EP0944697B1 - Water-free mixtures of surface-active agents - Google Patents
Water-free mixtures of surface-active agents Download PDFInfo
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- EP0944697B1 EP0944697B1 EP97951883A EP97951883A EP0944697B1 EP 0944697 B1 EP0944697 B1 EP 0944697B1 EP 97951883 A EP97951883 A EP 97951883A EP 97951883 A EP97951883 A EP 97951883A EP 0944697 B1 EP0944697 B1 EP 0944697B1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
Definitions
- the invention relates to anhydrous surfactant mixtures having a reduced irritant potential selected fatty alcohol sulfates and alkylbenzenesulfonates in selected mixing ratios as well as their use for the production of surface-active agents.
- Fatty alcohol sulfates are because of their good application properties and their excellent Ecological compatibility represents anionic surfactants, which are increasingly used in manufacturing of detergents, dishwashing detergents and cleaning agents are becoming increasingly important.
- DE-C2 2857292 discloses detergent preparations containing alkyl sulfates and alkylbenzenesulfonates, which contain selected polymers as soil repellants.
- free-flowing surfactant granules are also obtained by 33 to 55% by weight of a liquid, acidic anionic surfactant mixture (for example alkylbenzenesulfonic acid or alkylsulfuric acid half-ester) with 20 to 50% by weight of zeolite and 2 to 25 % By weight of alkali metal carbonate mixes.
- a liquid, acidic anionic surfactant mixture for example alkylbenzenesulfonic acid or alkylsulfuric acid half-ester
- the complex object of the invention was, however, to develop new anhydrous surfactant mixtures To make available, which improved at the same time by a significantly reduced potential for irritation Characterize pourability and solubility.
- the preparations according to the invention are synergistic Decrease in the potential for irritation with equally good application properties, in particular have improved flowability and solubility in cold water.
- Fatty alcohol sulfates which form component (a) are known anionic surfactants and are usually prepared by reacting fatty alcohols with sulfating agents such as sulfuric acid, oleum, chlorosulfonic acid and in particular gaseous sulfur trioxide. The resulting sulfuric acid semiesters are then neutralized with suitable bases.
- sulfating agents such as sulfuric acid, oleum, chlorosulfonic acid and in particular gaseous sulfur trioxide.
- the resulting sulfuric acid semiesters are then neutralized with suitable bases.
- the fatty alcohol sulfates of the formula (I) are sulfation products of fatty alcohols having 16 to 18 carbon atoms. Typical examples are the sulfates of cetyl alcohol and stearyl alcohol.
- Technical fatty alcohol cuts such as, for example, tallow alcohol are preferred, which may have shorter or longer-chain homologs in minor amounts.
- Alkylbenzenesulfonates which form component (b) are also known anionic surfactants, which are usually prepared by core sulfonation of linear alkylbenzenes and then in a more suitable manner Way neutralized. Typical examples are sulfonation products of decylbenzene, dodecylbenzene and tetradecylbenzene and their technical mixtures, which are in the form of their sodium or Potassium salts are used.
- the mixing of the components is not critical. In the simplest case, those after the Neutralization of the crude sulfonation resulting aqueous pastes for example in one Schugi mixer mixed and processed into an anhydrous, lumpy product at the same time. In in the same way, dry-neutralized or spray-dried or steam-dried powders of both components are mixed. It is also possible to mix in an appropriate situ by co-sulfonation of fatty alcohols and alkylbenzenes, subsequent neutralization and if necessary Manufacture drying. Finally, the acid sulfonation products can also work together neutralized and then processed further.
- a tower powder produced according to conventional processes which besides typical detergent ingredients already contain one of the two anionic surfactant components can.
- the powder is placed in a mixer and continuously with at least one of the two Anion surfactant components, preferably mixed in the form of an aqueous paste, mixed, dried and optionally further mechanically solidified.
- the result is a dry detergent powder, granules or extrudates with excellent detergent properties, high dissolution rate and reduced potential for irritation.
