EP0201016B1 - Builder-free liquid detergents with softening properties - Google Patents

Builder-free liquid detergents with softening properties Download PDF

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Publication number
EP0201016B1
EP0201016B1 EP86105800A EP86105800A EP0201016B1 EP 0201016 B1 EP0201016 B1 EP 0201016B1 EP 86105800 A EP86105800 A EP 86105800A EP 86105800 A EP86105800 A EP 86105800A EP 0201016 B1 EP0201016 B1 EP 0201016B1
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EP
European Patent Office
Prior art keywords
weight
component
acid
detergent
fatty acids
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EP86105800A
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German (de)
French (fr)
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EP0201016A2 (en
EP0201016A3 (en
Inventor
Karl Schwadtke
Eduard Dr. Smulders
Hans Dr. Andree
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE19853516091 external-priority patent/DE3516091A1/en
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Priority to AT86105800T priority Critical patent/ATE49608T1/en
Publication of EP0201016A2 publication Critical patent/EP0201016A2/en
Publication of EP0201016A3 publication Critical patent/EP0201016A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to a skeletal salt-free, liquid detergent concentrate which, due to its surfactant composition in combination with specially selected fatty acid diethanolamides, has textile-softening and grip-improving properties, so that the textiles washed therewith do not require any aftertreatment with a special softening agent.
  • conditioning agents which, in addition to quaternary ammonium salts with 2 long-chain alkyl radicals, additionally contain fatty acid monoethanolamides and their mixtures with fatty acid diethanolamides in which the fatty acids have 12 to 18 carbon atoms and are preferably derived from tallow fatty acids, which are known to have high proportions contain stearic acid.
  • the problem of how such compounds behave or can be used in detergent-containing detergents is not addressed in these publications. Furthermore, it has been shown that the stearic acid derivatives cannot be used in an effective amount in storage-stable liquid detergents.
  • liquid detergent formulations which have more or less large contents of fatty acid mono- or diethanolamides. These are always those alkanolamides which are derived from fatty acid mixtures with a high proportion of G2-COs fatty acids, for example coconut fatty acids. These alkanolamides are said to increase washing and foaming power or to improve skin tolerance. These remedies do not have an aviva effect.
  • Such agents are those according to DE-A 1 047 973, DE-A 2 022 064, DE-A 2 703 998 (FR-A 2 378 852, US-A 4 153 570), DE-A 2 819 455 , DE-A 3 022 767, DE-A 3 161 222, EP-A 38 101, US-A 2 861 956, US-A 2 943 058.
  • the agent according to the invention described below is suitable for avoiding the deficiencies mentioned.
  • the invention relates to a liquid detergent containing (a) sodium alkylbenzenesulfonate with 10 to 14 carbon atoms in the linear alkyl group, (b) water-soluble, ethoxylated alcohols with 12 to 18 carbon atoms in the hydrocarbon radical and 5 to 10 glycol ether groups, (c ) a water-soluble soap derived from saturated and / or unsaturated fatty acids with 12 to 18 carbon atoms, (d) fatty acid diethanolamide, (e) sequestering agents from the class of polycarboxylic acids and polyphosphonic acids, (f) water-miscible organic solvents and water, thereby characterized in that the proportion of component (a) 5 to 15 wt .-%, component (b) 7 to 20 wt .-%, component (c), based on fatty acid, 6 to 16 wt .-%, the Component (d) is 7 to 15% by weight, component (e) is 0.2 to 3% by weight and component (f) is
  • the proportion of the linear sodium alkylbenzenesulfonate (a) is 5 to 15% by weight, preferably 6 to 10% by weight. Dodecylbenzenesulfonate is preferably used.
  • Suitable nonionic ethoxylated alcohols are fatty alcohols or oxo alcohols with 12 to 18, preferably 12 to 16, carbon atoms which are methyl-branched in the 2-position.
  • the number of attached ethylene oxide groups (EO) is 5 to 10.
  • Ethoxylated alcohols whose HLB value is 9 to 14, in particular 11 to 13.5, have proven to be very suitable. Examples of this are ethoxylated coconut fatty alcohols, from which the preliminary alcohols (10 and fewer carbon atoms) are separated and essentially consist of lauryl and myristyl alcohol in addition to small amounts of cetyl and stearyl alcohol.
  • ethoxylated oxo alcohols or alcohols produced by ethylene polymerization which essentially consist of alcohol mixtures with 12 to 16 carbon atoms.
  • the degree of ethoxylation of these preferred alcohols or alcohol mixtures is in particular 6 to 9.
  • the proportion of component (b) is 7 to 20% by weight, preferably 8 to 15% by weight.
  • Suitable soaps (c) are sodium and potassium soaps and soaps from alkanolamines, in particular triethanolamine, which are derived from saturated and monounsaturated fatty acids having 12 to 18 carbon atoms. Due to their low cloud point, soaps from coconut fatty acids (after separation of the fatty acids with less than 12 carbon atoms) and oleic acid or from oleic acid-rich fatty acid mixtures and combinations of these soaps are particularly suitable. These soap mixtures are preferably used in the form of sodium soaps or as mixtures of sodium soaps and triethanolamine soaps.
  • the proportion of soaps (c) is 6 to 16% by weight, preferably 8 to 15% by weight, based in each case on the fatty acid content.
  • Component (d) are fatty acid diethanolamides which are derived from monounsaturated fatty acids with 16 to 18 carbon atoms and their mixtures with saturated fatty acids of the same chain length, but the proportion of unsaturated compounds is at least 50% by weight, preferably is at least 65% by weight.
  • Diethanolamides derived from oleic acid and palmitoleic acid and their mixtures with the corresponding palmitic acid and stearic acid derivatives as are obtainable from naturally occurring fatty acid mixtures rich in oleic acid, for example from tallow fatty acids or tall oil fatty acids, by isolating the unsaturated portions by known separation processes (network separation) are particularly suitable.
  • Fatty acid fractions which can be used well contain, for example, 50 to 100% by weight, preferably 65 to 95% by weight of oleic acid and 0 to 50% by weight, preferably 5 to 35% by weight, of palmitic acid and stearic acid, and in industrial mixtures also small amounts, ie up to 5%, of myristic acid may be present.
