EP0011166A1 - Liquid, cold-stable detergent concentrate and its use - Google Patents

Liquid, cold-stable detergent concentrate and its use Download PDF

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Publication number
EP0011166A1
EP0011166A1 EP79104170A EP79104170A EP0011166A1 EP 0011166 A1 EP0011166 A1 EP 0011166A1 EP 79104170 A EP79104170 A EP 79104170A EP 79104170 A EP79104170 A EP 79104170A EP 0011166 A1 EP0011166 A1 EP 0011166A1
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weight
composition according
carbon atoms
acid
potassium
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EP79104170A
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German (de)
French (fr)
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EP0011166B1 (en
Inventor
Wolfgang Bechstedt
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT79104170T priority Critical patent/ATE975T1/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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • 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 subject of DE-OS 26 09 752 is a clear, cold-resistant detergent concentrate with a solids content of up to 55% by weight, containing 8 to 18% by weight of one Potassium fatty acid soap, which is derived from fatty acids with 12 to 18 carbon atoms and mainly consists of oleic acid, 10 to 25% by weight of ethoxylated alcohols with 8 to 12 carbon atoms and an average of 5 to 10 ethylene glycol ether groups and 4 to 10% by weight sodium alkylbenzenesulfonates with 10 up to 14 carbon atoms in the alkyl group, furthermore optical brighteners and conventional solubilizers or water-miscible solvents.
  • Potassium fatty acid soap which is derived from fatty acids with 12 to 18 carbon atoms and mainly consists of oleic acid, 10 to 25% by weight of ethoxylated alcohols with 8 to 12 carbon atoms and an average of 5 to 10 ethylene glycol ether groups and 4 to 10% by weight sodium al
  • Means of this type are primarily intended for use in large laundry companies with automatically operated washing, drying and ironing machines, in which the individual work cycles overlap.
  • the composition of a detergent suitable for this must be coordinated in such a way that there are no interferences affecting the functioning of the machines or interrupting the work cycle.
  • the loading and unloading flaps running in grooves no longer have the necessary ease of movement and therefore no longer open and close according to the clock. Problems with spinning and hot ironing can also occur.
  • compacted laundry can only be detached from the drum wall with additional force, or problems can arise during the transport and smoothing of the laundry on the mangling line.
  • the ethoxylated alcohols listed under B) are derived from native or synthetic alcohols, in particular oxo alcohols having 8 to 14, preferably 9 to 12, carbon atoms.
  • the oxo alcohols can be linearly branched or methyl-branched in the 2-position. Mixtures of native alcohols and alcohols obtained by oxo reaction are also suitable.
  • the number of ethylene glycol ether groups is on average 5 to 10, preferably 6 to 8.
  • the proportion of ethoxylated alcohols in the liquid concentrates should be 5 to 9, preferably 6 to 8% by weight.
  • Component C) consists of linear sodium alkylbenzenesulfonate, in particular dodecylbenzenesulfonate, in proportions of 4 to 10, preferably 6 to 8,% by weight.
  • Optical brighteners of the formula I are preferably used, in which R 1 and R 2 are morpholino-, diethanolamino- or anili-. represent nest.
  • the optical brighteners are present in proportions of 0.05 to 1, preferably 0.1 to 0.7,% by weight.
  • Component D) serves to make the solution or the wash liquor alkaline.
  • the amount of potassium hydroxide is preferably such that it exceeds the stoichiometric amount required to form the potassium fatty acid soaps by 10 to 50 mol percent, in particular by 20 to 35 mol percent.
  • the triethanolamine (component F) improves the cold resistance of the concentrates and is present in amounts of up to 6% by weight, preferably 2 to 5% by weight.
  • Component G) consists of aliphatic C 1 -C 3 alcohols, ie methanol, ethanol, propanol and in particular isopropanol, and of the mixtures of the alcohols mentioned.
  • the content of these alcohols in the compositions is preferably 12 to 18% by weight.
  • Agents with fractions of less than 12% of the alcohols mentioned can also contain hydrotropic ether alcohols which are derived from C 1 -C 4 monoalcohols or ethylene glycol or propylene glycol or diglycols, or hydrotropic alkylbenzenesulfonates with short alkyl chains. 2 .B. Are suitable.
  • the proportion of these solution-improving substances can be up to 5%.
  • the water content of the detergent concentrate should not fall below 30% by weight. There are no limits in the direction of more dilution, but it is advisable not to exceed a water content of 55% in order to save on packaging and transport volume. In general, a water content of 30 to 50% by weight is sufficient to achieve optimal results, i.e. Such concentrates remain clear even after storage for several weeks at a temperature of -10 ° C and do not tend to solidify, gel or separate under such extreme conditions.
  • additives may also include biocides, fragrances, dyes, stabilizers, sequestering agents, neutral salts and optical brighteners of other constitution, but the total amount of such additives should not exceed 10% by weight and preferably less than 5% by weight, in particular less than 2 wt .-%, so that a negative influence on the cold stability is avoided.
  • the detergents according to the invention are used in an amount of 3 to 10 g per kg of dry laundry, preferably using softened water. They are suitable as pre or main detergents for textiles of all kinds, e.g. those made from cellulose, synthetic and semi-synthetic fibers. Preferred areas of application are fully automatic washing, drying and ironing devices, as are customary in large commercial laundries.
  • the potassium soaps used in the recipes still had the following fatty acid composition (in% by weight):
  • Component B An oxo alcohol of chain length C 9 -C 11 with 7 ethylene glycol ether groups was used as the ethoxylated alcohol (component B).
  • Component C consisted of linear Na dodecylbenzenesulfonate.
  • the sodium salt of the compound of the formula I in which R 1 and R 2 were morpholino radicals was used as the optical brightener (component D).
  • Component G consisted of isopropanol.
  • the component “salts” means small amounts of Na 2 SO 4 and NaCl which were present as accompanying substances of the alkylbenzenesulfonate and the optical brightener.
  • Table 2 The composition is shown in Table 2.
  • the soap including the excess potassium hydroxide solution, was first mixed together in the form of a 65% strength aqueous paste with the ethoxylate and the alkylbenzenesulfonate, which was in the form of a 50% strength aqueous solution, then the optical brightener dissolved in isopropanol was stirred in, and finally triethanolamine and water was added to the specified amount.
  • the concentrates were in the form of yellowish, clear solutions which were thin at room temperature and which remained clear and homogeneous when stored for three weeks in a climatic cabinet at -10 ° C and + 50 ° C. A multiple temperature change between + 50 ° and -10 ° C also did not change the appearance and behavior of the samples.
  • the concentrates were miscible with water in all proportions.