- the surfactant mixtures according to the invention are not only distinguished by very good detergent properties, but above all also through a synergistic reduced stimulus potential, i.e. improved skin and eye mucosa tolerance. They are therefore suitable for production of detergents, dishwashing detergents and cleaning agents, especially solid detergents, in which they are used in quantities from 1 to 90, preferably 10 to 50% by weight, based on the composition, can be present.
- Typical examples of detergents, dishwashing detergents and cleaning agents which contain the water-free according to the invention
- Mixtures of surfactants can include liquid to pasty fabric softeners, hand dishwashing detergents, machine dishwashing detergent, rinse aid and universal, household and sanitary cleaner as well as powdered or granulated universal detergents.
- the agents can contain other typical ingredients such as builders, enzymes, enzyme stabilizers, bleaches, optical brighteners, Thickeners, soil repellants, foam inhibitors, solubilizers, inorganic salts as well Have fragrances and dyes.
- Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H 2 O 2 -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
- the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent.
- thickeners which can be used are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
- the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% maleic acid.
- the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
- Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are particularly suitable. Examples of these are polymers obtainable under the name Carbopol® 940 and 941.
- the crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight.
- Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentes are preferably used, their proportion can be about 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
- the agents can contain further enzyme stabilizers .
- enzyme stabilizers 0.5 to 1% by weight sodium formate can be used.
- proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
- boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
- Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes.
- the free-flowing properties of the products were subjectively determined in the clump test; (+) means high flowability, (-) restricted flowability and (-) high tendency to clump.
- (+) means high flowability, (-) restricted flowability and (-) high tendency to clump.
- 10 g of the anhydrous formulations were dissolved or dispersed in 100 ml of water (30 ° C., 16 ° d). After 120 s, the solutions or dispersions were filtered and the residue was dried and weighed out. The information is given in% -rel based on the amount used.
- the irritation potential was determined in accordance with OECD Method No.404 and the EEC Directive 84/449 EEC, Pt.B.4. The specified stimulus sum scores were formed from the stimulus scores obtained after 24, 48 and 72 hours.
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Description
Die Erfindung betrifft wasserfreie Tensidgemische mit einem verminderten Reizpotential, enthaltend ausgewählte Fettalkoholsulfate und Alkylbenzolsulfonate in ausgewählten Mischungsverhältnissen sowie deren Verwendung zur Herstellung von oberflächenaktiven Mitteln.The invention relates to anhydrous surfactant mixtures having a reduced irritant potential selected fatty alcohol sulfates and alkylbenzenesulfonates in selected mixing ratios as well as their use for the production of surface-active agents.
Fettalkoholsulfate stellen wegen ihren guten anwendungstechnischen Eigenschaften und ihrer ausgezeichneten ökologischen Verträglichkeit Aniontenside dar, die in zunehmendem Maße für die Herstellung von Wasch-, Spül- und Reinigungsmitteln an Bedeutung gewinnen.Fatty alcohol sulfates are because of their good application properties and their excellent Ecological compatibility represents anionic surfactants, which are increasingly used in manufacturing of detergents, dishwashing detergents and cleaning agents are becoming increasingly important.
Für Lagerung und Transport sind naturgemäß möglichst hoch konzentrierte wäßrige bzw. wasserfreie, feste Anbietungsformen anionischer Tenside erwünscht. Diese haben jedoch den Nachteil, im Gegensatz zu den auf die Anwendungskonzentration verdünnten Produkten als stark haut- bzw. schleimhautreizend gekennzeichnet werden zu müssen, was im Hinblick auf das Inverkehrbringen erhöhte Anforderungen an die Arbeitssicherheit stellt. Ein weiterer Nachteil besteht darin, daß Zubereitungen des Stands der Technik weder eine ausreichende Rieselfähigkeit noch Löslichkeit, insbesondere in kaltem Wasser, zeigen.For storage and transport, naturally highly concentrated aqueous or water-free, solid forms of anionic surfactants desired. However, these have the disadvantage, in contrast to the products diluted to the application concentration as strongly irritating to the skin or mucous membranes need to be labeled, which increases requirements with regard to placing on the market to occupational safety. Another disadvantage is that preparations of the State of the art neither sufficient flowability nor solubility, especially in cold Water, show.