  • the ethanolamides which can be prepared from these fatty acids by reaction with diethanolamine are technical mixtures which usually contain 85 to 95% by weight of N-acyl compound and 2 to 10% by weight of O-acyl compound. In addition, small amounts, i.e. up to 5% by weight of unreacted starting material, mainly free diethanolamine and very small amounts of free fatty acid. These usual additions do not interfere in the present compositions, but can be regarded as functional constituents, especially since the compositions already contain soap and, in a preferred embodiment, also alkanolamines.
  • the proportion of component (d) is 7 to 15% by weight, preferably 8 to 15% by weight and in particular 10 to 12% by weight.
  • Suitable sequestering agents are polycarboxylic acids and polyphosphonic acids.
  • Suitable polycarboxylic acids are citric acid, nitrilotriacetic acid, ethylenediaminoetetraacetic acid and their higher homologues.
  • Suitable polyphosphonic acids are aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), diethylenetriaminepenta- (methylenephosphonic acid) and their higher homologues. Said acids can be used as salts of sodium, potassium and alkanolamines, e.g. of triethanolamine.
  • Citric acid ethylenediaminetetra- (methylenephosphonic acid) and diethylenetriaminepenta- (methylenephosphonic acid) and mixtures thereof are particularly suitable. They are present in the agents in proportions of 0.2 to 3% by weight, preferably 0.4 to 2% by weight.
  • Water-miscible organic solvents which are present in the compositions in proportions of 5 to 15% by weight, preferably 7 to 13% by weight, are e.g. Alcohols, glycols, polyglycols and ether alcohols, such as methanol, ethanol, propanol, isopropanol, glycerin, glycol, diethylene glycol, triethylene glycol and low molecular weight polyethylene glycols, propylene glycol and oligomeric propylene glycol ethers, furthermore ether alcohols, such as methyl propyl glycol, methyl butyl glycol or methyl ethyl glycol. Mixtures of ethanol and propylene glycol in a ratio of 1: 4 to 4: 1 are preferably used as solvents.
  • Alcohols, glycols, polyglycols and ether alcohols such as methanol, ethanol, propanol, isopropanol, glycerin, glycol, diethylene glycol, triethylene glycol and
  • Additional ingredients which are advantageously added to the agents are enzymes, enzyme stabilizers, compounds for adjusting the pH, optical brighteners, hydrotropes, foam inhibitors, dyes or color pigments and agents which act as opacifiers or give the solutions a silky sheen.
  • Suitable enzymes are proteases and amylases obtained from fungi or bacteria in a known manner and mixtures thereof, e.g. enzymes obtained from Bacillus subtilis or Bacillus licheniformis.
  • the commercially available enzyme preparations usually also contain activators, such as calcium and magnesium salts, and extenders and binders. The content of the agents in these enzyme preparations is generally 0.1 to 1.5% by weight.
  • the stability of the enzymes can be increased by adding alkanolamines, especially triethanolamine.
  • the triethanolamine is expediently present in excess, as a result of which a desired weakly alkaline reaction of 7.2 to 9, preferably 7.5 to 8.5, can be set.
  • Low molecular weight acids such as formic acid, acetic acid and lactic acid are suitable as further enzyme stabilizers, which, based on free acid, can be present in proportions of 0.1 to 2, preferably 0.2 to 1,% by weight. Due to the basic reaction of the agents, these acids are predominantly or completely in the form of their salts, e.g. as sodium, potassium or alkanolamine salts.
  • Disulfonic acid or diphenyl-distyryl-disulfonic acid in the form of their water-soluble salts - as optical brighteners are those known derivatives of the bis-triazinyl-4,4 'diaminostilbene-2,2' are suitable.
  • Examples of these are salts of 4,4-bis (-2 " -anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2-disulfonic acid or of 4,4- Bis (2-sulfostyryl) diphenyl, 4,4-bis (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl) -4- (2-sulfostyryl) diphenyl.
  • Suitable foam inhibitors are water-dispersible silicones, e.g. Dimethylpolysiloxanes, which can optionally be modified with polyglycol ether groups, and mixtures of such compounds with polysiloxane resins or finely divided silica, which is preferably silanated.
  • the content of optical brighteners and silicone defoamers in the agents can be in the order of 0.01 to 1% by weight.
  • the water content of the agents should be adjusted so that a homogeneous, easily pourable solution that is not segregated by precipitation results.
  • the water content is generally between 25 and 45% by weight, preferably between 33 and 40% by weight.
  • the agents according to the invention are notable for high washing and cleaning properties as well as favorable softening and grip-improving properties. They are suitable both for hand washing and due to their balanced foam behavior for use in washing machines.
  • EO attached ethylene oxide
  • the reflectance of the samples was determined photometrically and the handle (degree of softness) was assessed. The mean was formed from 9 measurements or samples.
  • comparative samples were used which had been washed under similar conditions with a commercially available high-performance detergent (V2) without further textile aftertreatment.
  • V3 commercially available high-performance detergent
  • the grip properties were determined after 1 wash treatment and after 5 wash treatments.
  • the handle assessments were carried out on terry towels washed once. The results are shown in the following tables. They demonstrate the superiority of the agents according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A liquid, readily pourable detergent concentrate having fabric-softening properties is free from builder salts and contains the following constituents: (a) from about 5 to about 15% by weight of sodium alkylbenzene sulfonate, (b) from about 7 to about 20% by weight of ethoxylated alcohols containing from 12 to 18 carbon atoms in the alcohol residue and from 5 to 10 glycol ether groups, (c) from about 6 to about 16% by weight, based on the weight of the fatty acids used to form the soap, of saturated or monounsaturated fatty acids containing from 12 to 18 C-atoms, present as a water-soluble soap, (d) from about 7 to about 15% by weight of a fatty acid diethanolamide derived from C16-C18 fatty acids of which at least 50% are monounsaturated, (e) from about 0.2 to about 3% by weight of sequestering agents, (f) from about 5 to about 15% by weight of low molecular weight alcohols and from about 25 to about 45% by weight of water. The ratio by weight of (a) to (b) to (c) to (d) is in the range of 1:(1-2):(1-2):(1.5-2.5).

