigment-Anschmutzungen 2) Kosmetik-Anschmutzungen 3) Mineralöl-Anschmutzung HOS = C₁₈ diolsulfonate Na salt based on Ocenol 90/95 (oleyl alcohol, technical)
HOES5 = C₁₈ diol ether sulfonate Na salt based on Ocenol 90/95 with an average of 5 mol EO ethoxylated
HOES10 = C₁₈ diol ether sulfonate Na salt based on Ocenol 90/95 with an average of 10 mol EO ethoxylated
AG = C 12/14 glucoside (degree of oligomerization 1.3)
Zeolite NaA = product that is used as an undried stabilized suspension that is still moist from manufacture. Enriched in the recipes as an anhydrous substance. Calcium binding capacity 165 mg CaO / g, determined according to DE 24 12 837A1.
Sokalan R CP5 = copolymer of acrylic acid and maleic acid. ABS = dodecylbenzenesulfonate Na salt. Recipes (% by weight): A) 3.0 Water glass B) 3.0 Water glass 1.5 Coconut fatty acid, sodium salt 1.5 Coconut fatty acid, sodium salt 20.0 Zeolite NaA 20.0 Zeolite NaA 3.5 Sokalan CP5 3.5 Sokalan CP5 7.0 soda 7.0 soda 41.0 Sodium sulfate 41.0 Sodium sulfate 13.5 SECTION 7.5 Alkyl glucoside 1.5 C 16/18 fatty alcohol ethoxylated with an average of 8 mol EO 7.5 HOS C) 3.0 Water glass D) 3.0 Water glass 1.5 Coconut fatty acid, sodium salt 1.5 Coconut fatty acid, sodium salt 20.0 Zeolite NaA 20.0 Zeolite NaA 3.5 Sokalan CP5 3.5 Sokalan CP5 7.0 soda 7.0 soda 41.0 Sodium sulfate 41.0 Sodium sulfate 7.5 Alkyl glucoside 7.5 Alkyl glucoside 7.5 HOES5 7.5 HOES10 Recipe Remiss. 1. 1) Remiss. 2. 2) Remiss. 3. 3) % % % A (comparison) 44.5 33.5 43.5 B 55.0 33.0 47.0 C. 57.5 35.0 48.5 D 56.0 36.0 49.0 Test soiling: 1) Fat-pigment soiling 2) Cosmetic stains 3) Mineral oil contamination

Waschbedingungen:Washing conditions:

Miele W760, 85 g/Maschine, 30 °C, 1-Laugen Programm Buntwäsche, Beladung mit 3,5 kg sauberer Wäsche, 16 °dH, 3fach-Bestimmung.
Vergleicht man die Rezeptur nach dem Stand der Technik auf ABS-Basis (Rezeptur A) mit den Rezepturen, die die erfindungs­gemäße Detergensmischung enthalten (Rezepturen B bis D), so findet man für die erfindungsgemäßen Waschmittel ein deutlich verbessertes Waschvermögen. Insbesondere bei Fett-Pigment-An­ schmutzungen und Mineralölanschmutzung tritt dieser Effekt in unerwarteter Art und Weise auf. Die für die erfindungsgemäßen Detergensmischungen in einer phosphatfreien Rezeptur erhaltenen Remissionswerte übertreffen selbst die in Anwendungsbeispiel 2 dokumentierten Remissionswerte für eine phosphathaltige Rezep­tur.Miele W760, 85 g / machine, 30 ° C, 1-wash program colored laundry, loading with 3.5 kg clean laundry, 16 ° dH, triple determination.
If one compares the formulation according to the state of the art based on ABS (formulation A) with the formulations containing the detergent mixture according to the invention (formulations B to D), the detergents according to the invention have a significantly improved washing capacity. Especially with fat pigment an dirt and mineral oil contamination, this effect occurs in an unexpected way. The reflectance values obtained for the detergent mixtures according to the invention in a phosphate-free formulation even exceed the reflectance values documented in application example 2 for a phosphate-containing formulation.