Aus der DE-C2 2857292 sind Waschmittelzubereitungen mit einem Gehalt an Alkylsulfaten und Alkylbenzolsulfonaten bekannt, die ausgewählte Polymere als soil repellants enthalten. Gemäß der internationalen Patentanmeldung WO 95/02036 (Unilever) werden ferner rieselfähige Tensidgranulate erhalten, indem man 33 bis 55 Gew.-% einer flüssigen, sauren Aniontensidmischung (z.B. Alkylbenzolsulfonsäure oder Alkylschwefelsäurehalbester) mit 20 bis 50 Gew.-% Zeolith und 2 bis 25 Gew.-% Alkalimetallcarbonat mischt. DE-C2 2857292 discloses detergent preparations containing alkyl sulfates and alkylbenzenesulfonates, which contain selected polymers as soil repellants. According to international patent application WO 95/02036 (Unilever), free-flowing surfactant granules are also obtained by 33 to 55% by weight of a liquid, acidic anionic surfactant mixture (for example alkylbenzenesulfonic acid or alkylsulfuric acid half-ester) with 20 to 50% by weight of zeolite and 2 to 25 % By weight of alkali metal carbonate mixes.
Die komplexe Aufgabe der Erfindung hat indes darin bestanden, neue wasserfreie Tensidgemische zur Verfügung zu stellen, die sich gleichzeitig durch ein signifikant vermindertes Reizpotential, verbesserte Rieselfähigkeit und Löslichkeit auszeichnen.The complex object of the invention was, however, to develop new anhydrous surfactant mixtures To make available, which improved at the same time by a significantly reduced potential for irritation Characterize pourability and solubility.
Gegenstand der Erfindung sind wasserfreie Tensidgemische, enthaltend
Überraschenderweise wurde gefunden, daß die erfindungsgemäßen Zubereitungen eine synergistische Abnahme des Reizpotentials bei gleichermaßen sehr guten anwendungstechnischen Eigenschaften, insbesondere verbesserter Rieselfähigkeit und Löslichkeit in kaltem Wasser aufweisen.Surprisingly, it has been found that the preparations according to the invention are synergistic Decrease in the potential for irritation with equally good application properties, in particular have improved flowability and solubility in cold water.
Fettalkoholsulfate, die die Komponente (a) bilden, stellen bekannte anionische Tenside dar und werden üblicherweise durch Umsetzung von Fettalkoholen mit Sulfatierungsmitteln wie Schwefelsäure, Oleum, Chlorsulfonsäure und insbesondere gasförmigem Schwefeltrioxid hergestellt. Die resultierenden Schwefelsäurehalbester werden anschließend mit geeigneten Basen neutralisiert. Im Sinne der Erfindung sind unter den Fettalkoholsulfaten der Formel (I) Sulfatierungsprodukte von Fettalkoholen mit 16 bis 18 Kohlenstoffatomen zu verstehen. Typische Beispiele sind die Sulfate von Cetylalkohol und Stearylalkohol. Vorzugsweise kommen technische Fettalkoholschnitte wie beispielsweise Talgalkohol in Betracht, die in untergeordneten Mengen noch kürzer- oder längerkettige Homologe aufweisen können. Es ist ferner möglich, technische Fettalkoholschnitte in solcher Weise abzumischen, daß ein Alkoholgemisch mit einem Schwerpunkt der C-Kettenverteilung im Bereich von 16 bis 18 Kohlenstoffatomen resultiert. Dies ist beispielsweise dann vorteilhaft, wenn man den Anteil an pflanzlichen Alkoholen im Gemisch möglichst hoch einstellen will.Fatty alcohol sulfates which form component (a) are known anionic surfactants and are usually prepared by reacting fatty alcohols with sulfating agents such as sulfuric acid, oleum, chlorosulfonic acid and in particular gaseous sulfur trioxide. The resulting sulfuric acid semiesters are then neutralized with suitable bases. For the purposes of the invention, the fatty alcohol sulfates of the formula (I) are sulfation products of fatty alcohols having 16 to 18 carbon atoms. Typical examples are the sulfates of cetyl alcohol and stearyl alcohol. Technical fatty alcohol cuts such as, for example, tallow alcohol are preferred, which may have shorter or longer-chain homologs in minor amounts. It is also possible to mix technical fatty alcohol cuts in such a way that an alcohol mixture with a focus on the C chain distribution in the range from 16 to 18 carbon atoms results. This is advantageous, for example, if you want to set the proportion of vegetable alcohols in the mixture as high as possible.