Abstract

A clear, cold-stable liquid washing agent concentrate consisting essentially of: (A) from 22.5% to 35% by weight of a potassium soap of fatty acids having 12 to 18 carbon atoms and a melting point of below 55 DEG C., (B) from 5% to 9% by weight of an ethoxylated primary alcohol having 5 to 10 oxyethylene units, (C) from 4% to 10% by weight of a sodium C10-C14 alkylbenzenesulfonate, (D) from 0.05% to 1% by weight of at least one optical brightener, (E) from 0.1% to 5% by weight of potassium hydroxide. (F) from 0 to 6% by weight of triethanolamine, (G) from 8% to 20% by weight of at least one C1-3 alcohol, and (H) the remainder up to 100% of water, wherein the amount of water is at least 30% by weight and the concentration of the total of components (A) to (E) does not exceed 50% by weight of the concentrate. The washing agent concentrate can be employed in all type of washings of textiles in soft or hard waters, preferably in amounts of from 3 to 10 gm per kg of dry wash.

Description

Bekanntlich bereitet es erhebliche Schwierigkeiten, klare wäßrige Waschmittelkonzentrate herzustellen, die sich bei niedrigen Temperaturen, insbesondere unterhalb des Gefrierpunktes bis -10 °C nicht entmischen bzw. verfestigen. Dies gilt insbesondere für seifenhaltige Konzentrate mit einem Wirkstoffgehalt von 50 und mehr Gew.-%. Zusätzliche Schwierigkeiten können auftreten, wenn derartige Mittel optische Aufheller enthalten. Durch niedrige Temperaturen bzw. Gefrieren der Lösungen verursachte Phasentrennungen bzw. Ausfällungen lassen sich vielfach auch nach dem Wiedererwärmen nicht mehr rückgängig machen. Durch stärkeres Verdünnen der Lösungen bzw. Anwendung größerer Mengen organischer Lösungsmittel kann man zwar derartigen Schwierigkeiten begegnen, jedoch erfordern verdünnte Lösungen ein höheres Verpackungs- und Transportvolumen, während große Mengen organischer Lösungsmittel wegen der damit verbundenen höheren Kosten sowie der leichteren Brennbarkeit Probleme aufwerfen.It is known that there are considerable difficulties in producing clear aqueous detergent concentrates which do not separate or solidify at low temperatures, in particular below freezing point down to -10 ° C. This applies in particular to soap-containing concentrates with an active substance content of 50% or more by weight. Additional difficulties can arise if such agents contain optical brighteners. Phase separations or precipitations caused by low temperatures or freezing of the solutions can often not be reversed even after reheating. While such dilutions can be addressed by diluting the solutions more or using larger amounts of organic solvents, diluted solutions require a higher volume of packaging and transportation, while large amounts of organic solvents pose problems because of the associated higher costs and easier flammability.

Gegenstand der DE-OS 26 09 752, durch welche diese Probleme im wesentlichen gelöst werden, ist ein klarflüssiges, kältebeständiges Waschmittelkonzentrat mit einem Feststoffgehalt bis 55 Gew.-%, enthaltend 8 bis 18 Gew.-% einer Kaliumfettsäureseife, die sich von Fettsäuren mit 12 bis 18 Kohlenstoffatomen ableitet und überwiegend aus ölsäure besteht, 10 bis 25 Gew.-% an ethoxylierten Alkoholen mit 8 bis 12 Kohlenstoffatomen und durchschnittlich 5 bis 10 Ethylenglycolethergruppen sowie 4 bis 10 Gew.-% Natriumalkylbenzolsulfonaten mit 10 bis 14 Kohlenstoffatomen in der Alkylgruppe, ferner optische Aufheller und übliche Lösungsvermittler bzw. mit Wasser mischbare Lösungsmittel.The subject of DE-OS 26 09 752, by means of which these problems are essentially solved, is a clear, cold-resistant detergent concentrate with a solids content of up to 55% by weight, containing 8 to 18% by weight of one Potassium fatty acid soap, which is derived from fatty acids with 12 to 18 carbon atoms and mainly consists of oleic acid, 10 to 25% by weight of ethoxylated alcohols with 8 to 12 carbon atoms and an average of 5 to 10 ethylene glycol ether groups and 4 to 10% by weight sodium alkylbenzenesulfonates with 10 up to 14 carbon atoms in the alkyl group, furthermore optical brighteners and conventional solubilizers or water-miscible solvents.

