EP0164072B1 - Washing agent with intensified washing power - Google Patents

Washing agent with intensified washing power Download PDF

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Publication number
EP0164072B1
EP0164072B1 EP19850106659 EP85106659A EP0164072B1 EP 0164072 B1 EP0164072 B1 EP 0164072B1 EP 19850106659 EP19850106659 EP 19850106659 EP 85106659 A EP85106659 A EP 85106659A EP 0164072 B1 EP0164072 B1 EP 0164072B1
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EP
European Patent Office
Prior art keywords
weight
detergent
acid
mol
ethylene oxide
Prior art date
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EP19850106659
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German (de)
French (fr)
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EP0164072A2 (en
EP0164072A3 (en
Inventor
Erich Frieser
Franz Pfeifer
Giesela Nitsch
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/18—Sulfonic acids or sulfuric acid esters; Salts thereof derived from amino alcohols
    • C11D1/20—Fatty acid condensates
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • DE-PS 23 27 describes 867 a washing process using a detergent with a combination of aliphatic polyethylene glycols from the group of ethoxylated C12 to C20 alcohols, alkanediols, amines, carboxylic acids, carbonamides or sulfonamides with degrees of ethoxylation from 2 to 6 and from 8 to 20 , wherein the mixing ratio of the low ethoxylated compound to the higher ethoxylated compound is 1: 5 to 2: 1.
  • washing and washing aids for carrying out a washing process are known, the surfactant combination of 20 to 90 wt .-% anionic, zwitterionic or nonionic surfactants and 10 to 80 wt .-% of a fabric softener, which contains a fatty acid condensation product with a certain proportion of fatty acid partial glycerides, the fatty acid condensation product being prepared by reacting a triglyceride from higher fatty acids with a hydroxyalkyl polyamine.
  • This detergent has both cleaning and fabric softening properties. The production of a detergent with particularly good detergency at low washing temperatures cannot be derived from this.
  • the low ethoxylated aliphatic C12 to C20 alcohols can be natural or synthetically produced linear or branched, saturated or unsaturated alcohols with 12 to 20 carbon atoms, to which 2 to 6 moles of ethylene oxide have been added. Ethylene oxide adducts of fatty alcohols or oxo alcohols or combinations of fatty alcohols or oxo alcohols are generally used.
  • Component a) can additionally or alternatively also consist of alkylphenol ethoxylates whose alkyl group contains 6 to 15 carbon atoms and to which 1.5 to 4 moles of ethylene oxide are attached.
  • the higher ethoxylated aliphatic C12 to C20 alcohols are also derived from natural or synthetic alcohols with 12 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated and to which 8 to 20 moles of ethylene oxide have been added per mole of alcohol.
  • Component b) also or additionally comprises higher ethoxylated alkylphenols having 6 to 15 carbon atoms in the alkyl group to which 6 to 20 moles of ethylene oxide have been added.
  • the weight ratio of component a): b) in the context of the present invention is in the range from 1: 0.5 to 1: 5.
  • the stated combination of the nonionic surfactants with a low and a high proportion of ethylene oxide relates to combinations which consist both of low ethoxylated aliphatic alcohols with higher ethoxylated alkylphenols and also combinations of lower ethoxylated alkylphenols with higher ethoxylated alcohols. In any case, it is important that the combination contains low ethoxylated constituents and higher ethoxylated constituents in a ratio of 1: 0.5 to 1: 5.
  • a condensation product which can be used according to the invention contains, for example, 2 to 20, preferably 5 to 15% by weight of diamide ester, 20 to 60, preferably 25 to 45% by weight of diamide, 5 to 40, preferably 10 to 35% by weight of monoamides, 5 to 40, preferably 10 to 30 wt .-% unreacted fatty acid triglyceride, the rest up to 100 wt .-% consists of free fatty acids, free amine, glycerin.
  • a particularly suitable condensation product is obtained, for example, by reacting 1 mol of fatty acid triglyceride, preferably 1 mol of hardened beef tallow, corresponding to 3 mol of fatty acid residues and 1 mol of hydroxyethylethylenediamine, which is acidified, if desired, with an inorganic or with a non-surfactant organic acid.
  • the reaction can be carried out until the reaction equilibrium is established; However, products in which the fatty acid condensation product makes up at least 50% by weight and preferably 60 to 90% by weight of the reaction product can also be used for technical purposes.
  • the reaction product is cooled in a known manner and, if necessary, brought into a specific shape, for example flake shape or granule shape or powder shape.
  • the reaction melt can also be mixed beforehand with a water-soluble non-surfactant organic or inorganic acid and the reaction product can be made slightly alkaline to slightly acidic.
  • Suitable water-soluble organic or inorganic acids are, for example, acetic acid, oxalic acid, glycolic acid, lactic acid, citric acid, tartaric acid and hydrochloric acid, sulfuric acid or phosphoric acid. Glycolic acid is preferably used.