Auch Alkylbenzolsulfonate, die die Komponente (b) bilden, stellen bekannte anionische Tenside dar, die man üblicherweise durch Kernsulfonierung von linearen Alkylbenzolen herstellt und dann in geeigneter Weise neutralisiert. Typische Beispiele sind Sulfonierungsprodukte von Decylbenzol, Dodecylbenzol und Tetradecylbenzol sowie deren technische Mischungen, die in Form ihrer Natrium- oder Kaliumsalze eingesetzt werden.Alkylbenzenesulfonates which form component (b) are also known anionic surfactants, which are usually prepared by core sulfonation of linear alkylbenzenes and then in a more suitable manner Way neutralized. Typical examples are sulfonation products of decylbenzene, dodecylbenzene and tetradecylbenzene and their technical mixtures, which are in the form of their sodium or Potassium salts are used.
Das Vermischen der Komponenten ist unkritisch. Im einfachsten Fall werden die nach der Neutralisation der rohen Sulfierprodukte resultierenden wäßrigen Pasten beispielsweise in einem Schugi-Mischer vermischt und gleichzeitig zu einem wasserfreien, stückigen Produkt verarbeitet. In gleicher Weise können auch trockenneutralisierte bzw. sprüh- oder heißdampfgetrockente Pulver der beiden Komponenten ausgemischt werden. Weiterhin ist es möglich, eine entsprechende Mischung in situ durch Co-Sulfierung von Fettalkoholen und Alkylbenzolen, nachfolgende Neutralisation und gegebenenfalls Trocknung herzustellen. Schließlich können die sauren Sulfierprodukte auch gemeinsam neutralisiert und dann weiterverarbeitet werden. In einer bevorzugten Ausführungsform der Erfindung geht man von einem nach konventionellen Verfahren hergestelltem Turmpulver aus, das neben typischen Waschmittelbestandteilen auch bereits eine der beiden Aniontensidkomponenten enthalten kann. Das Pulver wird in einem Mischer vorgelegt und kontinuierlich mit mindestens einer der beiden Aniontensidkomponenten, vorzugsweise in Form einer wäßrigen Paste versetzt, gemischt, getrocknet und gegebenenfalls weiter mechanisch verfestigt. Es resultiert ein trockenes Waschmittelpulver, - granulat oder -extrudat mit ausgezeichneten Detergenseigenschaften, hoher Auflösungsgeschwindigkeit und verminderten Reizpotential. In einer bevorzugten Ausführungsform der vorliegenden Erfindung können wäßrige Pasten mit einem Aktivsubstanzgehalt von 10 bis 60, vorzugsweise 30 bis 50 Gew.-% in einem sogenannten Flashdryer, wie er von der VRV/IT erhältlich ist, getrocknet und gleichzeitig granuliert werden.The mixing of the components is not critical. In the simplest case, those after the Neutralization of the crude sulfonation resulting aqueous pastes for example in one Schugi mixer mixed and processed into an anhydrous, lumpy product at the same time. In in the same way, dry-neutralized or spray-dried or steam-dried powders of both components are mixed. It is also possible to mix in an appropriate situ by co-sulfonation of fatty alcohols and alkylbenzenes, subsequent neutralization and if necessary Manufacture drying. Finally, the acid sulfonation products can also work together neutralized and then processed further. In a preferred embodiment of the invention one assumes a tower powder produced according to conventional processes, which besides typical detergent ingredients already contain one of the two anionic surfactant components can. The powder is placed in a mixer and continuously with at least one of the two Anion surfactant components, preferably mixed in the form of an aqueous paste, mixed, dried and optionally further mechanically solidified. The result is a dry detergent powder, granules or extrudates with excellent detergent properties, high dissolution rate and reduced potential for irritation. In a preferred embodiment of the present invention can aqueous pastes with an active substance content of 10 to 60, preferably 30 to 50 wt .-% in a so-called flash dryer, as it is available from VRV / IT, dried and simultaneously be granulated.