Mittel dieser Art sind in erster Linie zum Einsatz in Großwäschereibetrieben mit automatisch betriebenen Wasch-, Trocken- und Bügelmaschinen bestimmt, bei denen die einzelnen Arbeitstakte ineinander übergreifen. Die Zusammensetzung eines hierfür geeigneten Waschmittels muß so abgestimmt sein, daß keine die Funktion der Maschinen beeinträchtigende bzw. den Arbeitstakt unterbrechende Störungen eintreten. An bestimmten neuzeitlichen Waschautomaten hat sich nun gezeigt, daß bei Einsatz üblicher Waschmittel und in gewissem - allerdings geringerem - Maße auch bei Einsatz der Mittel gemäß DE-OS 26 09 752 die in Nuten laufenden Beschickungs- bzw. Entladungsklappen nicht mehr die notwendige Leichtgängigkeit aufweisen und daher nicht mehr taktgerecht öffren und schließen. Weiterhin kann es zu Problemen beim Schleudern und Heißmangeln kommen. Beispielsweise läßt sich in selbstzentrifugierenden Waschmaschinen kompaktierte Wäsche nur mit zusätzlichem Kraftaufwand von der Trommelwandung ablösen bzw. auf der Mangelstraße kann es zu Problemen beim Transport und Glätten der-Wäsche kommen.Means of this type are primarily intended for use in large laundry companies with automatically operated washing, drying and ironing machines, in which the individual work cycles overlap. The composition of a detergent suitable for this must be coordinated in such a way that there are no interferences affecting the functioning of the machines or interrupting the work cycle. In certain modern washing machines it has now been shown that when using conventional detergents and to a certain - but to a lesser extent - even when using the agents according to DE-OS 26 09 752, the loading and unloading flaps running in grooves no longer have the necessary ease of movement and therefore no longer open and close according to the clock. Problems with spinning and hot ironing can also occur. For example, in self-centrifuging washing machines, compacted laundry can only be detached from the drum wall with additional force, or problems can arise during the transport and smoothing of the laundry on the mangling line.

Es bestand nun die Aufgabe, diese zum Teil konstruktiv bedingten Probleme durch eine Änderung der Waschmittelrezeptur zu lösen, ohne auf die übrigen vorteilhaften Eigenschaften der Mittel, nämlich Klarlöslichkeit, Homogenität und Lagerbeständigkeit im Temperaturbereich zwischen -10 ° und +40 °C und daraus resultierende einwandfreie Pump-, Gieß- und Dosierfähigkeiten zu verzichten. Diese Aufgabenstellung wird durch die vorliegende Erfindung gelöst.The task now was to solve these problems, some of which were due to the design, by changing the detergent formulation, without affecting the other advantageous properties of the agents, namely clear solubility, homogeneity to dispense and storage stability in the temperature range between -10 ° and + 40 ° C and the resulting proper pumping, G and ieß- Dosierfähigkeiten. This problem is solved by the present invention.

Gegenstand der Erfindung ist ein klarflüssiges, wäßriges Waschmittelkonzentrat mit hoher Kältebeständigkeit, gekennzeichnet durch einen Gehalt an

  • A) 22,5 bis 35 Gew.-% einer Kaliümfettsäureseife, die sich von Fettsäuren mit 12 bis 18 Kohlenstoffatomen ableitet und zu 60 bis 100 Gew.-% aus gesättigten Fettsäuren mit 12 bis 14 Kohlenstoffatomen und/oder ölsäure besteht,
  • B) 5 bis 9 Gew.-% eines ethoxylierten primären linearen bzw. in 2-Stellung methylverzweigten Alkohols mit 8 bis 14 Kohlenstoffatomen und durchschnittlich 5 bis 10 Ethylenglycolethergruppen,
  • C) 4 bis 10 Gew.-% eines Natriumalkylbenzolsulfonats mit linearen, 10 bis 14 Kohlenstoffatomen aufweisenden Alkylketten,
  • D) 0,05 bis 1 Gew.-% mindestens eines optischen Aufhellers aus der Klasse der substituierten Stilbensulfonsäuren in Form des Na- oder K-Salzes,
  • E) 0,1 bis 5 Gew.-% Kaliumhydroxid,
  • F) O bis 6 Gew.-% Triethanolamin,
  • G) 8 bis 20 Gew.-% eines Alkohols mit 1 bzw. 3 Kohlenstoffatomen,

wobei die Konzentration der unter A) bis E) genannten Stoffe insgesamt 50 Gew.-% nicht übersteigt,The invention relates to a clear, liquid detergent concentrate with high low temperature resistance, characterized by a content of
  • A) 22.5 to 35% by weight of a potassium fatty acid soap which is derived from fatty acids with 12 to 18 carbon atoms and 60 to 100% by weight consists of saturated fatty acids with 12 to 14 carbon atoms and / or oleic acid,
  • B) 5 to 9% by weight of an ethoxylated primary linear or methyl-branched alcohol in the 2-position with 8 to 14 carbon atoms and an average of 5 to 10 ethylene glycol ether groups,
  • C) 4 to 10% by weight of a sodium alkylbenzenesulfonate with linear alkyl chains having 10 to 14 carbon atoms,
  • D) 0.05 to 1% by weight of at least one optical brightener from the class of substituted stilbene sulfonic acids in the form of the Na or K salt,
  • E) 0.1 to 5% by weight of potassium hydroxide,
  • F) 0 to 6% by weight of triethanolamine,
  • G) 8 to 20% by weight of an alcohol with 1 or 3 carbon atoms,

the concentration of the substances mentioned under A) to E) not exceeding a total of 50% by weight,