  • the fatty acid condensation product is combined in the detergent according to the invention, in addition to the combination of low-ethoxylated and higher-ethoxylated alcohols or alkylphenols, with 5 to 60% by weight of other detergent constituents and, if appropriate, with anionic surfactants, but the amount of these is not more than the amount of the nonionic surfactants turn off.
  • Suitable anionic surfactants are alkali metal or ammonium or amine salts of linear alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alpha-sulfofatty acid ester salts and alkyl sulfates.
  • the other detergent components that can be contained in the process product and combined with the condensation product include, for example, framework substances of the water-soluble inorganic phosphate type; Also suitable are alkali metal salts of aminopolycarboxylic acids, such as, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid; alkali salts are also suitable organic phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid; Also suitable are polymeric carboxylic acids, such as polyacrylic acid, polyhydroxyacrylic acid, and copolymers of maleic acid with vinyl methyl ether or acrylic acid; Insoluble builders are also suitable, such as the sodium aluminosilicates of type Zeolite A 4, which have recently been used increasingly as a phosphate substitute.
  • alkali metal salts of aminopolycarboxylic acids such as,
  • Suitable builders are sodium carbonate and sodium or magnesium silicate.
  • Other common detergent ingredients are graying inhibitors, such as carboxymethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose and ethoxylated starch.
  • Alkali salts of saturated fatty acids with 12 to 22 carbon atoms and / or silicone oils and / or paraffins in amounts of up to 4% are suitable as foam inhibitors.
  • Compounds which are generally derived from diaminostilbenedisulfonic acids are suitable as optical brighteners; but also derivatives of the diarylpyrazoline, aminocoumarin, distirylbiphenyl, thiophene type, each alone or in mixtures, can be used as optical brighteners.
  • bleaching agent is often added to detergents, which preferably means active oxygen carriers, such as sodium perborate, sodium percarbonate, in each case alone or in combination with organic, peracid-forming n-acyl compounds, for example tetraacetylethylene diamine, tetraacetylglycoluril as bleach activators.
  • active oxygen carriers such as sodium perborate, sodium percarbonate
  • organic, peracid-forming n-acyl compounds for example tetraacetylethylene diamine, tetraacetylglycoluril
  • H2O2-providing salts such as, for example, caroates, perbenzoates or peroxyphthalates, and also organic or inorganic active chlorine carriers, such as, for example, alkali metal hypochlorites, dichloro- or trichloroisocyanuric acid or their alkali metal salts, can be used as bleaching agents.
  • the detergents according to the invention occasionally contain enzymes, with proteases and amylases resistant to alkali, perborate and surfactants being preferred. So much is used on proteases that there is a protease activity of 100 to 2500 LVE per gram of finished product, and so much is used on amylases that there is an amylase activity of 20 to 2,000 SKBE per gram of finished product.
  • Powdered detergents can be prepared by first preparing the condensation product and then suspending it together with the other detergent constituents, insofar as they are heat-stable, into an aqueous suspension and then spray drying. The spray-dried product can then be mixed with the remaining ingredients such as bleaching agents, bleach activators, enzymes and fragrances. To produce liquid detergents, the condensation product, which is in molten or emulsified form, is worked into the preferably warm solution of the other constituents in water. The detergents according to the invention show significantly improved washing performance and controlled foaming behavior when used.
  • Example 1 shows the production of a detergent according to the invention (Example 1) and the production of detergents according to the prior art (Example 2, without the addition of a condensation product) and the production of a further detergent according to the prior art without the addition of a condensation product and without addition a combination of nonionic surfactants, consisting of low ethoxylated and highly ethoxylated compounds (Example 3).
  • Example 1 5% by weight of tallow fatty alcohol + 4 moles of ethylene oxide and 5% by weight of tallow fatty alcohol + 14 moles of ethylene oxide were sprayed onto the basic detergent of Example 1, as described in Example 1.
  • washing tests were carried out in a 4 kg dry laundry household washing machine. Normally soiled household laundry and test fabrics with test soiling were used. The water hardness was 9 ° dH, the dosage in the two-eye washing process in the pre-wash and main wash was 80 g each.
  • the whiteness (reflectance in%) of the washed test fabric was determined using an Elrephomat DFC 5 (Zeiss company) with a FL 46 filter and statistically evaluated. The following results were obtained: example Remission 1 69.3 2nd 64.7 3rd 60.9