Die erfindungsgemäßen Tensidgemische zeichnen sich nicht nur durch sehr gute Detergenseigenschaften, sondern vor allem auch durch ein in synergistischer Weise vermindertes Reizpotential, d.h. verbesserte Haut- und Augenschleimhautverträglichkeit aus. Sie eignen sich daher zur Herstellung von Wasch-, Spül- und Reinigungsmitteln, insbesondere festen Waschmitteln, in denen sie in Mengen von 1 bis 90, vorzugsweise 10 bis 50 Gew.-% - bezogen auf die Mittel - enthalten sein können.The surfactant mixtures according to the invention are not only distinguished by very good detergent properties, but above all also through a synergistic reduced stimulus potential, i.e. improved skin and eye mucosa tolerance. They are therefore suitable for production of detergents, dishwashing detergents and cleaning agents, especially solid detergents, in which they are used in quantities from 1 to 90, preferably 10 to 50% by weight, based on the composition, can be present.
Typische Beispiele für Wasch-, Spül- und Reinigungsmittel, die die erfindungsgemäßen wasserfreien Tensidgemische enthalten können, sind flüssige bis pastöse Textilweichspülmittel, Handgeschirrspülmittel, maschinelle Geschirrspülmittel, Klarspülmittel sowie Universal-, Haushalts- und Sanitärreiniger sowie pulverförmige bzw. granulierte Universalwaschmittel. Die Mittel können weitere typische Inhaltsstoffe wie beispielsweise Builder, Enzyme, Enzymstabilisatoren, Bleichmittel, optische Aufheller, Verdickungsmittel, Soil repellants, Schauminhibitoren, Lösungsvermittler, anorganische Salze sowie Duft- und Farbstoffe aufweisen.Typical examples of detergents, dishwashing detergents and cleaning agents which contain the water-free according to the invention Mixtures of surfactants can include liquid to pasty fabric softeners, hand dishwashing detergents, machine dishwashing detergent, rinse aid and universal, household and sanitary cleaner as well as powdered or granulated universal detergents. The agents can contain other typical ingredients such as builders, enzymes, enzyme stabilizers, bleaches, optical brighteners, Thickeners, soil repellants, foam inhibitors, solubilizers, inorganic salts as well Have fragrances and dyes.
Geeignete Builder sind Zeolithe, Schichtsilicate, Phosphate sowie Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Citronensäure sowie anorganische Phosphonsäuren.Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids.
Unter den als Peroxy-Bleichmittel dienenden Verbindungen haben das Natriumperborat-Tetrahydrat und das Natriumperborat-Monohydrat eine besondere Bedeutung. Weitere Bleichmittel sind beispielsweise Peroxycarbonat, Citratperhydrate sowie H2O2-liefernde persaure Salze der Persäuren wie Perbenzoate, Peroxyphthalate oder Diperoxydodecandisäure. Sie werden üblicherweise in Mengen von 8 bis 25 Gew.-% eingesetzt. Bevorzugt ist der Einsatz von Natriumperborat-Monohydrat in Mengen von 10 bis 20 Gew.-% und insbesondere von 10 bis 15 Gew.-%. Durch seine Fähigkeit, unter Ausbildung des Tetrahydrats freies Wasser binden zu können , trägt es zur Erhöhung der Stabilität des Mittels bei.Among the compounds serving as peroxy bleaching agents , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H 2 O 2 -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent.