Anwendungsbeispiele 2:Application examples 2: Waschvermögen von Mischungen aus Hydroxysulfonaten (Diolsul­fonaten) und Alkylglucosiden in einer phosphathaltigen Ein­fachrezepturWashability of mixtures of hydroxysulfonates (diolsulfonates) and alkyl glucosides in a phosphate-based single formulation

Die eingesetzten Substanzen hatten die in Anwendungsbeispiel 1 definierte chemische Zusammensetzung. Rezepturen (Gew.-%): A) 5,0 Wasserglas B) 5,0 Wasserglas 2,0 Kokosfettsäure-Natriumsalz 2,0 Kokosfettsäure-Natriumsalz 20,0 Natriumtripolyphosphat 20,0 Natriumtripolyphosphat 13,5 ABS 7,5 Alkylglucosid 1,5 C16/18-Fettalkohol mit durchschnittlich 8 mol EO ethoxyliert 7,5 HOS Rest: Natriumsulfat und Wasser Rest: Natriumsulfat und Wasser Rezeptur Remiss.1. 1) Remiss.2. 2) Remiss.3. 3) % % % A (Vergleich) 52,3 32,5 45,1 B 54,7 33,0 39,7 C 59,0 34,0 48,0 D 58,4 35,0 48,3 (Tensidteil der Rezepturen C und D wie in Beispiel 1, Rezepturen sonst wie in B oben). Test-Anschmutzungen: 1) Fett-Pigment-Anschmutzungen 2) Kosmetik-Anschmutzungen 3) Mineralöl-Anschmutzung The substances used had the chemical composition defined in Application Example 1. Recipes (% by weight): A) 5.0 Water glass B) 5.0 Water glass 2.0 Coconut fatty acid sodium salt 2.0 Coconut fatty acid sodium salt 20.0 Sodium tripolyphosphate 20.0 Sodium tripolyphosphate 13.5 SECTION 7.5 Alkyl glucoside 1.5 C 16/18 fatty alcohol ethoxylated with an average of 8 mol EO 7.5 HOS Rest: sodium sulfate and water Rest: sodium sulfate and water Recipe Remiss. 1. 1) Remiss. 2. 2) Remiss. 3. 3) % % % A (comparison) 52.3 32.5 45.1 B 54.7 33.0 39.7 C. 59.0 34.0 48.0 D 58.4 35.0 48.3 (Part of surfactant of formulations C and D as in example 1, formulations otherwise as in B above). Test soiling: 1) Fat-pigment soiling 2) Cosmetic stains 3) Mineral oil contamination

Waschbedingungen:Washing conditions:

Miele W760, 85 g/Maschine, 30 °C, 1-Laugen Programm Buntwäsche, Beladung mit 3,5 kg sauberer Wäsche, 16 °dH, 3fach-Bestimmung.
Vergleicht man die Rezeptur nach dem Stand der Technik auf ABS-Basis (Rezeptur A) mit der Rezeptur, die die erfindungs­gemäße Detergensmischung enthält (Rezeptur B), so findet man für die erfindungsgemäße Detergensmischung ein besseres Wasch­vermögen.Miele W760, 85 g / machine, 30 ° C, 1-wash program colored laundry, loading with 3.5 kg clean laundry, 16 ° dH, triple determination.
If you compare the ABS-based formulation according to the prior art (formulation A) with the formulation containing the detergent mixture according to the invention (formulation B), the detergent mixture according to the invention has better washing power.