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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)

Description

Die zunehmende Bedeutung von Pflegeleichtwäsche aus Baumwolle, Synthesefasern und Baumwoll/Synthesefaser-Gemischen bedingt infolge der festen Haftung von Fett-/Öl- und Pigmentschmutz an diesen Textilien gesteigerte Anforderungen an die Waschwirkung von Textilwaschmitteln für den Haushalt und für gewerbliche Wäschereien. Hinzu kommt, daß man bestrebt ist, zur Einsparung von Energie die 95 °C-Kochwäsche durch Waschverfahren bei 40 bis 80 °C zu ersetzen.The increasing importance of easy-care laundry made of cotton, synthetic fibers and cotton / synthetic fiber blends means that due to the firm adhesion of grease / oil and pigment soils to these textiles, the requirements for the washing effect of textile detergents for the household and for commercial laundries are increasing. In addition, efforts are being made to replace the 95 ° C. hot wash with washing processes at 40 to 80 ° C. in order to save energy.

Eine der Möglichkeiten zur Verbesserung der Waschkraft beim Waschen bei niedrigen Temperaturen besteht in der Verwendung von nichtionischen Tensiden, allein oder auch in Kombination mit anionischen Tensiden vom Typ der Alkylbenzolsulfonate, Fettalkoholsulfate, Alkansulfonate, Olefinsulfonate usw. So beschreibt zum Beispiel die DE-PS 23 27 867 ein Waschverfahren unter Verwendung eines Waschmittels mit einer Kombination von aliphatischen Polyethylenglykolen aus der Gruppe der ethoxylierten C₁₂- bis C₂₀-Alkohole, -Alkandiole, -Amine, -Carbonsäuren, -Carbonamiden oder -Sulfonamiden mit Ethoxylierungsgraden von 2 bis 6 und von 8 bis 20, wobei das Mischungsverhältnis der niedrig ethoxylierten Verbindung zur höher ethoxylierten Verbindung 1 : 5 bis 2 : 1 beträgt. Aus der DE-PS 19 22 046 sind Wasch- und Waschhilfsmittel zur Durchführung eines Waschverfahrens bekannt, dessen Tensidkombination aus 20 bis 90 Gew.-% anionischen, zwitterionischen oder nichtionischen Tensiden und 10 bis 80 Gew.-% eines Textilweichmachers besteht, der ein Fettsäurekondensationsprodukt mit einem bestimmten Anteil an Fettsäureteilglyceriden enthält, wobei das Fettsäurekondensationsprodukt durch Umsetzung eines Triglycerids aus höheren Fettsäuren mit einem Hydroxyalkylpolyamin hergestellt wird. Dieses Waschmittel besitzt gleichzeitig reinigende und textilweichmachende Eigenschaften. Die Herstellung eines Waschmittels mit besonders guter Waschkraft bei niedrigen Waschtemperaturen läßt sich hieraus nicht ableiten.One of the ways to improve the washing power when washing at low temperatures is to use nonionic surfactants, alone or in combination with anionic surfactants of the alkylbenzenesulfonate type, fatty alcohol sulfates, alkanesulfonates, olefin sulfonates, etc. For example, DE-PS 23 27 describes 867 a washing process using a detergent with a combination of aliphatic polyethylene glycols from the group of ethoxylated C₁₂ to C₂₀ alcohols, alkanediols, amines, carboxylic acids, carbonamides or sulfonamides with degrees of ethoxylation from 2 to 6 and from 8 to 20 , wherein the mixing ratio of the low ethoxylated compound to the higher ethoxylated compound is 1: 5 to 2: 1. From DE-PS 19 22 046 washing and washing aids for carrying out a washing process are known, the surfactant combination of 20 to 90 wt .-% anionic, zwitterionic or nonionic surfactants and 10 to 80 wt .-% of a fabric softener, which contains a fatty acid condensation product with a certain proportion of fatty acid partial glycerides, the fatty acid condensation product being prepared by reacting a triglyceride from higher fatty acids with a hydroxyalkyl polyamine. This detergent has both cleaning and fabric softening properties. The production of a detergent with particularly good detergency at low washing temperatures cannot be derived from this.

Es wurde nun gefunden, daß ein Waschmittel, enthaltend nichtionische und gegebenenfalls anionische Tenside und ein Kondensationsprodukt, hergestellt durch Umsetzung eines Triglycerids aus höheren Fettsäuren und einem Hydroxyalkylpolyamin sowie andere übliche Waschmittel, verstärkte Waschkraft aufweist, wenn es

4 bis 30 Gew.-%
einer Kombination aus
  • a) niedrig ethoxylierten aliphatischen C₁₂- bis C₂₀- Alkoholen mit 2 bis 6 Mol Ethylenoxid und/oder niedrig ethoxylierten C6-15 Alkylphenolen mit 1,5 bis 4 Mol Ethylenoxid
  • b) höher ethoxylierten aliphatischen C₁₂- bis C₂₀- Alkoholen mit 8 bis 20 Mol Ethylenoxid und/oder höher ethoxylierten C6-15 Alkylphenolen mit 6 bis 20 Mol Ethylenoxid,
wobei das Verhältnis von a) : b) im Bereich von 1 : 0,5 bis 1 : 5 liegt,
1 bis 10 Gew.-%
eines Umsetzungsproduktes von Triglyceriden höherer Fettsäuren mit 10 bis 22 Kohlenstoffatomen im Fettsäurerest mit Hydroxyalkylpolyaminen, die wenigstens eine Hydroxyethyl-, Hydroxypropyl- oder Dihydroxypropylgruppe und wenigstens zwei an Stickstoff gebundene Wasserstoffatome enthalten
5 bis 60 Gew.-%
sonstiger üblicher Waschmittelbestandteile außer anionischen Tensiden
0 bis 30 Gew.-%
anionische Tenside, jedoch nicht mehr anionische Tenside als nichtionische Tenside
enthält.It has now been found that a detergent containing nonionic and optionally anionic surfactants and a condensation product, prepared by reacting a triglyceride from higher fatty acids and a hydroxyalkyl polyamine and other conventional detergents, has increased detergency if it
4 to 30% by weight
a combination of
  • a) Low ethoxylated aliphatic C₁₂ to C₂₀ alcohols with 2 to 6 moles of ethylene oxide and / or low ethoxylated C6-15 alkylphenols with 1.5 to 4 moles of ethylene oxide
  • b) higher ethoxylated aliphatic C₁₂ to C₂₀ alcohols with 8 to 20 moles of ethylene oxide and / or higher ethoxylated C6-15 alkylphenols with 6 to 20 moles of ethylene oxide,
the ratio of a): b) being in the range from 1: 0.5 to 1: 5,
1 to 10% by weight
a reaction product of triglycerides of higher fatty acids with 10 to 22 carbon atoms in the fatty acid residue with hydroxyalkyl polyamines which have at least one hydroxyethyl, hydroxypropyl or dihydroxypropyl group and at least two Contain nitrogen-bound hydrogen atoms
5 to 60% by weight
other common detergent ingredients other than anionic surfactants
0 to 30% by weight
anionic surfactants, but no more anionic surfactants than nonionic surfactants
contains.