Als Verdickungsmittel können beispielsweise gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, die vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-, Kalium-, Aluminium-, Magnesium- und Titanstearate oder die Natrium- und/oder Kaliumsalze der Behensäure, sowie weitere polymere Verbindungen eingesetzt werden. Zu den letzten gehören bevorzugt Polyvinylpyrrolidon, Urethane und die Salze polymerer Polycarboxylate, beispielsweise homopolymerer oder copolymerer Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 bis 10% Maleinsäure. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100000, die der Copolymeren zwischen 2000 und 200000, vorzugsweise zwischen 50000 bis 120000, bezogen auf die freie Säure. Insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1% eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb 1000000 besitzen Beispiele hierfür sind unter dem Namen Carbopol® 940 und 941 erhältliche Polymere. Die quervernetzten Polyacrylate werden vorzugsweise in Mengen nicht über 1 Gew.-% besonders bevorzugt in Mengen von 0,2 bis 0,7 Gew.-% eingesetzt. Examples of thickeners which can be used are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are particularly suitable. Examples of these are polymers obtainable under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipase, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus lichenformis und Strptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentes gewonnen werden, eingesetzt, Ihr Anteil kann etwa 0,2 bis 2 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsorbiert oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentes are preferably used, their proportion can be about 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
Zusätzlich zu mono- und polyfunktionellen Alkoholen und Phosphonaten können die Mittel weitere Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Calciumgehalt von vorzugsweise etwa 1,2 Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B4O7).In addition to mono- and polyfunctional alcohols and phosphonates, the agents can contain further enzyme stabilizers . For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
Beim Einsatz im maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Geeignete Schauminhibitoren enthalten beispielsweise bekannte Organopolysiloxane, Paraffine oder Wachse. When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes.
Die Rieselfähigkeit der Produkte wurde subjektiv im Klumptest bestimmt; dabei bedeutet (+) hohe Rieselfähigkeit,
(-) eingeschränkte Rieselfähigkeit und (--) hohe Tendenz zur Verklumpung. Zur Bestimmung
der Löslichkeit wurden 10 g der wasserfreien Rezepturen in 100 ml Wasser (30°C, 16°d) gelöst
bzw. dispergiert. Nach 120 s wurden die Lösungen bzw. Dispersionen filtriert und der Rückstand
getrocknet und ausgewogen. Die Angabe erfolgt in %-rel bezogen auf die eingesetzte Menge. Die
Bestimmung des Reizpotentials erfolgte gemäß der OECD-Methode No.404 und der EEC Directive
84/449 EEC, Pt.B.4. Die angegebenen Reizsummenscores wurden aus den nach 24, 48 und 72 Stunden
erhaltenen Reizscores gebildet. Dabei wurde der im Vergleichsversuch V1 ermittelte Reizsummenscore
für ein 100 %iges C16/18-Talgalkoholsulfat-Natriumsalz zu 100 % gesetzt und die in den übrigen
Versuchen erhaltenen Reizsummenscores zu diesem ins Verhältnis gesetzt. Die Ergebnisse sind in Tabelle
1 zusammengefaßt. Die Rezepturen 1 bis 4 sind erfindungsgemäß, die Rezepturen V1 bis V4 dienen
dem Vergleich.
Claims (4)
- A water free surfactant composition comprising:(a) a fatty alcohol sulfate corresponding to the formula (I)(b) an alkyl benzenesulfonate corresponding to the formula (II)
- The surfactant composition of claim 1 wherein the weight ratio of (a) to (b) is from 60:40 to 85:15.
- The surfactant composition of claim 1 wherein the weight ratio of (a) to (b) is from 75:25 to 80:20.