Anwendungsbeispiel 3:Example of use 3: Waschvermögen von Detergensmischungen aus Hydroxysulfonaten (Diol(ether)sulfonaten) und Alkylglucosiden und Vergleich mit ABSWashing power of detergent mixtures made from hydroxysulfonates (diol (ether) sulfonates) and alkyl glucosides and comparison with ABS

Die eingesetzten Substanzen hatten die im Anwendungsbeispiel 1 definierte chemische Zusammensetzung. HOS HOES5 AG ABS Remiss. 1) Remiss. 2) Gew.-% Gew.-% Gew.-% Gew.-% Gew.-% Gew.-% 100 34,0 41,6 100 0 31,9 41,7 90 10 32,8 40,8 75 25 33,7 39,2 50 50 33,0 36,5 25 75 31,4 32,2 10 90 28,3 28,6 0 100 25,7 26,7 100 0 31,9 41,7 90 10 33,1 41,2 75 25 35,4 42,3 50 50 35,9 41,6 25 75 36,4 39,8 10 90 35,4 37,2 0 100 34,3 35,5 Rezeptur: Die angegebenen Remissionsmessungen beziehen sich auf folgende builderhaltige bzw. builderfreie Rezepturen: 1) 0,5 g AS/l + 2,0 g Natriumsulfat 2) 0,5 g AS/l + 1,5 g NaTPP/Zeolith NaA (1:1) The substances used had the chemical composition defined in Application Example 1. HOS HOES5 AG SECTION Remiss. 1) Remiss. 2) % By weight % By weight % By weight % By weight % By weight % By weight 100 34.0 41.6 100 0 31.9 41.7 90 10th 32.8 40.8 75 25th 33.7 39.2 50 50 33.0 36.5 25th 75 31.4 32.2 10th 90 28.3 28.6 0 100 25.7 26.7 100 0 31.9 41.7 90 10th 33.1 41.2 75 25th 35.4 42.3 50 50 35.9 41.6 25th 75 36.4 39.8 10th 90 35.4 37.2 0 100 34.3 35.5 Recipe: The specified reflectance measurements refer to the following builder-containing or builder-free recipes: 1) 0.5 g AS / l + 2.0 g sodium sulfate 2) 0.5 g AS / l + 1.5 g NaTPP / zeolite NaA (1: 1)

Waschbedingungen:Washing conditions:

16 °dH, Flotte = 1:30, 10 Stahlkugeln Beschwerung, 30 min Waschen, 4 x 30 sec. Spülen, H-SH-PBV-Gewebe, 40 °C.
Vergleicht man das Waschvermögen nach dem Stand der Technik (ABS) mit dem Waschvermögen der erfindungsgemäßen Detergens­mischungen, so findet man insbesondere bei alkoxylierten Hy­droxysulfonaten in Gegenwart oder Abwesenheit eines Builders ein verbessertes Waschvermögen.16 ° dH, liquor = 1:30, 10 steel balls weight, 30 min washing, 4 x 30 sec. Rinsing, H-SH-PBV fabric, 40 ° C.
If one compares the washability according to the prior art (ABS) with the washability of the detergent mixtures according to the invention, an improved washability is found in particular in the case of alkoxylated hydroxysulfonates in the presence or absence of a builder.

Beispiel 1:Example 1: Biologische Abbaubarkeit im Geschlossenen FlaschentestBiodegradability in the closed bottle test

Die Abbaubarkeit von Tensiden läßt sich anhand des biochemi­schen Sauerstoffbedarfs (BSB) bei der mikrobiellen Oxidation bewerten. Dabei wird der theoretische BSBT-Wert (in %), der die Menge O₂ angibt, die zur vollständigen Oxidation der Testsub­stanz zu CO₂, H₂O, SO₄²⁻, NO₃⁻ etc. erforderlich ist, zu dem tatsächlich gefundenen Wert in Beziehung gesetzt (vgl. "Tenside Detergents" 8,4 (1971) 182).The degradability of surfactants can be assessed based on the biochemical oxygen demand (BOD) in microbial oxidation. The theoretical BOD value (in%), which indicates the amount of O₂ that is required for the complete oxidation of the test substance to CO₂, H₂O, SO₄²⁻, NO₃⁻ etc., is related to the value actually found (cf. "Tenside Detergents" 8.4 (1971) 182).