Die niedrig ethoxylierten aliphatischen C₁₂- bis C₂₀-Alkohole (Bestandteil a)) können natürliche oder synthetisch hergestellte lineare oder verzweigte, gesättigte oder ungesättigte Alkohole mit 12 bis 20 Kohlenstoffatomen sein, an die man 2 bis 6 Mol Ethylenoxid angelagert hat. Im allgemeinen verwendet man Ethylenoxidaddukte von Fettalkoholen oder Oxoalkoholen oder von Kombinationen aus Fettalkoholen oder Oxoalkoholen. Bestandteil a) kann zusätzlich beziehungsweise alternativ auch aus Alkylphenol-Ethoxylaten bestehen, deren Alkylgruppe 6 bis 15 Kohlenstoffatome enthält und an die 1,5 bis 4 Mol Ethylenoxid angelagert sind. Die höher ethoxylierten aliphatischen C₁₂- bis C₂₀-Alkohole leiten sich ebenfalls von natürlichen oder synthetischen Alkoholen mit 12 bis 20 Kohlenstoffatomen ab, die linear oder verzweigt, gesättigt oder ungesättigt sein können und an die man 8 bis 20 Mol Ethylenoxid pro Mol Alkohol angelagert hat. Bestandteil b) umfaßt außerdem oder zusätzlich höher ethoxylierte Alkylphenole mit 6 bis 15 Kohlenstoffatomen in der Alkylgruppe, an die man 6 bis 20 Mol Ethylenoxid angelagert hat. Das Gewichtsverhältnis von Bestandteil a) : b) liegt im Rahmen der vorliegenden Erfindung im Bereich von 1 : 0,5 bis 1 : 5.The low ethoxylated aliphatic C₁₂ to C₂₀ alcohols (component a)) can be natural or synthetically produced linear or branched, saturated or unsaturated alcohols with 12 to 20 carbon atoms, to which 2 to 6 moles of ethylene oxide have been added. Ethylene oxide adducts of fatty alcohols or oxo alcohols or combinations of fatty alcohols or oxo alcohols are generally used. Component a) can additionally or alternatively also consist of alkylphenol ethoxylates whose alkyl group contains 6 to 15 carbon atoms and to which 1.5 to 4 moles of ethylene oxide are attached. The higher ethoxylated aliphatic C₁₂ to C₂₀ alcohols are also derived from natural or synthetic alcohols with 12 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated and to which 8 to 20 moles of ethylene oxide have been added per mole of alcohol. Component b) also or additionally comprises higher ethoxylated alkylphenols having 6 to 15 carbon atoms in the alkyl group to which 6 to 20 moles of ethylene oxide have been added. The weight ratio of component a): b) in the context of the present invention is in the range from 1: 0.5 to 1: 5.

Die genannte Kombination der nichtionischen Tenside mit einem niedrigen und einem hohen Anteil an Ethylenoxid bezieht sich auf Kombinationen, die sowohl aus niedrig ethoxylierten aliphatischen Alkoholen mit höher ethoxylierten Alkylphenolen als auch auf Kombinationen von niedrig ethoxylierten Alkylphenolen mit höher ethoxylierten Alkoholen. Wichtig ist jedenfalls, daß die Kombination niedrig ethoxylierte Bestandteile und höher ethoxylierte Bestandteile im Verhältnis von 1 : 0,5 bis 1 : 5 enthält.The stated combination of the nonionic surfactants with a low and a high proportion of ethylene oxide relates to combinations which consist both of low ethoxylated aliphatic alcohols with higher ethoxylated alkylphenols and also combinations of lower ethoxylated alkylphenols with higher ethoxylated alcohols. In any case, it is important that the combination contains low ethoxylated constituents and higher ethoxylated constituents in a ratio of 1: 0.5 to 1: 5.

Bei der Herstellung des Fettsäure/Hydroxyalkylpolyamin-Produktes setzt man pro Mol Hydroxyalkylpolyamin zweckmäßigerweise 1,3 bis 4, vorzugsweise 1,5 bis 3 Mol Fettsäurereste ein. Ein erfindungsgemäß verwendbares Kondensationsprodukt enthält beispielsweise 2 bis 20, vorzugsweise 5 bis 15 Gew.-% Diamidester, 20 bis 60, vorzugsweise 25 bis 45 Gew.-% Diamid, 5 bis 40, vorzugsweise 10 bis 35 Gew.-% Monoamide, 5 bis 40, vorzugsweise 10 bis 30 Gew.-% nichtumgesetztes Fettsäuretriglycerid, der Rest bis auf 100 Gew.-% besteht aus freien Fettsäuren, freiem Amin, Glycerin. Ein besonders geeignetes Kondensationsprodukt erhält man beispielsweise durch Umsetzung von 1 Mol Fettsäuretriglycerid, vorzugsweise 1 Mol gehärtetem Rindertalg, entsprechend 3 Mol Fettsäureresten und 1 Mol Hydroxyethylethylendiamin, das man gewünschtenfalls mit einer anorganischen oder mit einer nichttensidischen organischen Säure absäuert.In the preparation of the fatty acid / hydroxyalkylpolyamine product, 1.3 to 4, preferably 1.5 to 3, moles of fatty acid residues are advantageously used per mole of hydroxyalkylpolyamine. A condensation product which can be used according to the invention contains, for example, 2 to 20, preferably 5 to 15% by weight of diamide ester, 20 to 60, preferably 25 to 45% by weight of diamide, 5 to 40, preferably 10 to 35% by weight of monoamides, 5 to 40, preferably 10 to 30 wt .-% unreacted fatty acid triglyceride, the rest up to 100 wt .-% consists of free fatty acids, free amine, glycerin. A particularly suitable condensation product is obtained, for example, by reacting 1 mol of fatty acid triglyceride, preferably 1 mol of hardened beef tallow, corresponding to 3 mol of fatty acid residues and 1 mol of hydroxyethylethylenediamine, which is acidified, if desired, with an inorganic or with a non-surfactant organic acid.