Description

Die vorliegende Erfindung betrifft ein gerüstsalzfreies, flüssiges Waschmittelkonzentrat, das aufgrund seiner Tensidzusammensetzung in Verbindung mit speziell ausgewählten Fettsäurediethanolamiden textilweichmachende und griffverbessernde Eigenschaften besitzt, so daß die damit gewaschenen Textilien keiner Nachbehandlung mit einem speziellen Avivagemittel bedürfen.The present invention relates to a skeletal salt-free, liquid detergent concentrate which, due to its surfactant composition in combination with specially selected fatty acid diethanolamides, has textile-softening and grip-improving properties, so that the textiles washed therewith do not require any aftertreatment with a special softening agent.

Es ist aus der Zeitschrift "Soap and Chemical Specialities", November 1958, Seiten 48 bis 50; bekannt, daß gewisse Stearinsäurederivate von Alkylolaminen als weichmachendes Agens in Textilbehandlungsmitteln eingesetzt werden. Aus GB-A 1 104 441 sind Avivagemittel bekannt, die neben quartären Ammoniumsalzen mit 2 langkettigen Akylresten zusätzlich Fettsäuremonoethanolamide und deren Gemische mit Fettsäurediethanolamiden enthalten, in denen die Fettsäuren 12 bis 18 C-Atome aufweisen und sich bevorzugt von Talgfettsäuren ableiten, die bekanntlich hohe Anteile an Stearinsäure enthalten. Das Problem, wie sich derartige Verbindungen in tensidhaltigen Waschmitteln verhalten bzw. eingesetzt werden können, wird in diesen Publikationen nicht berührt. Im übrigen hat sich gezeigt, daß die Stearinsäurederivate sich nicht in wirksamer Menge in lagerstabile Flüssigwaschmittel einsetzen lassen.It is from the journal "Soap and Chemical Specialties", November 1958, pages 48 to 50; It is known that certain stearic acid derivatives of alkylolamines are used as softening agents in textile treatment agents. From GB-A 1 104 441, conditioning agents are known which, in addition to quaternary ammonium salts with 2 long-chain alkyl radicals, additionally contain fatty acid monoethanolamides and their mixtures with fatty acid diethanolamides in which the fatty acids have 12 to 18 carbon atoms and are preferably derived from tallow fatty acids, which are known to have high proportions contain stearic acid. The problem of how such compounds behave or can be used in detergent-containing detergents is not addressed in these publications. Furthermore, it has been shown that the stearic acid derivatives cannot be used in an effective amount in storage-stable liquid detergents.

Ferner sind zahlreiche Flüssigwaschmittel-Rezepturen bekannt, die mehr oder weniger große Gehalte an Fettsäuremono- bzw. diethanolamiden aufweisen. Stets handelt es sich dabei um solche Alkanolamide, die sich von Fettsäuregemischen mit hohem Anteil an G2-COs-Fettsäuren, beispielsweise Cocosfettsäuren, ableiten. Diese Alkanolamide sollen die Wasch- und Schaumkraft steigern bzw. die Hautverträglichkeit verbessern. Eine Avivagewirkung kommt diesen Mitteln nicht zu. Als Beispiele für derartige Mittel seien die gemäß DE-A 1 047 973, DE-A 2 022 064, DE-A 2 703 998 (FR-A 2 378 852, US-A 4 153 570), DE-A 2 819 455, DE-A 3 022 767, DE-A 3 161 222, EP-A 38 101, US-A 2 861 956, US-A 2 943 058 aufgeführt.Furthermore, numerous liquid detergent formulations are known which have more or less large contents of fatty acid mono- or diethanolamides. These are always those alkanolamides which are derived from fatty acid mixtures with a high proportion of G2-COs fatty acids, for example coconut fatty acids. These alkanolamides are said to increase washing and foaming power or to improve skin tolerance. These remedies do not have an aviva effect. Examples of such agents are those according to DE-A 1 047 973, DE-A 2 022 064, DE-A 2 703 998 (FR-A 2 378 852, US-A 4 153 570), DE-A 2 819 455 , DE-A 3 022 767, DE-A 3 161 222, EP-A 38 101, US-A 2 861 956, US-A 2 943 058.

Weiterhin wurde bereits vorgeschlagen, Waschmitteln mit einem Gehalt an Aniontensiden avivierend wirkende Quartärsalze zuzusetzen, wobei die Quartärsalze längerkettige Fettsäurereste bzw. Fettalkylreste aufweisen. Da jedoch Aniontenside mit derartigen Quartärsalzen im allgemeinen unverträglich sind bzw. unter Bildung inaktiver Elektroneutralsalze reagieren, wird die erwünschte Wirkung in der Regel nicht erzielt.Furthermore, it has already been proposed to add detergents containing quaternary salts with an anionic surfactant effect, the quaternary salts having longer-chain fatty acid residues or fatty alkyl residues. However, since anionic surfactants are generally incompatible with quaternary salts of this type or react to form inactive electroneutral salts, the desired effect is generally not achieved.