Durchgeführt wurde der Test über einen Zeitraum von 30 Tagen in einem geschlossenen System bei einer Prüfkonzentration von 2 mg AS/I (zur Testmethode vgl. "Fette Seifen Anstrm." 65 (1963) 37).The test was carried out over a period of 30 days in a closed system at a test concentration of 2 mg AS / I (for the test method see "Fette Seifen Anstrm." 65 (1963) 37).

Setzt man den unter diesen Bedingungen ermittelten BSB-Wert des ABS gleich 100 %, dann findet man für die erfindungsgemäß bean­spruchten Detergensgemische (Substanzen, wie in Anwendungsbei­spiel 1 definiert): ABS (Vergleich) = 100 % HOS : AG = 90 : 10 = 160 % HOS : AG = 50 : 50 = 140 % HOS : AG = 10 : 90 = 122 % HOES5 : AG = 90 : 10 = 155 % HOES5 : AG = 50 : 50 = 138 % HOES5 : AG = 10 : 90 = 122 % HOES10 : AG = 90 : 10 = 153 % HOES10 : AG = 50 : 50 = 137 % HOES10 : AG = 10 : 90 = 122 % Aus dem Beispiel geht hervor, daß die erfindungsgemäß bean­spruchten Detergensmischungen deutlich leichter abbaubar sind als ABS.If the BOD value of the ABS determined under these conditions is set to 100%, one finds for the detergent mixtures claimed according to the invention (substances as defined in application example 1): ABS (comparison) = 100% HOS : AG = 90: 10 = 160% HOS : AG = 50:50 = 140% HOS : AG = 10: 90 = 122% HOES5 : AG = 90: 10 = 155% HOES5 : AG = 50:50 = 138% HOES5 : AG = 10: 90 = 122% HOES10 : AG = 90: 10 = 153% HOES10 : AG = 50:50 = 137% HOES10 : AG = 10: 90 = 122% The example shows that the detergent mixtures claimed according to the invention are significantly easier to degrade than ABS.

Beispiel 2:Example 2: Hautverträgichkeit im EpidermisquelltestSkin compatibility in the epidermal swelling test

Zum Test auf Hautverträglichkeit wird eine Schweineepidermis in eine wäßrige Lösung des zu testenden Tensids gebracht und die Quellung gegenüber reinem Wasser verglichen. Dabei gilt, daß ein Tensid umso hautverträglicher ist, je geringer die Quellung ist. Erfahrungsgemäß korrelieren die über diese Methode gefun­denen Quellfaktoren für Aniontenside und aniontensidhaltige Systeme sehr gut mit Messungen der Hautverträglichkeit in vivo (vgl. J. Soc. Cosmet. Chem. Jap. 20 (1986) 17).To test for skin tolerance, a pig epidermis is placed in an aqueous solution of the surfactant to be tested and the swelling compared to pure water. The fact that the less swelling is, the more skin-compatible the surfactant is. Experience has shown that the swelling factors for anionic surfactants and systems containing anionic surfactants found using this method correlate very well with measurements of skin tolerance in vivo (cf. J. Soc. Cosmet. Chem. Jap. 20 (1986) 17).