Zur Herstellung des Kondensationsproduktes geht von einem Hydroxyalkylpolyamin aus, das man mit einem Triglycerid unter Erwärmen auf Temperaturen von 90 bis 150 °C, vorzugsweise von 90 bis 130 °C reagieren läßt. Je nach der angewandten Temperatur sind bis zu 15, vorzugsweise bis zu 18 Stunden notwendig, um das Reaktionsgleichgewicht einzustellen. Setzt man 1 Mol gehärteten Talg mit einem Mol Hydroxyethylethylendiamin unter den genannten Bedingungen um, erhält man Kondensationsprodukte etwa der folgenden Zusammensetzung:

2 - 6 Gew.-%
Diamidester,
15 - 52 Gew.-%
Diamide,
11 - 27 Gew.-%
Monoamide,
9 - 27 Gew.-%
Talgfettsäuremono-, Di- und Triglyceride.
Der Rest bis auf 100 % sind freie Säuren, Glycerin und Wasser.The preparation of the condensation product is based on a hydroxyalkyl polyamine which is allowed to react with a triglyceride while heating to temperatures from 90 to 150 ° C., preferably from 90 to 130 ° C. Depending on the temperature used, up to 15, preferably up to 18, hours are necessary to set the reaction equilibrium. If 1 mol of hardened tallow is reacted with one mol of hydroxyethylethylenediamine under the conditions mentioned, condensation products of approximately the following composition are obtained:
2 - 6% by weight
Diamides,
15 - 52% by weight
Diamides,
11-27% by weight
Monoamides,
9-27% by weight
Tallow fatty acid mono-, di- and triglycerides.
The rest up to 100% are free acids, glycerin and water.

Man kann die Umsetzung bis zur Einstellung des Reaktionsgleichgewichts durchführen; für technische Zwecke sind allerdings auch Produkte brauchbar, bei denen das Fettsäurekondensationsprodukt wenigstens 50 Gew.-% und vorzugsweise 60 bis 90 Gew.-% des Reaktionsproduktes ausmacht. Zur Beendigung der Reaktion wird das Reaktionsprodukt in bekannter Weise abgekühlt und gegebenenfalls in eine bestimmte Form, beispielsweise Schuppenform oder Granulatform oder Pulverform gebracht. Man kann aber auch vorher die Reaktionsschmelze mit einer wasserlöslichen nichtensidischen organischen oder anorganischen Säure versetzen und das Reaktionsprodukt schwach alkalisch bis schwach sauer einstellen. Geeignete wasserlösliche organische oder anorganische Säuren sind zum Beispiel Essigsäure, Oxalsäure, Glykolsäure, Milchsäure, Zitronensäure, Weinsäure sowie Salzsäure, Schwefelsäure oder Phosphorsäure. Bevorzugt verwendet man Glykolsäure.The reaction can be carried out until the reaction equilibrium is established; However, products in which the fatty acid condensation product makes up at least 50% by weight and preferably 60 to 90% by weight of the reaction product can also be used for technical purposes. To terminate the reaction, the reaction product is cooled in a known manner and, if necessary, brought into a specific shape, for example flake shape or granule shape or powder shape. However, the reaction melt can also be mixed beforehand with a water-soluble non-surfactant organic or inorganic acid and the reaction product can be made slightly alkaline to slightly acidic. Suitable water-soluble organic or inorganic acids are, for example, acetic acid, oxalic acid, glycolic acid, lactic acid, citric acid, tartaric acid and hydrochloric acid, sulfuric acid or phosphoric acid. Glycolic acid is preferably used.