Das nachfolgend beschriebene erfindungsgemäße Mittel ist geeignet, die genannten Mängel zu vermeiden.The agent according to the invention described below is suitable for avoiding the deficiencies mentioned.

Gegenstand der Erfindung ist ein Flüssigwaschmittel mit einem Gehalt an (a) Natriumalkylbenzolsulfonat mit 10 bis 14 C-Atomen in der linearen Alkylgruppe, (b) wasserlöslichen, ethoxylierten Alkoholen mit 12 bis 18 C-Atomen im Kohlenwasserstoffrest und 5 bis 10 Glykolethergruppen, (c) einer wasserlöslichen Seife, abgeleitet von gesättigten und/oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen, (d) Fettsäurediethanolamid, (e) Sequestrierungsmitteln aus der Klasse der Polycarbonsäuren und Polyphosphonsäuren, (f) mit Wasser mischbaren organischen Lösungsmitteln und Wasser, dadurch gekennzeichnet, daß der Anteil der Komponente (a) 5 bis 15 Gew.-%, der Komponente (b) 7 bis 20 Gew.-%, der Komponente (c), auf Fettsäure bezogen, 6 bis 16 Gew.-%, der Komponente (d) 7 bis 15 Gew.-%, der Komponente (e) 0,2 bis 3 Gew.-% und der Komponente (f) 5 bis 15 Gew.-% beträgt, mit der Maßgabe, daß das Verhältnis von (a):(b):(c):(d) = 1:(1-2):(1-2):(1,5-2,5) beträgt und die Komponente (d) sich von Fettsäuren mit 16 bis 18 Kohlenstoffatomen mit mehr als 50% an einfach ungesättigten Fettsäuren ableitet.The invention relates to a liquid detergent containing (a) sodium alkylbenzenesulfonate with 10 to 14 carbon atoms in the linear alkyl group, (b) water-soluble, ethoxylated alcohols with 12 to 18 carbon atoms in the hydrocarbon radical and 5 to 10 glycol ether groups, (c ) a water-soluble soap derived from saturated and / or unsaturated fatty acids with 12 to 18 carbon atoms, (d) fatty acid diethanolamide, (e) sequestering agents from the class of polycarboxylic acids and polyphosphonic acids, (f) water-miscible organic solvents and water, thereby characterized in that the proportion of component (a) 5 to 15 wt .-%, component (b) 7 to 20 wt .-%, component (c), based on fatty acid, 6 to 16 wt .-%, the Component (d) is 7 to 15% by weight, component (e) is 0.2 to 3% by weight and component (f) is 5 to 15% by weight, with the proviso that the ratio of ( a) :( b) :( c) :( d) = 1: (1-2) :( 1-2) :( 1.5-2.5) and component (d) is derived from fatty acids with 16 to 18 carbon atoms with more than 50% of monounsaturated fatty acids.

Der Anteil des linearen Natrium-alkylbenzolsulfonats (a) beträgt 5 bis 15 Gew.-%, vorzugsweise 6 bis 10 Gew.-%. Vorzugsweise wird Dodecylbenzolsulfonat eingesetzt.The proportion of the linear sodium alkylbenzenesulfonate (a) is 5 to 15% by weight, preferably 6 to 10% by weight. Dodecylbenzenesulfonate is preferably used.

Als nichtionische ethoxylierte Alkohole (b) kommen Fettalkohole bzw. in 2-Stellung methylverzweigte Oxo-Alkohole mit 12 bis 18, vorzugsweise 12 bis 16 C-Atomen infrage. Die Anzahl der angelagerten Ethylenoxidgruppen (EO) beträgt 5 bis 10. Als gut geeignet haben sich solche ethoxylierten Alkohole erwiesen, deren HLB-Wert 9 bis 14, insbesondere 11 bis 13,5 beträgt. Beispiele hierfür sind ethoxylierte Cocosfettalkohole, von denen die Vorlaufalkohole (10 und weniger C-Atome) abgetrennt sind und im wesentlichen aus Lauryl- und Myristylalkohol neben geringen Anteilen an Cetyl- und Stearylalkohol bestehen. Besonders geeignet sind ferner ethoxylierte Oxoalkohole bzw. durch Ethylenpolymerisation hergestellte Alkohole, die im wesentlichen aus Alkoholgemischen mit 12 bis 16 C-Atomen bestehen. Der Ethoxylierungsgrad dieser bevorzugten Alkohole bzw. Alkoholgemische beträgt insbesondere 6 bis 9. Der Anteil der Komponente (b) beträgt 7 bis 20 Gew.-%, vorzugsweise 8 bis 15 Gew.-%.Suitable nonionic ethoxylated alcohols (b) are fatty alcohols or oxo alcohols with 12 to 18, preferably 12 to 16, carbon atoms which are methyl-branched in the 2-position. The number of attached ethylene oxide groups (EO) is 5 to 10. Ethoxylated alcohols whose HLB value is 9 to 14, in particular 11 to 13.5, have proven to be very suitable. Examples of this are ethoxylated coconut fatty alcohols, from which the preliminary alcohols (10 and fewer carbon atoms) are separated and essentially consist of lauryl and myristyl alcohol in addition to small amounts of cetyl and stearyl alcohol. Also particularly suitable are ethoxylated oxo alcohols or alcohols produced by ethylene polymerization, which essentially consist of alcohol mixtures with 12 to 16 carbon atoms. The degree of ethoxylation of these preferred alcohols or alcohol mixtures is in particular 6 to 9. The proportion of component (b) is 7 to 20% by weight, preferably 8 to 15% by weight.