Die unter A) aufgeführten Kaliumseifen leiten sich von Fettsäuren natürlichen oder synthetischen Ursprungs ab, di zu 60 bis 100 Gew.-%, vorzugsweise 65 bis 95 Gew.-% aus Laurinsäure, Myristinsäure oder ölsäure bestehen. Gemische aus Laurinsäure und Myristinsäure sollen mindestens zur Hälfte, vorzugsweise mindestens zu zwei Dritteln aus Laurinsäure bestehen. Außer den genannten Säuren können auch mehrfach ungesättigte Fettsäuren, z.B. Linolsäure, in Anteilen von 0 bis 25, vorzugsweise von 0,1 bis 15 Gew.-% in den Fettsäuren enthalten sein. Der Anteil der gesättigten Fettsäuren mit 16 bis 18 Kohlenstoffatomen beträgt O bis höchstens 20, vorzugsweise 1 bis 15 Gew.-%, wobei zweckmäßigerweise der Anteil der Stearinsäure 5 Gew. und insbesondere 3 Gew.-% nicht überschreiten soll. Geeignete Fettsäuregemische weisen beispielsweise die folgende Zusammensetzung auf (in Gew.-%):

  • I) 50 - 95 %, vorzugsweise 60 - 90 % Laurinsäure, 5 - 50 %, vorzugsweise 10 - 40 % Myristinsäure, O - 10 %, vorzugsweise 1 - 10 % Palmitinsäure, O - 5 %, vorzugsweise 0,1 - 3 % Stearinsäure.
  • II) 60 - 100 %, vorzugsweise 65 - 95 % ölsäure, O - 25 %, vorzugsweise 0,1 - 15 % Linolsäure, O - 40 %, vorzugsweise 1 - 20 % Laurinsäure, O - 20 %, vorzugsweise 1 - 10 % Myristinsäure, O - 10 %, vorzugsweise 0,5 - 6 % Palmitinsäure, O - 5 %, vorzugsweise 0,1 - 3 % Stearinsäure.
  • III) 10 - 60 %, vorzugsweise 25 - 50 % Ölsäure, 40 - 70 %, vorzugsweise 25 - 50 % Laurinsäure, O - 20 %, vorzugsweise 5 - 25 % Myristinsäure, O - 10 %, vorzugsweise 0,5 - 5 % Palmitinsäure, O - 5 %, vorzugsweise 0,1 - 3 % Stearinsäure, O - 10 %, vorzugsweise 0,1 - 10 % Linolsäure.
The potassium soaps listed under A) are derived from fatty acids of natural or synthetic origin, ie 60 to 100% by weight, preferably 65 to 95% by weight, of lauric acid, myristic acid or oleic acid. Mixtures of lauric acid and myristic acid should consist of at least half, preferably at least two thirds, of lauric acid. In addition to the acids mentioned, polyunsaturated fatty acids, for example linoleic acid, can also be present in the fatty acids in proportions of 0 to 25, preferably 0.1 to 15% by weight. The proportion of saturated fatty acids with 16 to 18 carbon atoms is 0 to at most 20, preferably 1 to 15% by weight, the proportion of stearic acid expediently not exceeding 5% by weight and in particular 3% by weight. Suitable fatty acid mixtures have, for example, the following composition (in% by weight):
  • I) 50-95%, preferably 60-90% lauric acid, 5-50%, preferably 10-40% myristic acid, O-10%, preferably 1-10% palmitic acid, O- 5%, preferably 0.1-3% Stearic acid.
  • II) 60-100%, preferably 65-95% oleic acid, O-25%, preferably 0.1-15% linoleic acid, O-40%, preferably 1-20% lauric acid, O-20%, preferably 1-10% Myristic acid, O - 10%, preferably 0.5 - 6% palmitic acid, O - 5%, preferably 0.1 - 3% stearic acid.
  • III) 10-60%, preferably 25-50% oleic acid, 40-70%, preferably 25-50% lauric acid, O-20%, preferably 5-25% myristic acid, O-10%, preferably 0.5-5% Palmitic acid, O - 5%, preferably 0.1 - 3% stearic acid, O - 10%, preferably 0.1 - 10% linoleic acid.

Besonders bevorzugt sind Mittel auf der Grundlage der Zusammensetzung II. /5 Die unter B) aufgeführten ethoxylierten Alkohole leiten sich von nativen oder synthetischen Alkoholen, insbesondere Oxoalkoholen mit 8 bis 14, vorzugsweise 9 bis 12 Kohlenstoffatomen ab. Die Oxoalkohole können sowohl linear als auch in 2-Stellung methylverzweigt sein. Auch Gemische von nativen und durch Oxoreaktion erhaltenen Alkoholen sind geeignet. Die Zahl der Ethylenglycolethergruppen beträgt im Durchschnitt 5 bis 10, vorzugsweise 6 bis 8. Der Anteil der ethoxylierten Alkohole in den flüssigen Konzentraten soll 5 bis 9, vorzugsweise 6 bis 8 Gew.-% betragen.Agents based on the composition II. / 5 are particularly preferred The ethoxylated alcohols listed under B) are derived from native or synthetic alcohols, in particular oxo alcohols having 8 to 14, preferably 9 to 12, carbon atoms. The oxo alcohols can be linearly branched or methyl-branched in the 2-position. Mixtures of native alcohols and alcohols obtained by oxo reaction are also suitable. The number of ethylene glycol ether groups is on average 5 to 10, preferably 6 to 8. The proportion of ethoxylated alcohols in the liquid concentrates should be 5 to 9, preferably 6 to 8% by weight.

Die Komponente C) besteht aus linearem Natriumalkylbenzolsulfonat, insbesondere Dodecylbenzolsulfonat, in Anteilen von 4 bis 10, vorzugsweise 6 bis 8 Gew.-%.Component C) consists of linear sodium alkylbenzenesulfonate, in particular dodecylbenzenesulfonate, in proportions of 4 to 10, preferably 6 to 8,% by weight.