Setzt man die Quellung, die mit einer wäßrigen 2 %igen ABS-­Lösung erreicht wird, gleich 100 %, findet man für die erfin­ dungsgemäß beanspruchten Detergensmischungen (Substanzen, wie in Anwendungsbeispiel 1 definiert): ABS (Vergleich) = 100 % HOS : AG = 90 : 10 = 11 % HOS : AG = 50 : 50 = 12 % HOS : AG = 10 : 90 = 18 % HOES5 : AG = 90 : 10 = 10 % HOES5 : AG = 50 : 50 = 14 % HOES5 : AG = 10 : 90 = 18 % HOES10 : AG = 90 : 10 = 6 % HOES10 : AG = 50 : 50 = 12 % HOES10 : AG = 10 : 90 = 18 % Man erkennt, daß die erfindungsgemäß beanspruchten Detergens­gemische deutlich hautverträglicher sind als ABS.If one sets the swelling, which is achieved with an aqueous 2% ABS solution, to 100%, one finds for the inventors Detergent mixtures claimed in accordance with the invention (substances as defined in application example 1): ABS (comparison) = 100% HOS : AG = 90: 10 = 11% HOS : AG = 50:50 = 12% HOS : AG = 10: 90 = 18% HOES5 : AG = 90: 10 = 10% HOES5 : AG = 50:50 = 14% HOES5 : AG = 10: 90 = 18% HOES10 : AG = 90: 10 = 6% HOES10 : AG = 50:50 = 12% HOES10 : AG = 10: 90 = 18% It can be seen that the detergent mixtures claimed according to the invention are significantly more skin-friendly than ABS.

Claims (7)