Als Seifen (c) kommen Natrium- und Kaliumseifen sowie Seifen von Alkanolaminen, insbesondere Triethanolamin, infrage, die sich von gesättigten und einfach ungesättigten Fettsäuren mit 12 bis 18 C-Atomen ableiten. Aufgrund ihres niedrig liegenden Trübungspunktes eignen sich insbesondere Seifen von Cocosfettsäuren (nach Abtrennung der Fettsäuren mit weniger als 12 C-Atomen) sowie der Ölsäure bzw. von ölsäurereichen Fettsäuregemischen sowie Kombinationen dieser Seifen. Diese Seifengemische werden vorzugsweise in Form der Natriumseifen bzw. als Gemische von Natriumseifen und Triethanolaminseifen eingesetzt.Suitable soaps (c) are sodium and potassium soaps and soaps from alkanolamines, in particular triethanolamine, which are derived from saturated and monounsaturated fatty acids having 12 to 18 carbon atoms. Due to their low cloud point, soaps from coconut fatty acids (after separation of the fatty acids with less than 12 carbon atoms) and oleic acid or from oleic acid-rich fatty acid mixtures and combinations of these soaps are particularly suitable. These soap mixtures are preferably used in the form of sodium soaps or as mixtures of sodium soaps and triethanolamine soaps.

Der Anteil der Seifen (c) beträgt 6 bis 16 Gew.-%, vorzugsweise 8 bis 15 Gew.-%, jeweils bezogen auf den Gehalt an Fettsäure.The proportion of soaps (c) is 6 to 16% by weight, preferably 8 to 15% by weight, based in each case on the fatty acid content.

Als Komponente (d) kommen Fettsäurediethanolamide infrage, die sich von einfach ungesättigten Fettsäuren mit 16 bis 18 C-Atomen sowie deren Gemischen mit gesättigten Fettsäuren gleicher Kettenlänge ableiten, wobei jedoch der Anteil der ungesättigten Verbindungen mindestens 50 Gew.-%, vorzugsweise mindestens 65 Gew.-% beträgt. Geeignet sind insbesondere von Ölsäure und Palmitoleinsäure abgeleitete Diethanolamide sowie deren Gemische mit den entsprechenden Palmitinsäure- und Stearinsäurederivaten, so wie sie aus natürlich vorkommenden ölsäurereichen Fettsäuregemischen, z.B. aus Taigfettsäuren oder Tallölfettsäuren, durch Isolierung der ungesättigten Anteile nach bekannten Trennverfahren (Umnetztrennung) zugänglich sind. Gut brauchbare Fettsäurefraktionen enthalten z.B. 50 bis 100 Gew.-%, vorzugsweise 65 bis 95 Gew.-% Ölsäure und 0 bis 50 Gew.-%, vorzugsweise 5 bis 35 Gew.-%, Palmitinsäure und Stearinsäure, wobei in technischen Gemischen auch noch geringe Mengen, d.h. bis zu 5%, an Myristinsäure vorliegen können.Component (d) are fatty acid diethanolamides which are derived from monounsaturated fatty acids with 16 to 18 carbon atoms and their mixtures with saturated fatty acids of the same chain length, but the proportion of unsaturated compounds is at least 50% by weight, preferably is at least 65% by weight. Diethanolamides derived from oleic acid and palmitoleic acid and their mixtures with the corresponding palmitic acid and stearic acid derivatives, as are obtainable from naturally occurring fatty acid mixtures rich in oleic acid, for example from tallow fatty acids or tall oil fatty acids, by isolating the unsaturated portions by known separation processes (network separation) are particularly suitable. Fatty acid fractions which can be used well contain, for example, 50 to 100% by weight, preferably 65 to 95% by weight of oleic acid and 0 to 50% by weight, preferably 5 to 35% by weight, of palmitic acid and stearic acid, and in industrial mixtures also small amounts, ie up to 5%, of myristic acid may be present.

Die aus diesen Fettsäuren durch Umsetzung mit Diethanolamin herstellbaren Ethanolamide stellen technische Gemische dar, die üblicherweise 85 bis 95 Gew.-% N-Acylverbindung und 2 bis 10 Gew.-% O-Acylverbindung enthalten. Darüber hinaus können geringe Mengen, d.h. bis zu 5 Gew.-%, an nicht umgesetztem Ausgangsmaterial, hauptsächlich freies Diethanolamin sowie sehr geringe Mengen an freier Fettsäure anwesend sein. Diese üblichen Beimengungen stören in den vorliegenden Mitteln nicht, sondern können als funktionelle Bestandteile betrachtet werden, zumal die Mittel ohnehin Seife und in einer bevorzugten Ausführungsform auch Alkanolamine enthalten.The ethanolamides which can be prepared from these fatty acids by reaction with diethanolamine are technical mixtures which usually contain 85 to 95% by weight of N-acyl compound and 2 to 10% by weight of O-acyl compound. In addition, small amounts, i.e. up to 5% by weight of unreacted starting material, mainly free diethanolamine and very small amounts of free fatty acid. These usual additions do not interfere in the present compositions, but can be regarded as functional constituents, especially since the compositions already contain soap and, in a preferred embodiment, also alkanolamines.

Der Anteil der Komponente (d) beträgt 7 bis 15 Gew.-%, vorzugsweise 8 bis 15 Gew.-% und insbesondere 10 bis 12 Gew.-%.The proportion of component (d) is 7 to 15% by weight, preferably 8 to 15% by weight and in particular 10 to 12% by weight.