Das Fettsäurekondensationsprodukt kombiniert man im erfindungsgemäßen Waschmittel außer mit der Kombination niedrig ethoxylierter und höher ethoxylierter Alkohole bzw. Alkylphenole weiterhin mit 5 bis 60 Gew.-% sonstigen Waschmittelbestandteilen und gegebenenfalls mit anionischen Tensiden, die jedoch in ihrer Menge nicht mehr als die Menge der nichtionischen Tenside ausmachen. Als anionische Tenside kommen Alkali- oder Ammonium- oder Aminsalze von linearen Alkylbenzolsulfonaten, Alkansulfonaten, Olefinsulfonaten, alpha-Sulfofettsäureestersalzen und Alkylsulfaten in Frage. Zu den sonstigen Waschmittelbestandteilen, die in dem Verfahrensprodukt enthalten sein können und mit dem Kondensationsprodukt kombiniert werden, gehören beispielsweise Gerüstsubstanzen vom Typ der wasserlöslichen anorganischen Phosphate; ferner sind geeignet Alkalisalze von Aminopolycarbonsäuren, wie zum Beispiel Nitrilotriessigsäure, Ethylendiamintetraessigsäure; außerdem sind geeignet Alkalisalze organischer Phosphonsäuren, wie zum Beispiel 1-Hydroxyethan-1,1-diphosphonsäure, Aminotrimethylentriphosphonsäure, Ethylendiamintetramethylenphosphonsäure, Diethylentriaminpentamethylenphosphonsäure; außerdem geeignet sind polymere Carbonsäuren, wie zum Beispiel Polyacrylsäure, Polyhydroxyacrylsäure, sowie Copolymere von Maleinsäure mit Vinylmethylether bzw. Acrylsäure; auch unlösliche Gerüstsubstanzen sind geeignet wie zum Beispiel die in letzter Zeit als Phosphatsubstitut in zunehmendem Maße verwendeten Natriumalumosilikate vom Typ Zeolith A 4. Ebenfalls geeignete Gerüstsubstanzen sind Natriumcarbonat und Natrium- bzw. Magnesiumsilikat. Andere übliche Waschmittelbestandteile sind Vergrauungsinhibitoren, wie zum Beispiel Carboxymethylcellulose, Methylcellulose, Methylhydroxypropylcellulose, Hydroxyethylcellulose und ethoxylierte Stärke. Als Schauminhibitoren sind Alkalisalze gesättigter Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Siliconöle und/oder Paraffine in Mengen bis zu 4 % geeignet. Als optische Aufheller sind Verbindungen geeignet, die sich in der Regel von Diaminostilbendisulfonsäuren ableiten; aber auch Derivate vom Typ der Diarylpyrazoline, des Aminocumarins, des Distirylbiphenyls, des Thiophens jeweils allein oder in Mischungen, können als optische Aufheller eingesetzt werden. Zur Entfernung bleichbarer Verschmutzungen werden in Waschmitteln häufig 10 bis 20 Gew.-% Bleichmittel zugesetzt, worunter vorzugsweise Aktivsauerstoffträger verstanden werden, wie zum Beispiel Natriumperborat, Natriumpercarbonat, jeweils alleine oder in Kombination mit organischen, Persäure bildenden n-Acylverbindungen, zum Beispiel Tetraacetylethylendiamin, Tetraacetylglykoluril als Bleichaktivatoren. Auch H₂O₂ liefernde Salze wie zum Beispiel Caroate, Perbenzoate oder Peroxyphthalate, sowie organische oder anorganische Aktivchlorträger, wie zum Beispiel Alkalihypochlorite, Dichlor- oder Trichlorisocyanursäure bzw. deren Alkalisalze können als Bleichmittel eingesetzt werden.The fatty acid condensation product is combined in the detergent according to the invention, in addition to the combination of low-ethoxylated and higher-ethoxylated alcohols or alkylphenols, with 5 to 60% by weight of other detergent constituents and, if appropriate, with anionic surfactants, but the amount of these is not more than the amount of the nonionic surfactants turn off. Suitable anionic surfactants are alkali metal or ammonium or amine salts of linear alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alpha-sulfofatty acid ester salts and alkyl sulfates. The other detergent components that can be contained in the process product and combined with the condensation product include, for example, framework substances of the water-soluble inorganic phosphate type; Also suitable are alkali metal salts of aminopolycarboxylic acids, such as, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid; alkali salts are also suitable organic phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid; Also suitable are polymeric carboxylic acids, such as polyacrylic acid, polyhydroxyacrylic acid, and copolymers of maleic acid with vinyl methyl ether or acrylic acid; Insoluble builders are also suitable, such as the sodium aluminosilicates of type Zeolite A 4, which have recently been used increasingly as a phosphate substitute. Also suitable builders are sodium carbonate and sodium or magnesium silicate. Other common detergent ingredients are graying inhibitors, such as carboxymethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose and ethoxylated starch. Alkali salts of saturated fatty acids with 12 to 22 carbon atoms and / or silicone oils and / or paraffins in amounts of up to 4% are suitable as foam inhibitors. Compounds which are generally derived from diaminostilbenedisulfonic acids are suitable as optical brighteners; but also derivatives of the diarylpyrazoline, aminocoumarin, distirylbiphenyl, thiophene type, each alone or in mixtures, can be used as optical brighteners. To remove bleachable soiling, 10 to 20% by weight of bleaching agent is often added to detergents, which preferably means active oxygen carriers, such as sodium perborate, sodium percarbonate, in each case alone or in combination with organic, peracid-forming n-acyl compounds, for example tetraacetylethylene diamine, tetraacetylglycoluril as bleach activators. H₂O₂-providing salts such as, for example, caroates, perbenzoates or peroxyphthalates, and also organic or inorganic active chlorine carriers, such as, for example, alkali metal hypochlorites, dichloro- or trichloroisocyanuric acid or their alkali metal salts, can be used as bleaching agents.

Zur Beseitigung von Eiweiß- und Stärkeverschmutzungen enthalten die erfindungsgemäßen Waschmittel gelegentlich Enzyme, wobei alkali-, perborat- und tensidbeständige Proteasen und Amylasen bevorzugt werden. An Proteasen verwendet man soviel, daß eine Protease-Aktivität von 100 bis 2 500 LVE pro Gramm Fertigprodukt vorliegt, und an Amylasen verwendet man soviel, daß pro Gramm Fertigprodukt eine Amylase-Aktivität von 20 bis 2 000 SKBE vorliegt. Pulverförmige Waschmittel können hergestellt werden, indem man zunächst das Kondensationsprodukt herstellt und dann dieses zusammen mit den anderen Waschmittelbestandteilen, soweit sie hitzestabil sind, zu einer wäßrigen Suspension suspendiert und anschließend sprühtrocknet. Das sprühgetrocknete Produkt kann dann mit den restlichen Bestandteilen wie Bleichmitteln, Bleichaktivatoren, Enzymen und Duftstoffen vermischt werden. Zur Herstellung flüssiger Waschmittel arbeitet man das in geschmolzener oder emulgierter Form vorliegende Kondensationsprodukt in die vorzugsweise warme Lösung der übrigen Bestandteile in Wasser ein. Die erfindungsgemäßen Waschmittel zeigen deutlich verbesserte Waschleistung und kontrolliertes Schaumverhalten bei der Anwendung.To remove protein and starch contamination, the detergents according to the invention occasionally contain enzymes, with proteases and amylases resistant to alkali, perborate and surfactants being preferred. So much is used on proteases that there is a protease activity of 100 to 2500 LVE per gram of finished product, and so much is used on amylases that there is an amylase activity of 20 to 2,000 SKBE per gram of finished product. Powdered detergents can be prepared by first preparing the condensation product and then suspending it together with the other detergent constituents, insofar as they are heat-stable, into an aqueous suspension and then spray drying. The spray-dried product can then be mixed with the remaining ingredients such as bleaching agents, bleach activators, enzymes and fragrances. To produce liquid detergents, the condensation product, which is in molten or emulsified form, is worked into the preferably warm solution of the other constituents in water. The detergents according to the invention show significantly improved washing performance and controlled foaming behavior when used.