1. Detergensmischung, enthaltend
A) mindestens ein Alkylglykosid der allgemein Formel (I)
RO(G)x      (I)
in der
R einen aliphatischen Rest mit wenigstens 8 C-Atomen, ins­besondere den Rest eines primären Alkohols und ganz be­sonders einen Fettalkyl- oder Fettalkenyl-Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet,
G ein Symbol ist, das für eine Glykoseeinheit steht, d.h. das sich von einem reduzierenden Saccharid mit 5 oder 6 C-Atomen ableitet,
und
x für eine Zahl zwischen 1 und 10 steht,
B) ein anionisches Tensid sowie
C) übliche Hilfs- und Zusatzstoffe,
die dadurch gekennzeichnet ist, daß das anionische Tensid B) mindestens ein Hydroxysulfonat, das ganz oder überwiegend aus Verbindungen der Formel (II) oder (III)
Figure imgb0003
 oder deren Alkali-, Erdalkali- und Ammoniumsalzen zusammenge­setzt ist, wobei y und z = O oder Zahlen von 1 bis 18, p = 0, 1 oder 2 und die Summe (y + z + p) eine Zahl von 4 bis 18, x = 0 oder eine Zahl bis 30 und n eine ganze Zahl von 2 bis 4 sein kann, ist.1. Detergent mixture containing
A) at least one alkyl glycoside of the general formula (I)
RO (G) x (I)
in the
R denotes an aliphatic radical with at least 8 carbon atoms, in particular the radical of a primary alcohol and very particularly a fatty alkyl or fatty alkenyl radical with 8 to 22, preferably 12 to 18, carbon atoms,
G is a symbol which stands for a glycose unit, ie which is derived from a reducing saccharide with 5 or 6 carbon atoms,
and
x represents a number between 1 and 10,
B) an anionic surfactant as well
C) usual auxiliaries and additives,
which is characterized in that the anionic surfactant B) has at least one hydroxysulfonate which is composed entirely or predominantly of compounds of the formula (II) or (III)
Figure imgb0003
 or their alkali, alkaline earth and ammonium salts are composed, where y and z = O or numbers from 1 to 18, p = 0, 1 or 2 and the sum (y + z + p) a number from 4 to 18, x = 0 or a number up to 30 and n can be an integer from 2 to 4. 2. Detergensmischung nach Anspruch 1, dadurch gekennzeichnet, daß in dem Hydroxysulfonat der Formeln (II) und (III) die Summe (y + z + p) eine Zahl von 12 bis 18, vorzugsweise 12 bis 14, ist und x und n die oben angegebenen Bedeutungen haben.2. Detergent mixture according to claim 1, characterized in that in the hydroxysulfonate of the formulas (II) and (III) the sum (y + z + p) is a number from 12 to 18, preferably 12 to 14, and x and n are the have the meanings given above. 3. Detergensmischung nach Anspruch 1 oder 2, dadurch gekenn­zeichnet, daß in dem Hydroxysulfonat der Formeln (II) und (III) x = 0 bis 20, vorzugsweise 1 bis 10, ist und die Summe (y + z + p) und n die oben genannten Bedeutungen haben.3. Detergent mixture according to claim 1 or 2, characterized in that in the hydroxysulfonate of the formulas (II) and (III) x = 0 to 20, preferably 1 to 10, and the sum (y + z + p) and n the have the meanings given above. 4. Detergensmischung nach Ansprüchen 1 bis 3 dadurch gekenn­zeichnet, daß in dem Hydroxysulfonat der Formeln (II) und (III) n für 2 steht und die Summe (y + z + p) und x die oben angege­benen Bedeutungen haben.4. Detergent mixture according to claims 1 to 3, characterized in that in the hydroxysulfonate of the formulas (II) and (III) n is 2 and the sum (y + z + p) and x have the meanings given above. 5. Detergensmischung nach Ansprüchen 1 bis 4, dadurch gekenn­zeichnet, daß die Hydroxysulfonate der allgemeinen Formeln (I) und (III) aus Oleylalkohol oder aus oleylalkoholhaltigen Fett­alkylresten hergestellt worden sind.5. Detergent mixture according to claims 1 to 4, characterized in that the hydroxysulfonates of the general formulas (I) and (III) have been prepared from oleyl alcohol or from oleyl alcohol-containing fatty alkyl radicals. 6. Detergensmischung nach Ansprüchen 1 bis 5, dadurch gekenn­zeichnet, daß in dem Hydroxysulfonat, das ganz oder vorwiegend aus Verbindungen der Formeln (II) und (III) besteht, die Summe (y + z + p) eine Zahl von 12 bis 18, vorzugsweise 12 bis 14, x = 0 bis 20, vorzugsweise 1 bis 10 ist und n für 2 steht.6. Detergent mixture according to claims 1 to 5, characterized in that in the hydroxysulfonate, which consists wholly or predominantly of compounds of the formulas (II) and (III), the sum (y + z + p) is a number from 12 to 18, is preferably 12 to 14, x = 0 to 20, preferably 1 to 10 and n is 2. 7. Verwendung einer Detergensmischung gemäß Ansprüchen 1 bis 6 als Bestandteil von phosphatreduzierten Waschmitteln oder Reinigungsmitteln.7. Use of a detergent mixture according to claims 1 to 6 as a component of reduced phosphate detergents or cleaning agents.
EP89111881A 1988-07-07 1989-06-29 Detergent mixture containing non-ionic and anionic surfactants, and their use Expired - Lifetime EP0349906B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89111881T ATE92096T1 (en) 1988-07-07 1989-06-29 DETERGENT MIXTURE OF NONIONIC AND ANIONIC SURFACTANTS AND THEIR USE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3822997A DE3822997A1 (en) 1988-07-07 1988-07-07 DETERGENT MIXTURE FROM NON-IONIC AND ANIONIC SURFACES AND THEIR USE
DE3822997 1988-07-07

Publications (3)

Publication Number Publication Date
EP0349906A2 true EP0349906A2 (en) 1990-01-10
EP0349906A3 EP0349906A3 (en) 1990-03-14
EP0349906B1 EP0349906B1 (en) 1993-07-28

Family

ID=6358151

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89111881A Expired - Lifetime EP0349906B1 (en) 1988-07-07 1989-06-29 Detergent mixture containing non-ionic and anionic surfactants, and their use
EP89907163A Pending EP0423165A1 (en) 1988-07-07 1989-06-29 Detergent mixture of non-ionic and anionic tensides and use thereof

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP89907163A Pending EP0423165A1 (en) 1988-07-07 1989-06-29 Detergent mixture of non-ionic and anionic tensides and use thereof

Country Status (7)