Als Sequestrierungsmittel (e) kommen Polycarbonsäuren und Polyphosphonsäuren infrage. Geeignete Polycarbonsäuren sind Citronensäure, Nitrilotriessigsäure, Ethylendiaminoetetraessigsäure und deren höhere Homologen. Geeignete Polyphosphonsäuren sind Aminotri-(methylenphosphonsäure), Ethy- lendiamintetra-(methylenphosphonsäure), Diethylentriaminpenta-(methylenphosphonsäure) sowie deren höhere Homologen. Die genannten Säuren können als Salze des Natriums, Kaliums und von Alkanolaminen, z.B. des Triethanolamins, vorliegen. Besonders geeignet sind Citronensäure, Ethylendiamintetra-(methylenphosphonsäure) und Diethylentriaminpenta-(methylenphosphonsäure) sowie deren Gemische. Sie sind in den Mitteln in Anteilen von 0,2 bis 3 Gew.-%, vorzugsweise 0,4 bis 2 Gew.-% anwesend.Suitable sequestering agents (e) are polycarboxylic acids and polyphosphonic acids. Suitable polycarboxylic acids are citric acid, nitrilotriacetic acid, ethylenediaminoetetraacetic acid and their higher homologues. Suitable polyphosphonic acids are aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), diethylenetriaminepenta- (methylenephosphonic acid) and their higher homologues. Said acids can be used as salts of sodium, potassium and alkanolamines, e.g. of triethanolamine. Citric acid, ethylenediaminetetra- (methylenephosphonic acid) and diethylenetriaminepenta- (methylenephosphonic acid) and mixtures thereof are particularly suitable. They are present in the agents in proportions of 0.2 to 3% by weight, preferably 0.4 to 2% by weight.

Mit Wasser mischbare organische Lösungsmittel, die in den Mitteln in Anteilen von 5 bis 15 Gew.-%, vorzugsweise 7 bis 13 Gew.-% vorliegen, sind z.B. Alkohole, Glykole, Polyglykole und Etheralkohole, wie Methanol, Ethanol, Propanol, Isopropanol, Glycerin, Glykol, Diethylenglykol, Triethylenglykol und niedermolekulare Polyethylenglykole, Propylenglykol und oligomere Propylenglykolether, ferner Etheralkohole, wie Methylpropylglykol, Methylbutylglykol oder Methylethylglykol. Vorzugsweise werden Gemische aus Ethanol und Propylenglykol im Verhältnis 1:4 bis 4:1 als Lösungsmittel verwendet.Water-miscible organic solvents, which are present in the compositions in proportions of 5 to 15% by weight, preferably 7 to 13% by weight, are e.g. Alcohols, glycols, polyglycols and ether alcohols, such as methanol, ethanol, propanol, isopropanol, glycerin, glycol, diethylene glycol, triethylene glycol and low molecular weight polyethylene glycols, propylene glycol and oligomeric propylene glycol ethers, furthermore ether alcohols, such as methyl propyl glycol, methyl butyl glycol or methyl ethyl glycol. Mixtures of ethanol and propylene glycol in a ratio of 1: 4 to 4: 1 are preferably used as solvents.

Zusätzliche Bestandteile, die den Mitteln vorteilhaft zugesetzt werden, sind Enzyme, Enzymstabilisatoren, Verbindungen zur Einstellung des pH-Wertes, optische Aufheller, Hydrotrope, Schauminhibitoren, Farbstoffe bzw. Farbpigmente und Mittel, die als Trübungsstoffe wirken bzw. den Lösungen einen Seidenglanz verleihen.Additional ingredients which are advantageously added to the agents are enzymes, enzyme stabilizers, compounds for adjusting the pH, optical brighteners, hydrotropes, foam inhibitors, dyes or color pigments and agents which act as opacifiers or give the solutions a silky sheen.

Als Enzyme eignen sich aus Pilzen oder Bakterien in bekannter Weise gewonnene Proteasen und Amylasen sowie deren Gemische, z.B. aus Bacillus subtilis oder Bacillus licheniformis gewonnene Enzyme. Die handelsüblichen Enzymzubereitungen enthalten in der Regel noch Aktivatoren, wie Calcium- und Magnesiumsalze, sowie Streck- und Bindemittel. Der Gehalt der Mittel an diesen Enzymzubereitungen beträgt im allgemeinen 0,1 bis 1,5 Gew.-%.Suitable enzymes are proteases and amylases obtained from fungi or bacteria in a known manner and mixtures thereof, e.g. enzymes obtained from Bacillus subtilis or Bacillus licheniformis. The commercially available enzyme preparations usually also contain activators, such as calcium and magnesium salts, and extenders and binders. The content of the agents in these enzyme preparations is generally 0.1 to 1.5% by weight.

Die Stabilität der Enzyme kann durch Zusatz von Alkanolaminen, insbesondere Triethanolamin, erhöht werden. Das Triethanolamin ist zweckmäßigerweise im Überschuß vorhanden, wodurch sich eine gewünschte schwach alkalische Reaktion von 7,2 bis 9, vorzugsweise von 7,5 bis 8,5 einstellen läßt.The stability of the enzymes can be increased by adding alkanolamines, especially triethanolamine. The triethanolamine is expediently present in excess, as a result of which a desired weakly alkaline reaction of 7.2 to 9, preferably 7.5 to 8.5, can be set.

Als weitere Enzymstabilisatoren eignen sich niedermolekulare Säuren wie Ameisensäure, Essigsäure und Milchsäure, die, auf freie Säure bezogen, in Anteilen von 0,1 bis 2, vorzugsweise 0,2 bis 1 Gew.-% anwesend sein können. Aufgrund der basischen Reaktion der Mittel liegen diese Säuren überwiegend oder vollständig in Form ihrer Salze vor, z.B. als Natrium-, Kalium- oder Alkanolaminsalze.Low molecular weight acids such as formic acid, acetic acid and lactic acid are suitable as further enzyme stabilizers, which, based on free acid, can be present in proportions of 0.1 to 2, preferably 0.2 to 1,% by weight. Due to the basic reaction of the agents, these acids are predominantly or completely in the form of their salts, e.g. as sodium, potassium or alkanolamine salts.