- 4. Use of surfactant compositions of claim 1 for the preparation of laundry detergents, dishwashing detergents and cleaners.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19648014 | 1996-11-20 | ||
| DE19648014A DE19648014C2 (en) | 1996-11-20 | 1996-11-20 | Anhydrous surfactant mixtures |
| PCT/EP1997/006273 WO1998022561A2 (en) | 1996-11-20 | 1997-11-11 | Water-free surface-active agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0944697A2 EP0944697A2 (en) | 1999-09-29 |
| EP0944697B1 true EP0944697B1 (en) | 2001-10-17 |
Family
ID=7812238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97951883A Expired - Lifetime EP0944697B1 (en) | 1996-11-20 | 1997-11-11 | Water-free mixtures of surface-active agents |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6165961A (en) |
| EP (1) | EP0944697B1 (en) |
| DE (2) | DE19648014C2 (en) |
| ES (1) | ES2166106T3 (en) |
| WO (1) | WO1998022561A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328597A (en) * | 1998-09-25 | 2001-12-26 | 宝洁公司 | Granules detergents |
| WO2007092580A2 (en) * | 2006-02-08 | 2007-08-16 | Phibro-Tech Inc. | Biocidal azole emulsion concentrates having high active ingredient content |
| US8933131B2 (en) | 2010-01-12 | 2015-01-13 | The Procter & Gamble Company | Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same |
| CN106715663A (en) | 2014-09-08 | 2017-05-24 | 宝洁公司 | Detergent compositions containing a branched surfactant |
| CN107001984B (en) | 2014-09-08 | 2019-11-12 | 宝洁公司 | Detergent composition comprising branched surfactants |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1317465A (en) * | 1969-07-07 | 1973-05-16 | Sterling Drug Inc | Process for drying and grinding fluorescent whitening agents |
| US3703772A (en) * | 1971-07-27 | 1972-11-28 | Colgate Palmolive Co | Drying of detergents |
| DE2226988A1 (en) * | 1972-06-02 | 1973-12-20 | Henkel & Cie Gmbh | DISHWASHER AND CLEANING AGENTS |
| US4116885A (en) * | 1977-09-23 | 1978-09-26 | The Procter & Gamble Company | Anionic surfactant-containing detergent compositions having soil-release properties |
| US4715979A (en) * | 1985-10-09 | 1987-12-29 | The Procter & Gamble Company | Granular detergent compositions having improved solubility |
| GB9012612D0 (en) * | 1990-06-06 | 1990-07-25 | Unilever Plc | Detergents compositions |
| US5066425A (en) * | 1990-07-16 | 1991-11-19 | The Procter & Gamble Company | Formation of high active detergent particles |
| DE4124701A1 (en) * | 1991-07-25 | 1993-01-28 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED |
| EP0560001B1 (en) * | 1992-03-10 | 1999-05-19 | The Procter & Gamble Company | High active detergent pastes |
| GB9313878D0 (en) * | 1993-07-05 | 1993-08-18 | Unilever Plc | Detergent composition or component containing anionic surfactant and process for its preparation |
| DE4332373C2 (en) * | 1993-09-23 | 2003-03-13 | Cognis Deutschland Gmbh | Anhydrous detergent mixtures |
| DE4415369C1 (en) * | 1994-05-02 | 1995-08-31 | Henkel Kgaa | Heterogeneous surfactant granulate useful in washing powder and detergent |
| DE4432365A1 (en) * | 1994-09-12 | 1996-03-14 | Henkel Kgaa | Anhydrous surfactant mixtures |
| DE19510099C1 (en) * | 1995-03-20 | 1996-08-22 | Henkel Kgaa | Anhydrous fatty alcohol sulphate surfactant mixts. for solid detergents show reduced skin initiation |
-
1996
- 1996-11-20 DE DE19648014A patent/DE19648014C2/en not_active Expired - Fee Related
-
1997
- 1997-11-11 DE DE59705005T patent/DE59705005D1/en not_active Expired - Lifetime
- 1997-11-11 US US09/308,539 patent/US6165961A/en not_active Expired - Lifetime
- 1997-11-11 EP EP97951883A patent/EP0944697B1/en not_active Expired - Lifetime
- 1997-11-11 ES ES97951883T patent/ES2166106T3/en not_active Expired - Lifetime
- 1997-11-11 WO PCT/EP1997/006273 patent/WO1998022561A2/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| DE19648014C2 (en) | 2002-09-19 |
| US6165961A (en) | 2000-12-26 |
| WO1998022561A3 (en) | 1998-10-15 |
| DE19648014A1 (en) | 1998-06-04 |
| EP0944697A2 (en) | 1999-09-29 |
| WO1998022561A2 (en) | 1998-05-28 |
| ES2166106T3 (en) | 2002-04-01 |
| DE59705005D1 (en) | 2001-11-22 |
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