Country Link
US (1) US5104585A (en)
EP (2) EP0349906B1 (en)
JP (1) JPH03505746A (en)
AT (1) ATE92096T1 (en)
DE (2) DE3822997A1 (en)
ES (1) ES2041897T3 (en)
WO (1) WO1990000592A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990008531A2 (en) * 1989-01-25 1990-08-09 Henkel Kommanditgesellschaft Auf Aktien Surface active mixtures
WO1991019777A1 (en) * 1990-06-21 1991-12-26 Henkel Kommanditgesellschaft Auf Aktien Liquid, pourable and pumpable tenside concentrate

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6042837A (en) * 1989-09-20 2000-03-28 Kalland; Terje Methods of staphylococcal enterotoxin directed cell-mediated cytotoxicity (SDCC)
US6126945A (en) * 1989-10-03 2000-10-03 Pharmacia Ab Tumor killing effects of enterotoxins, superantigens, and related compounds
US6197299B1 (en) 1990-07-20 2001-03-06 Pharmacia & Upjohn Ab Antibody conjugates
DE4029035A1 (en) * 1990-09-13 1992-03-19 Huels Chemische Werke Ag LAUNDRY DETERGENT
WO1993012806A1 (en) * 1991-12-24 1993-07-08 Amrad Corporation Limited A method for the treatment of tumours and sarcomas
US5352376A (en) * 1993-02-19 1994-10-04 Ecolab Inc. Thermoplastic compatible conveyor lubricant
DE4409321A1 (en) * 1994-03-18 1995-09-21 Henkel Kgaa Low m.pt fatty acid isethionate-based detergent mixt.
US5516747A (en) * 1994-04-18 1996-05-14 Henkel Corporation Pesticidal surfactant mixtures comprising alkyl polyglycosides and alkyl naphthalene sulfonates
FR2723858B1 (en) * 1994-08-30 1997-01-10 Ard Sa PROCESS FOR THE PREPARATION OF SURFACTANTS FROM WHEAT BY-PRODUCTS AND NOVEL ALKYL XYLOSIDES
DE19524973A1 (en) * 1995-07-08 1997-01-09 Huels Chemische Werke Ag Acid-cleavable surfactants based on alkyl glycosides
SE9601245D0 (en) 1996-03-29 1996-03-29 Pharmacia Ab Chimeric superantigens and their use
US6786223B2 (en) * 2001-10-11 2004-09-07 S. C. Johnson & Son, Inc. Hard surface cleaners which provide improved fragrance retention properties to hard surfaces
US9926486B2 (en) 2014-03-31 2018-03-27 Ecolab Usa Inc. Surfactant assisted oil recovery using alcohol ether sulfonates and cationic surfactants
WO2016140962A1 (en) 2015-03-03 2016-09-09 Ecolab Usa Inc. Foam assisted liquid removal using alcohol ether sulfonates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070074A2 (en) * 1981-07-13 1983-01-19 THE PROCTER &amp; GAMBLE COMPANY Foaming surfactant compositions
WO1986002943A1 (en) * 1984-11-06 1986-05-22 A.E. Staley Manufacturing Company Monoglycosides as viscosity modifiers in detergents

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4565647B1 (en) * 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US4536318A (en) * 1982-04-26 1985-08-20 The Procter & Gamble Company Foaming surfactant compositions
US4663069A (en) * 1982-04-26 1987-05-05 The Procter & Gamble Company Light-duty liquid detergent and shampoo compositions
US4732696A (en) * 1984-11-06 1988-03-22 A. E. Staley Manufacturing Company Monoglycosides as viscosity modifiers in detergents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070074A2 (en) * 1981-07-13 1983-01-19 THE PROCTER &amp; GAMBLE COMPANY Foaming surfactant compositions
WO1986002943A1 (en) * 1984-11-06 1986-05-22 A.E. Staley Manufacturing Company Monoglycosides as viscosity modifiers in detergents