Die unter D) aufgeführten optischen Aufheller leiten sich ab von Verbindungen der Formeln

Figure imgb0001
Figure imgb0002
 worin die einzelnen Symbole die folgende Bedeutung haben:

  • Me = Na, K
  • R1, R2 = -NHCH3, -NCH3(CH2CH2OH), -N(CH2CH2OH)2
    Figure imgb0003
  • R3, R4 = H, -CH3, -Cl, -OCH3, -COOCH3, -CN, -SO2NR5R6, -CONR5R6 mit R5 und R6 = H oder Alkylreste mit 1 bis 3 Kohlenstoffatomen.
The optical brighteners listed under D) are derived from compounds of the formulas
Figure imgb0001
Figure imgb0002
 where the individual symbols have the following meaning:
  • Me = Na, K
  • R 1 , R 2 = -NHCH 3 , -NCH 3 (CH 2 CH 2 OH), -N (CH 2 CH 2 OH) 2
    Figure imgb0003
  • R 3 , R 4 = H, -CH 3 , -Cl, -OCH 3 , -COOCH 3 , -CN, -SO 2 NR 5 R 6 , -CONR 5 R 6 with R 5 and R 6 = H or alkyl radicals with 1 to 3 carbon atoms.

Bevorzugt werden optische Aufheller der Formel I verwendet, in der R1 und R2 Morpholino-, Diethanolamino- oder Anili- . noreste darstellen. Die optischen Aufheller liegen in Anteilen von 0,05 bis 1, vorzugsweise von 0,1 bis 0,7 Gew.-% vor.Optical brighteners of the formula I are preferably used, in which R 1 and R 2 are morpholino-, diethanolamino- or anili-. represent nest. The optical brighteners are present in proportions of 0.05 to 1, preferably 0.1 to 0.7,% by weight.

Die Komponente D) dient dazu, die Lösung bzw. die Waschlauge alkalisch zu stellen. Vorzugsweise ist die Menge des Kaliumhydroxids so bemessen, daß sie die zur Bildung der Kaliumfettsäureseifen benötigten stöchiometrischen Menge um 10 bis 50 Mol-Prozent, insbesondere um 20 bis 35 Mol-Prozent übersteigt.Component D) serves to make the solution or the wash liquor alkaline. The amount of potassium hydroxide is preferably such that it exceeds the stoichiometric amount required to form the potassium fatty acid soaps by 10 to 50 mol percent, in particular by 20 to 35 mol percent.

Das Triethanolamin (Komponente F) verbessert die Kältebeständigkeit der Konzentrate und ist in Mengen bis zu 6 Gew.-%, vorzugsweise 2 bis 5 Gew.-% anwesend.The triethanolamine (component F) improves the cold resistance of the concentrates and is present in amounts of up to 6% by weight, preferably 2 to 5% by weight.

Die Komponente G) besteht aus aliphatischen C1-C3-Alkoholen, d.h. Methanol, Ethanol, Propanol und insbesondere Isopropanol sowie aus den Gemischen der genannten Alkohole. Bevorzugt beträgt der Gehalt der Mittel an diesen Alkoholen 12 bis 18 Gew.-%. Mittel mit Anteilen von weniger als 12 % der genannten Alkohole können auch hydrotrop wirkende Etheralkohole, die sich von C1-C4-Monoalkoholen bzw. Ethylenglycol oder Propyenglycol bzw. Diglycolen ableiten, oder hydrotrop wirkende Alkylbenzolsulfonate mit kurzen Alkylketten enthalten. Geeignet sind 2.B. die Monomethyl-, Monoethyl-, Monopropyl-, Monoisopropyl- oder Monobutylether des Ethylenglycols sowie aus der Gruppe der Alkylbenzolsulfonate das Toluolsulfonat, Ethylbenzolsulfonat, Cumolsulfonat und Xylolsulfonat in Form der Kalium- bzw. vorzugsweise Natriumsalze. Der Anteil dieser lösungsverbessernden Stoffe kann bis zu 5 % betragen.Component G) consists of aliphatic C 1 -C 3 alcohols, ie methanol, ethanol, propanol and in particular isopropanol, and of the mixtures of the alcohols mentioned. The content of these alcohols in the compositions is preferably 12 to 18% by weight. Agents with fractions of less than 12% of the alcohols mentioned can also contain hydrotropic ether alcohols which are derived from C 1 -C 4 monoalcohols or ethylene glycol or propylene glycol or diglycols, or hydrotropic alkylbenzenesulfonates with short alkyl chains. 2 .B. Are suitable. the monomethyl, monoethyl, monopropyl, monoisopropyl or monobutyl ether of ethylene glycol and from the group of the alkylbenzenesulfonates the toluenesulfonate, ethylbenzenesulfonate, cumene sulfonate and xylene sulfonate in the form of the potassium or preferably sodium salts. The proportion of these solution-improving substances can be up to 5%.

Der Wassergehalt des Waschmittelkonzentrates soll 30 Gew.-% nicht unterschreiten. In Richtung einer stärkeren Verdünnung sind keine Grenzen gesetzt, jedoch empfiehlt es sich, im Sinne einer Einsparung an Verpackungs- und Transportvolumen einen Wassergehalt von 55 % nicht zu überschreiten. Im allgemeinen reicht ein Wassergehalt von 30 bis 50 Gew.-% zur Erzielung optimaler Ergebnisse aus, d.h. solche Konzentrate bleiben auch bei mehrwöchiger Lagerung bei einer Temperatur von -10 °C klarflüssig und neigen unter derartigen extremen Bedingungen nicht zum Erstarren, Gelieren oder Entmischen.The water content of the detergent concentrate should not fall below 30% by weight. There are no limits in the direction of more dilution, but it is advisable not to exceed a water content of 55% in order to save on packaging and transport volume. In general, a water content of 30 to 50% by weight is sufficient to achieve optimal results, i.e. Such concentrates remain clear even after storage for several weeks at a temperature of -10 ° C and do not tend to solidify, gel or separate under such extreme conditions.