BeispieleExamples

Die folgenden Beispiele zeigen die Herstellung eines erfindungsgemäßen Waschmittels (Beispiel 1) sowie die Herstellung von Waschmitteln nach dem Stand der Technik (Beispiel 2, ohne Zusatz eines Kondensationsproduktes) und die Herstellung eines weiteren Waschmittels nach dem Stand der Technik ohne Zusatz eines Kondensationsproduktes und ohne Zusatz einer Kombination von nichtionischen Tensiden, bestehend aus niedrig ethoxylierten und hoch ethoxylierten Verbindungen (Beispiel 3).The following examples show the production of a detergent according to the invention (Example 1) and the production of detergents according to the prior art (Example 2, without the addition of a condensation product) and the production of a further detergent according to the prior art without the addition of a condensation product and without addition a combination of nonionic surfactants, consisting of low ethoxylated and highly ethoxylated compounds (Example 3).

Mit den so erhaltenen Waschmitteln wurden Waschversuche durchgeführt, aus denen erkennbar ist, daß das erfindungsgemäß hergestellte Waschmittel gemäß Beispiel 1 deutlich bessere Waschergebnisse liefert als die Waschmittel nach dem Stand der Technik.With the detergents obtained in this way, washing tests were carried out, from which it can be seen that the detergent produced according to the invention according to Example 1 delivers significantly better washing results than the detergents according to the prior art.

Beispiel 1example 1

Ein Fettsäurekondensationsprodukt aus gehärtetem Talg und Hydroxyethylethylendiamin, bei dem das Molverhältnis von Fettsäureresten zu Amin gleich 3 : 1 ist, wurde hergestellt, indem man 900 g gehärteten Rindertalg auf 95 °C erhitzte und 114 g N-Hydroxyethylethylendiamin innerhalb 35 Minuten unter Rühren zutropfte. Anschließend wurde 4 Stunden bei 100 °C nachgerührt. Man ließ auf 90 °C abkühlen, gab dann 42,6 g 70%ige wäßrige Glykolsäure hinzu, und ließ nach weiteren 30 Minuten Rührzeit bei 90 °C durch Abkühlen in dünner Schicht erstarren.A fatty acid condensation product of hardened tallow and hydroxyethylethylenediamine, in which the molar ratio of fatty acid residues to amine is 3: 1, was prepared by heating 900g of hardened beef tallow to 95 ° C and dropping 114g of N-hydroxyethylethylenediamine over 35 minutes with stirring. The mixture was then stirred at 100 ° C for 4 hours. The mixture was allowed to cool to 90 ° C., then 42.6 g of 70% strength aqueous glycolic acid were added, and after a further 30 minutes of stirring at 90 ° C. it was allowed to solidify by cooling in a thin layer.

In einem Mischer wurde dann ein Basiswaschmittel der folgenden Zusammensetzung hergestellt:

4 Gew.-%
Natriumdodecylbenzolsulfonat
25 Gew.-%
Natriumtripolyphosphat
20 Gew.-%
Natriumalumosilikat (Zeolith A 4)
4 Gew.-%
Wasserglas 1 : 3,35
3 Gew.-%
Natriumcarbonat
1,5 Gew.-%
Carboxymethylcellulose
2 Gew.-%
Natriumseife aus hydrierter Talgfettsäure
15 Gew.-%
Natriumperborat
2 Gew.-%
Tetraacetylethylendiamin
0,5 Gew.-%
Enzymprills, Typ Maxatase®
0,25 Gew.-%
optische Aufheller, Typ Tinopal® DMSX
Rest bis auf 90 Gew.-% Natriumsulfat.A basic detergent of the following composition was then prepared in a mixer:
4% by weight
Sodium dodecylbenzenesulfonate
25% by weight
Sodium tripolyphosphate
20% by weight
Sodium aluminosilicate (Zeolite A 4)
4% by weight
Water glass 1: 3.35
3% by weight
sodium
1.5% by weight
Carboxymethyl cellulose
2% by weight
Sodium soap from hydrogenated tallow fatty acid
15% by weight
Sodium perborate
2% by weight
Tetraacetylethylenediamine
0.5% by weight
Enzyme prills, type Maxatase®
0.25% by weight
optical brighteners, type Tinopal® DMSX
Balance up to 90% by weight sodium sulfate.