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990008531A2 (en) * 1989-01-25 1990-08-09 Henkel Kommanditgesellschaft Auf Aktien Surface active mixtures
WO1990008531A3 (en) * 1989-01-25 1990-11-01 Henkel Kgaa Surface active mixtures
WO1991019777A1 (en) * 1990-06-21 1991-12-26 Henkel Kommanditgesellschaft Auf Aktien Liquid, pourable and pumpable tenside concentrate

Also Published As

Publication number Publication date
DE58905025D1 (en) 1993-09-02
EP0349906A3 (en) 1990-03-14
ES2041897T3 (en) 1993-12-01
DE3822997A1 (en) 1990-01-18
ATE92096T1 (en) 1993-08-15
EP0349906B1 (en) 1993-07-28
WO1990000592A1 (en) 1990-01-25
US5104585A (en) 1992-04-14
EP0423165A1 (en) 1991-04-24
JPH03505746A (en) 1991-12-12

Similar Documents

Publication Publication Date Title
EP0349906B1 (en) Detergent mixture containing non-ionic and anionic surfactants, and their use
EP0712436B1 (en) Low-foaming washing or cleaning agents
EP0716680B1 (en) Use of aqueous detergent mixtures
EP0743975B1 (en) Hard surface cleaning agent
DE4029035A1 (en) LAUNDRY DETERGENT
DE4243643C1 (en)
DE4017922A1 (en) LIQUID ALKYL GLYCOSIDE-CONTAINING SURFACTANT
EP0370312A2 (en) Washing and cleaning agent containing a surfactant mixture of alkyl glycosides and anionic surfactants
EP0553099B1 (en) Liquid washing agent with increased viscosity
DE4026809A1 (en) Liq. aq. washing compsn. - contains anionic surfactant, nonionic surfactant and alkyl poly:glycoside as thickener, improving washing
EP0490040B1 (en) Liquid detergent
DE4011487A1 (en) TENSID MIXTURE FOR USE IN WASHING AND CLEANING AGENTS
EP0750034B1 (en) Storage stable, concentrated surfactant composition based on alkylglycosides
EP0518881B1 (en) Method for sulphonation of mixtures containing alkyl glycosides
WO1993019150A1 (en) Low-foaming surface-active mixture
CH635614A5 (en) Liquid detergent and process for its preparation
EP0403948A1 (en) Liquid detergent
EP0788537B1 (en) Aqueous hand washing-up liquid
DE2320527C3 (en) Detergent containing agent
CH676604A5 (en)
DE19534269A1 (en) Aq. surfactant preparation
DE3905671C2 (en) Detergent granules suitable for the production of aqueous concentrates
DE4041172A1 (en) LIQUID SOAP PREPARATION
EP0345490A2 (en) Mixtures of phosphoric acid partial esters, process for their preparation, their use and washing and cleaning agents containing them
DE19619956A1 (en) Skin friendly washing up liquids

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): ES GR

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): ES GR

17P Request for examination filed

Effective date: 19900912

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL

XX Miscellaneous (additional remarks)

Free format text: VERBUNDEN MIT 89907163.3/0423165 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) DURCH ENTSCHEIDUNG VOM 04.11.91.

17Q First examination report despatched

Effective date: 19920910

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19930728

REF Corresponds to:

Ref document number: 92096

Country of ref document: AT

Date of ref document: 19930815

Kind code of ref document: T

XX Miscellaneous (additional remarks)

Free format text: VERBUNDEN MIT 89907163.3/0423165 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) DURCH ENTSCHEIDUNG VOM 04.11.91.

ET Fr: translation filed
REF Corresponds to:

Ref document number: 58905025

Country of ref document: DE

Date of ref document: 19930902

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19931029

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2041897

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940629

Ref country code: AT

Effective date: 19940629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19940630

Ref country code: ES

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19940630

Ref country code: CH

Effective date: 19940630

Ref country code: BE

Effective date: 19940630

26N No opposition filed
BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19940630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19950101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19950301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19991007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050629