An weiteren Zusatzstoffen können noch Biocide, Duftstoffe, Farbstoffe, Stabilisierungsmittel, Sequestrierungsmittel, Neutralsalze und optische Aufheller anderer Konstitution anwesend sein, jedoch soll der Anteil an derartigen Zusatzstoffen insgesamt 10 Gew.-% nicht überschreiten und vorzugsweise weniger als 5 Gew.-%, insbesondere weniger als 2 Gew.-% betragen, damit ein negativer Einfluß auf die Kältestabilität vermieden wird.Other additives may also include biocides, fragrances, dyes, stabilizers, sequestering agents, neutral salts and optical brighteners of other constitution, but the total amount of such additives should not exceed 10% by weight and preferably less than 5% by weight, in particular less than 2 wt .-%, so that a negative influence on the cold stability is avoided.

Die erfindungsgemäßen Waschmittel werden in einer Menge von 3 bis 10 g pro kg Trockenwäsche angewendet, vorzugsweise unter Verwendung von enthärtetem Wasser. Sie eignen sich als Vor- oder Hauptwaschmittel für Textilien aller Art, z.B. solchen aus Cellulose-, Synthese- und halbsynthetischen Fasern. Bevorzugtes Einsatzgebiet sind vollautomatisch betriebene Wasch-, Trocken- und Bügelvorrichtungen, wie sie in gewerblich betriebenen Großwäschereien üblich sind.The detergents according to the invention are used in an amount of 3 to 10 g per kg of dry laundry, preferably using softened water. They are suitable as pre or main detergents for textiles of all kinds, e.g. those made from cellulose, synthetic and semi-synthetic fibers. Preferred areas of application are fully automatic washing, drying and ironing devices, as are customary in large commercial laundries.

In einer weiteren Anwendungsform können die Mittel als waschkraftverstärkende Zusätze zu Waschlaugen üblicher Zusammensetzung, d.h. solchen, die neben Tensiden z.B. noch Waschalkalien, Phosphate, Sequestrierungsmittel, Bleichmittel und vergrauungsverhütende Stoffe enthalten, hinzugesetzt werden. Ein für die Verwendung in automatischen Großwaschanlagen besonders geeignetes flüssiges Waschalkalikonzentrat, mit dem das erfindungsgemäße Mittel bei der Anwendung kombiniert werden kann, weist die folgende Zusammensetzung auf:

  • 0,5 - 5 Gew.-% Natriumtripolyphosphat,
  • O - 25 Gew.-% Kaliumtripolyphosphat, wobei die Gesamtmenge an Tripolyphosphaten vorzugsweise 5 bis 20 Gew.-% beträgt,
  • 0 - 10 Gew.-%, vorzugsweise 1 bis 5 Gew.-% Natriumsilikat der Zusammensetzung Na2O : Si02 = 1 : 1 - 1 : 3,5,
  • 0,5 - 5 Gew.-% Natriumethylendiaminotetraacetat,
  • O - 25 Gew.-%, vorzugsweise 5 bis 22 Gew.-% Kaliumhydroxid,
  • Rest Wasser.
In a further form of application, the agents can be added as washing-strengthening additives to washing liquors of conventional composition, ie those which, in addition to surfactants, also contain, for example, washing alkalis, phosphates, sequestering agents, bleaching agents and anti-graying substances. A liquid washing alkali concentrate which is particularly suitable for use in large automatic washing systems and with which the agent according to the invention can be combined in use has the following composition:
  • 0.5 - 5% by weight sodium tripolyphosphate,
  • O - 25% by weight potassium tripolyphosphate, the total amount of tripolyphosphates preferably being 5 to 20% by weight,
  • 0-10% by weight, preferably 1 to 5% by weight sodium silicate of the composition Na 2 O: Si0 2 = 1: 1 - 1: 3.5,
  • 0.5 - 5% by weight sodium ethylenediaminotetraacetate,
  • 0 - 25% by weight, preferably 5 to 22% by weight, potassium hydroxide,
  • Rest of water.

Es handelt sich ebenfalls um eine klare, kältestabile und leicht dosierbare Lösung. Auf 1 Gewichtsteil des erfindungsgemäßen flüssigen Waschmittelkonzentrats werden 1 bis 4 Gewichtsteile des vorstehenden Waschalkalikonzentrates angewendet. Diese Mischungen bewähren sich insbesondere beim Waschen stark verschmutzter Berufswäsche. /9It is also a clear, cold stable and easy to dose solution. 1 to 4 parts by weight of the above washing alkali concentrate are applied to 1 part by weight of the liquid detergent concentrate according to the invention. These blends are particularly useful when washing heavily soiled workwear. / 9

B e i s p i e 1 eExample: 1 e

Die in den Rezepturen verwendeten Kaliumseifen wiesen die noch folgende Fettsäurezusammensetzung (in Gew.-%) auf:

Figure imgb0004
The potassium soaps used in the recipes still had the following fatty acid composition (in% by weight):
Figure imgb0004

Als ethoxylierter Alkohol (Komponente B) wurde ein Oxoalkohol der Kettenlänge C9-C11 mit 7 Ethylenglycolethergruppen verwendet. Die Komponente C bestand aus linearem Na-Dodecylbenzolsulfonat. Als optischer Aufheller (Komponente D) wurde das Natriumsalz der Verbindung gemäß Formel I verwendet, worin R1 und R2 Morpholinoreste bedeuteten. Die Komponente G bestand aus Isopropanol. Unter dem Bestandteil "Salze" werden geringe Mengen an Na2SO4 und NaCl verstanden, die als Begleitstoffe des Alkylbenzolsulfonats und des optischen Aufhellers vorlagen. Die Zusammensetzung ist der Tabelle 2 zu entnehmen.