Als optische Aufheller eignen sich die bekannten Derivate der Bis-triazinyl-4,4'-diaminostilben-2,2'- disulfonsäure bzw. der Diphenyl-distyryl-disulfonsäure in Form ihrer wasserlöslichen Salze. Beispiele hierfür sind Salze der 4,4-Bis(-2"-anilino-4"-morpholino-1,3,5-triazinyl-6"-amino)-stilben-2,2-disulfonsäure bzw. des 4,4-Bis-(2-sulfostyryl)-diphenyls, 4,4-Bis(4-chlor-3-sulfostyryl)-diphenyls und 4-(4-Chlorstyryl)-4-(2-sulfostyryl)-diphenyls.Disulfonic acid or diphenyl-distyryl-disulfonic acid in the form of their water-soluble salts - as optical brighteners are those known derivatives of the bis-triazinyl-4,4 'diaminostilbene-2,2' are suitable. Examples of these are salts of 4,4-bis (-2 " -anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2-disulfonic acid or of 4,4- Bis (2-sulfostyryl) diphenyl, 4,4-bis (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl) -4- (2-sulfostyryl) diphenyl.

Als Schauminhibitoreh eignen sich in Wasser dispergierbare Silikone, z.B. Dimethylpolysiloxane, die gegebenenfalls mit Polyglykolethergruppen modifiziert sein können, sowie Gemische derartiger Verbindungen mit Polysiloxanharzen bzw. feinteiliger Kieselsäure, die vorzugsweise silaniert ist. Der Gehalt der Mittel an optischen Aufhellern und Silikonentschäumern kann in der Größenordnung 0,01 bis 1 Gew.- % liegen.Suitable foam inhibitors are water-dispersible silicones, e.g. Dimethylpolysiloxanes, which can optionally be modified with polyglycol ether groups, and mixtures of such compounds with polysiloxane resins or finely divided silica, which is preferably silanated. The content of optical brighteners and silicone defoamers in the agents can be in the order of 0.01 to 1% by weight.

Der Wassergehalt der Mittel soll so eingestellt sein, daß eine homogene, gut gießbare und nicht durch Ausfällungen entmischte Lösung entsteht. Der Wassergehalt liegt im allgemeinen zwischen 25 und 45 Gew.-%, vorzugsweise zwischen 33 und 40 Gew.-%.The water content of the agents should be adjusted so that a homogeneous, easily pourable solution that is not segregated by precipitation results. The water content is generally between 25 and 45% by weight, preferably between 33 and 40% by weight.

Die erfindungsgemäßen Mittel zeichnen sich durch ein hohes Wasch- und Reinigungsvermögen sowie günstige weichmachende und griffverbessernde Eigenschaften aus. Sie eignen sich sowohl für ein Waschen von Hand als auch aufgrund ihres ausgewogenen Schaumverhaltens zur Anwendung in Waschmaschinen.The agents according to the invention are notable for high washing and cleaning properties as well as favorable softening and grip-improving properties. They are suitable both for hand washing and due to their balanced foam behavior for use in washing machines.

BeispieleExamples

Zur Herstellung eines Mittels gemäß nachstehender Zusammensetzung wurde eine 50% wäßrige Paste von Natrium-dodecylbenzolsulfonat mit dem nichtionischen Tensid (Abkürzung EO = angelagertes Ethylenoxid) vermischt, anschließend das Lösungsmittel, das Fettsäurediethanolamid und die zur Seifenbildung benötigte Fettsäure sowie die Phosphonsäure (Diethylentriamin-pentamethylenphosphonsäure) und die Citronensäure zugemischt. Nach der Neutralisation mit Natronlauge und Triethanolamin erfolgte der Zusatz der übrigen Stoffe (Angaben in Gew.-%, bezogen auf wasserfreie Substanz). In dem Vergleichsprodukt V1 wurde das Olsäurediethanolamid zu gleichen Teilen durch Alkylbenzolsulfonat und nichtionisches Tensid ersetzt.

Figure imgb0001
To prepare an agent according to the composition below, a 50% aqueous paste of sodium dodecylbenzenesulfonate was mixed with the nonionic surfactant (abbreviation EO = attached ethylene oxide), then the solvent, the fatty acid diethanolamide and the fatty acid required for soap formation and the phosphonic acid (diethylenetriamine-pentamethylenephosphonic acid) and mixed in the citric acid. After neutralization with sodium hydroxide solution and triethanolamine, the other substances were added (figures in% by weight, based on the anhydrous substance). In the comparative product V1, the oleic acid diethanolamide was replaced in equal parts by alkylbenzenesulfonate and nonionic surfactant.
Figure imgb0001