Figure imgb0005
An oxo alcohol of chain length C 9 -C 11 with 7 ethylene glycol ether groups was used as the ethoxylated alcohol (component B). Component C consisted of linear Na dodecylbenzenesulfonate. The sodium salt of the compound of the formula I in which R 1 and R 2 were morpholino radicals was used as the optical brightener (component D). Component G consisted of isopropanol. The component "salts" means small amounts of Na 2 SO 4 and NaCl which were present as accompanying substances of the alkylbenzenesulfonate and the optical brightener. The composition is shown in Table 2.
Figure imgb0005

Zwecks Herstellung der Mittel wurden zunächst die Seife einschließlich der überschüssigen Kalilauge in Form einer 65 %igen wäßrigen Paste mit dem Ethoxylat und dem Alkylbenzolsulfonat, das als 50 %ige wäßrige Lösung vorlag, miteinander vermischt, darauf der in Isopropanol gelöste optische Aufheller eingerührt und abschließend Triethanolamin und Wasser bis zur angegebenen Menge zugefügt.For the preparation of the agents, the soap, including the excess potassium hydroxide solution, was first mixed together in the form of a 65% strength aqueous paste with the ethoxylate and the alkylbenzenesulfonate, which was in the form of a 50% strength aqueous solution, then the optical brightener dissolved in isopropanol was stirred in, and finally triethanolamine and water was added to the specified amount.

Die Konzentrate lagen als gelblich gefärbte, klare, bei Raumtemperatur dünnflüssige Lösungen vor, die bei dreiwöchiger Lagerung im Klimaschrank bei -10 °C und + 50 °C klar und homogen blieben. Ein mehrfacher Temperaturwechsel zwischen +50° und -10 °C veränderte das Aussehen und Verhalten der Proben ebenfalls nicht. Die Konzentrate waren in jedem Verhältnis mit Wasser mischbar.The concentrates were in the form of yellowish, clear solutions which were thin at room temperature and which remained clear and homogeneous when stored for three weeks in a climatic cabinet at -10 ° C and + 50 ° C. A multiple temperature change between + 50 ° and -10 ° C also did not change the appearance and behavior of the samples. The concentrates were miscible with water in all proportions.

Claims (11)

1. Klarflüssiges, wäßriges Waschmittelkonzentrat mit hoher Kältebeständigkeit, gekennzeichnet durch einen Gehalt an A) 22,5 bis 35 Gew.-% einer Kaliumfettsäureseife, die sich von Fettsäuren mit 12 bis 18 Kohlenstoffatomen ableitet und zu 60 bis 100 Gew.-% aus gesättigten Fettsäuren mit 12 bis 14 Kohlenstoffatomen und/oder ölsäure besteht, B) 5 bis 9 Gew.-% eines ethoxylierten primären linearen bzw. in 2-Stellung methylverzweigten Alkohols mit 8 bis 14 Kohlenstoffatomen und durchschnittlich 5 bis 10 Ethylenglycolethergruppen, C) 4 bis 10 Gew.-% eines Natriumalkylbenzolsulfonats mit linearen, 10 bis 14 Kohlenstoffatomen aufweisenden Alkylketten, D) 0,05 bis 1 Gew.-% mindestens eines optischen Aufhellers aus der Klasse der substituierten Stilbensulfonsäuren in Form des Na- oder K-Salzes, E) 0,1 bis 5 Gew.-% Kaliumhydroxid, F) O bis 6 Gew.-% Triethanolamin, G) 8 bis 20 Gew.-% eines Alkohols mit 1 bzw. 3 Kohlenstoffatomen,
wobei die Konzentration der unter A) bis E) genannten Stoffe insgesamt 50 Gew.-% nicht übersteigt.1. Clear, aqueous detergent concentrate with high cold resistance, characterized by a content of A) 22.5 to 35% by weight of a potassium fatty acid soap which is derived from fatty acids with 12 to 18 carbon atoms and 60 to 100% by weight consists of saturated fatty acids with 12 to 14 carbon atoms and / or oleic acid, B) 5 to 9% by weight of an ethoxylated primary linear or methyl-branched alcohol in the 2-position with 8 to 14 carbon atoms and an average of 5 to 10 ethylene glycol ether groups, C) 4 to 10% by weight of a sodium alkylbenzenesulfonate with linear alkyl chains having 10 to 14 carbon atoms, D) 0.05 to 1% by weight of at least one optical brightener from the class of substituted stilbene sulfonic acids in the form of the Na or K salt, E) 0.1 to 5% by weight of potassium hydroxide, F) 0 to 6% by weight of triethanolamine, G) 8 to 20% by weight of an alcohol with 1 or 3 carbon atoms,
the concentration of the substances mentioned under A) to E) does not exceed a total of 50% by weight. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die in der Kaliumseife enthaltene Fettsäure zu 65 bis 9,5, Gew.-% aus ölsäure besteht und nicht mehr als 3 Gew.-% Stearinsäure enthält.2. Composition according to claim 1, characterized in that the fatty acid contained in the potassium soap consists of 65 to 9.5 wt .-% of oleic acid and contains no more than 3 wt .-% stearic acid. 3. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die in der Kaliumseife enthaltende Fettsäure zu 75 bis 95 Gew.-% aus einem Gemisch von Laurinsäure und Myristinsäure bestehen, wovon mindestens die Hälfte, vorzugsweise mindestens zu zwei Drittel als Laurinsäure vorliegen.3. Composition according to claim 1, characterized in that the fatty acid contained in the potassium soap to 75 to 95 wt .-% consist of a mixture of lauric acid and myristic acid, of which at least half, preferably at least two-thirds are present as lauric acid. 4. Mittel nach Anspruch 1, dadurch_gekennzeichnet, daß die ethoxylierten Alkohole 9 bis 12 Kohlenstoffatome und 6 bis 8 Ethylenglykolethergruppen enthalten.4. Composition according to claim 1, characterized in that the ethoxylated alcohols contain 9 to 12 carbon atoms and 6 to 8 ethylene glycol ether groups. 5. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß das Alkylbenzolsulfonat als Na-Dodecylbenzolsulfonat in Anteilen von 6 bis 8 Gew.-% vorliegt.5. Composition according to claim 1, characterized in that the alkylbenzenesulfonate is present as Na-dodecylbenzenesulfonate in proportions of 6 to 8 wt .-%. 6. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die optischen Aufheller aus Verbindungen nachstehender Formeln bestehen:
Figure imgb0006
Figure imgb0007
 worin die einzelnen Symbole die folgende Bedeutung haben: Me =.Na, K R1, R2= -NHCH3, -NCH3(CH2CH2OH), -N(CH2CH2OH)2
Figure imgb0008
 R3, R4 = H, -CH3, -Cl, -OCH3, -COOCH3, -CN, -SO2NR5R6, -CONR5R6 mit R5 und R6 = H oder Alkylreste mit 1 bis 3 Kohlenstoffatomen. 6. Composition according to claim 1, characterized in that the optical brighteners consist of compounds of the following formulas:
Figure imgb0006
Figure imgb0007
 where the individual symbols have the following meaning: Me = .Na, KR 1 , R 2 = -NHCH 3 , -NCH 3 (CH 2 CH 2 OH), -N (CH 2 CH 2 OH) 2
Figure imgb0008
 R 3 , R 4 = H, -CH 3 , -Cl, -OCH 3 , -COOCH 3 , -CN, -SO 2 NR 5 R 6 , -CONR 5 R 6 with R 5 and R 6 = H or alkyl radicals with 1 to 3 carbon atoms. 7. Mittel nach Anspruch 6, dadurch gekennzeichnet, daß die Reste R1 und R2 Morpholino-, Diethanolamino- oder Anilinoreste darstellen.7. Composition according to claim 6, characterized in that the radicals R 1 and R 2 represent morpholino, diethanolamino or anilino residues. 8. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß der Anteil des unter F) aufgeführten Triethanolamins 2 bis 5 Gew.-% beträgt.8. Composition according to claim 1, characterized in that the proportion of the triethanolamine listed under F) is 2 to 5 wt .-%. 9. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die unter G) aufgeführten Alkohole in Anteilen von 12 bis 18 Gew.-% anwesend sind.9. Composition according to claim 1, characterized in that the alcohols listed under G) are present in proportions of 12 to 18 wt .-%. 10. Mittel nach Anspruch 9, dadurch gekennzeichnet, daß der Alkohol aus Isopropanol besteht.10. Composition according to claim 9, characterized in that the alcohol consists of isopropanol. 11. Verwendung der Mittel nach Anspruch 1 bis 10 als Waschmittel in automatisch betriebenen Waschvorrichtungen unter Einsatz von enthärtetem Wasser.11. Use of the agent according to claim 1 to 10 as a detergent in automatically operated washing devices using softened water.
EP79104170A 1978-11-02 1979-10-29 Liquid, cold-stable detergent concentrate and its use Expired EP0011166B1 (en)

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FR2526038A1 (en) * 1982-04-30 1983-11-04 Colgate Palmolive Co Liq. surfactant concentrate for industrial laundry - contains fatty acid soap, alkali metal alkyl benzene sulphonate and ethoxylated aliphatic alcohol
GB2187749A (en) * 1986-03-11 1987-09-16 Procter & Gamble Liquid detergent composition containing hydrophobic brightener
WO2002061024A2 (en) * 2000-10-31 2002-08-08 Colgate-Palmolive Company Cleansing composition

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US4561998A (en) * 1982-05-24 1985-12-31 The Procter & Gamble Company Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid
US4507219A (en) * 1983-08-12 1985-03-26 The Proctor & Gamble Company Stable liquid detergent compositions
EP0551396B1 (en) * 1990-09-28 1995-12-20 The Procter & Gamble Company Detergent compositions containing polyhydroxy fatty acid amide and alkyl ester sulfonate surfactants
ATE164390T1 (en) * 1990-09-28 1998-04-15 Procter & Gamble POLYHYDROXYFATTY ACID AMIDE SURFACTANT IN DETERGENT COMPOSITIONS CONTAINING BLEACH
US5174927A (en) * 1990-09-28 1992-12-29 The Procter & Gamble Company Process for preparing brightener-containing liquid detergent compositions with polyhydroxy fatty acid amines
ES2079680T3 (en) * 1990-09-28 1996-01-16 Procter & Gamble POLYHYDROXY-AMIDES OF FATTY ACIDS IN DETERGENT COMPOSITIONS CONTAINING AN AGENT FOR RELEASE OF DIRT.
US5254281A (en) * 1991-01-29 1993-10-19 The Procter & Gamble Company Soap bars with polyhydroxy fatty acid amides
US5589448A (en) * 1993-02-17 1996-12-31 The Clorox Company High water liquid enzyme prewash composition
US5789364A (en) * 1993-02-17 1998-08-04 The Clorox Company High water liquid enzyme prewash composition
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