Das Waschvermögen und die Avivagewirkung wurden unter praxisnahen Bedingungen getestet. Hierzu wurden Textilproben aus Baumwolle, die unter standardisierten Bedingungen mit Hautfett, Pigmentschmutz und Flecken von Rotwein, Tee und Blaubeeren angeschmutzt worden waren, zusammen mit 3 kg Ballastwäsche in einem Haushaltswaschautomaten (Kapazität 4 kg) bei 60°C und 90°C gewaschen. Die Waschdauer einschließlich Aufheizung betrug 20 Minuten, die Waschmittelkonzentration 7,5 g/Liter, das Verhältnis von Textilmenge (in kg) zu Waschlauge (in Liter) betrug 1:10, die Härte des Leitungswassers 16°dH (160 mg Ca0 pro Liter). Nach dreimaligem Nachspülen wurde geschleudert und getrocknet. Die Remission der Proben wurde photometrisch bestimmt und der Griff (Weichheitsgrad) beurteilt. Aus jeweils 9 Messungen bzw. Abmusterungen wurde der Mittelwert gebildet. Bei der Beurteilung der weichmachenden Eigenschaften wurden Vergleichsproben herangezogen, die unter gleichartigen Bedingungen mit einem handelsüblichen Hochleistungswaschmittel (V2) ohne weitere Textilnachbehandlung gewaschen worden waren. In einer dritten Versuchsreihe wurden Proben zum Vergleich herangezogen, die mit einem handelsüblichen Hochleistungswaschmittel (V3) gewaschen wurden, das einen avivierend wirkenden Zusatz auf Basis eines Cocosalkyl-trimethylammoniumsalzes enthielt. Die Bestimmung der Griffeigenschaften wurden nach 1 Waschbehandlung sowie nach 5 Waschbehandlungen vorgenommen. Zusätzlich wurden die Griffbeurteilungen an 1 mal gewaschener Frottierware vorgenommen. Die Ergebnisse sind den folgenden Tabellen zu entnehmen. Sie belegen die Überlegenheit der erfindungsgemäßen Mittel.

Figure imgb0002
The washability and the aviva effect were tested under practical conditions. For this purpose, textile samples made of cotton, which had been soiled with skin fat, pigment dirt and stains from red wine, tea and blueberries under standardized conditions, were washed together with 3 kg ballast laundry in a domestic washing machine (capacity 4 kg) at 60 ° C and 90 ° C. The washing time including heating was 20 minutes, the detergent concentration was 7.5 g / liter, the ratio of the amount of textile (in kg) to the washing solution (in liters) was 1:10, the hardness of the tap water was 16 ° dH (160 mg Ca0 per liter) . After rinsing three times, the product was spun and dried. The reflectance of the samples was determined photometrically and the handle (degree of softness) was assessed. The mean was formed from 9 measurements or samples. When evaluating the softening properties, comparative samples were used which had been washed under similar conditions with a commercially available high-performance detergent (V2) without further textile aftertreatment. In a third series of tests, samples were used for comparison, which were washed with a commercially available high-performance detergent (V3), which contained an anti-aging additive based on a cocoalkyl-trimethylammonium salt. The grip properties were determined after 1 wash treatment and after 5 wash treatments. In addition, the handle assessments were carried out on terry towels washed once. The results are shown in the following tables. They demonstrate the superiority of the agents according to the invention.
Figure imgb0002

Griff (0 = niedrigste, 6 = höchste Bewertung; 6 entspricht der Wirkung eines im 4. Spülgang eingesetzten hochwirksamen Avivagemittels)Handle (0 = lowest, 6 = highest rating; 6 corresponds to the effect of a highly effective anti-aging agent used in the 4th rinse)

Figure imgb0003
Figure imgb0003

Claims (10)

1. A liquid detergent containing (a) sodium alkylbenzene sulfonate containing from 10 to 14 carbon atoms in the linear alkyl group, (b) water-soluble, ethoxylated alcohols containing from 12 to 18 carbon atoms in the hydrocarbon radical and from 5 to 10 glycolether groups, (c) a water-soluble soap derived from saturated and/or unsaturated C12-C18 fatty acids, (d) fatty acid diethanolamide, (e) sequestering agents of the polycarboxylic acid and polyphosphonic acid type, (f) water-miscible organic solvents and water, characterized in that the percentage of component (a) is from 5 to 15% by weight, the percentage of component (b) from 7 to 20% by weight, the percentage of component (c), based on fatty acid, from 6 to 16% by weight, the percentage of component (d) from 7 to 15% by weight, the percentage of component (e) from 0.2 to 3% by weight and the percentage of component (f) from 5 to 15% by weight, with the proviso that the ratio of (a) to (b) to (c) to (d) is 1:(1-2):(1:2):(1.5-2.5) and component (d) is derived from C16-C18 fatty acids containing more than 50% of monounsaturated fatty acids.
2. A detergent as claimed in Claim 1, characterized in that component (a) consists of from 6 to 10% by weight of sodium dodecylbenzene sulfonate.
3. A detergent as claimed in Claim 1, characterized in that component (b) consists of from 8 to 15% by weight of ethoxylated fatty alcohols or oxoalcohols containing from 12 to 16 carbon atoms and from 6 to 9 glycolether groups.
4. A detergent as claimed in Claim 1., characterized in that component (c) consists of from 8 to 15% by weight (based on fatty acid) of sodium-or triethanolamine soaps derived from coconut oil fatty acids, oleic acid and mixtures thereof.
5. A detergent as claimed in Claim 1, characterized in that component (d) consists of from 8 to 15% by weight of fatty acid diethanolamides derived from fatty acids containing more than 65% by weight of oleic acid.
6. A detergent as claimed in Claim 1, characterized in that component (e) consists of water-soluble salts of citric acid, ethylene diamine tetra-(methylenephosphonic acid), or diethylene triamine penta-(methylenephosphonic acid) and mixtures thereof.
7. A detergent as claimed in Claim 1, characterized in that component (f) consists of from 7 to 13% by weight of ethanol and propylene glycol.
8. A detergent as claimed in Claims 1 to 7, characterized in that it contains from 0.1 to 1.5% by weight of enzymes.
9. A detergent as claimed in Claims 1 to 8, characterized in that it contains triethanolamine.
10. A detergent as claimed in Claims 1 to 9, characterized in that it has a pH value of from 7.2 to 9.
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ATE49608T1 (en) 1990-02-15
JPS61255999A (en) 1986-11-13
EP0201016A3 (en) 1987-09-23

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