Auf das in einem Mischer bewegte Basiswaschpulver wurden dann 2 Gew.-% einer Schmelze des wie oben hergestellten Fettsäurekondensationsproduktes sowie 4 Gew.-% Talgfettalkohol + 4 Mol Ethylenoxid und 4 Gew.-% Talgfettalkohol + 14 Mol Ethylenoxid in feiner Verteilung aufgesprüht. Nach 30 Minuten Bewegung des Waschmittels im Mischer lagen alle Bestandteile in gleichmäßig feiner Verteilung vor. Man ließ das Waschmittel auf Raumtemperatur abkühlen.2% by weight of a melt of the fatty acid condensation product prepared as above, 4% by weight of tallow fatty alcohol + 4 moles of ethylene oxide and 4% by weight of tallow fatty alcohol + 14 moles of ethylene oxide were then sprayed onto the base washing powder in a mixer. After moving the detergent in the mixer for 30 minutes, all the components were in an evenly fine distribution. The detergent was allowed to cool to room temperature.

Beispiel 2Example 2

Auf das Basiswaschmittel von Beispiel 1 wurden 5 Gew.-% Talgfettalkohol + 4 Mol Ethylenoxid und 5 Gew.-% Talgfettalkohol + 14 Mol Ethylenoxid aufgesprüht, wie in Beispiel 1 beschrieben.5% by weight of tallow fatty alcohol + 4 moles of ethylene oxide and 5% by weight of tallow fatty alcohol + 14 moles of ethylene oxide were sprayed onto the basic detergent of Example 1, as described in Example 1.

Beispiel 3Example 3

Auf das Basiswaschmittel von Beispiel 1 wurden 10 Gew.-% Talgfettalkohol + 14 Mol Ethylenoxid, wie in Beispiel 1 beschrieben, aufgesprüht. Der Talgfettalkohol in allen drei Beispielen bestand zu 60 bis 67 Gew.-% Fettalkohol mit 18 Kohlenstoffatomen, zu 25 bis 35 Gew.-% Fettalkohol mit 16 Kohlenstoffatomen und zu 4 bis 7 Gew.-% Fettalkohol mit 14 Kolenstoffatomen.10% by weight of tallow fatty alcohol + 14 moles of ethylene oxide, as described in Example 1, were sprayed onto the basic detergent of Example 1. The tallow fatty alcohol in all three examples consisted of 60 to 67 wt .-% fatty alcohol with 18 carbon atoms, 25 up to 35% by weight of fatty alcohol with 16 carbon atoms and up to 4 to 7% by weight of fatty alcohol with 14 carbon atoms.

Mit den Waschmitteln der Beispiele 1, 2 und 3 wurden Waschversuche in einer 4 kg Trockenwäsche fassenden Haushaltswaschmaschine durchgeführt. Es wurde normal verschmutzte Haushaltswäsche und Testgewebe mit Testanschmutzungen eingesetzt. Die Wasserhärte betrug 9 °dH, die Dosierung betrug im Zweilaugenwaschverfahren in Vor- und Hauptwaschgang jeweils 80 g. Der Weißgrad (Remission in %) der gewaschenen Testgewebe wurde mittels eines Elrephomats DFC 5 (Firma Zeiss) mit Filter FL 46 ermittelt und statistisch ausgewertet. Man erhielt folgende Ergebnisse: Beispiel Remission 1 69.3 2 64.7 3 60.9 With the detergents of Examples 1, 2 and 3, washing tests were carried out in a 4 kg dry laundry household washing machine. Normally soiled household laundry and test fabrics with test soiling were used. The water hardness was 9 ° dH, the dosage in the two-eye washing process in the pre-wash and main wash was 80 g each. The whiteness (reflectance in%) of the washed test fabric was determined using an Elrephomat DFC 5 (Zeiss company) with a FL 46 filter and statistically evaluated. The following results were obtained: example Remission 1 69.3 2nd 64.7 3rd 60.9

Aus diesen Ergebnissen geht die überlegene Waschleistung des erfindungsgemäßen Waschmittels gemaß Beispiel 1 gegenüber den Waschmitteln des Standes der Technik gemäß Beispiel 2 und 3 hervor. Ähnliche Unterschiede zwischen erfindungsgemäßen Waschmitteln und Waschmitteln nach dem Stand der Technik erhielt man, wenn man statt des Talgfettalkohol-Ethoxylats andere nichtionische Tenside, beispielsweise Oleyl-/Cethylalkoholgemische, Oxoalkoholgemische, Nonylphenol oder Alkohol/Nonylphenol, jeweils in Form ihrer Ethylenoxidkondensationsprodukte als Kombination niedrig ethoxylierter und hoch ethoxylierter nichtionischer Tenside einsetzte.These results show the superior washing performance of the detergent according to the invention according to Example 1 compared to the detergents of the prior art according to Examples 2 and 3. Similar differences between detergents according to the invention and detergents according to the prior art were obtained if, instead of the tallow fatty alcohol ethoxylate, other nonionic surfactants, for example oleyl / methyl alcohol mixtures, oxo alcohol mixtures, nonylphenol or alcohol / nonylphenol, each in the form of their ethylene oxide condensation products as a combination of low ethoxylated and used highly ethoxylated nonionic surfactants.

Claims (8)

  1. A detergent of enhanced detergent power containing nonionic and optionally anionic surfactants and a condensation product prepared by reaction of a triglyceride of higher fatty acids and a hydroxyalkyl polyamine and other typical detergent constituents, characterized in that it contains
    4 to 30% by weight   of a combination of
    a) aliphatic C₁₂₋₂₀ alcohols containing 2 to 6 mol ethylene oxide and/or C₆₋₁₅ alkyl phenols containing 1.5 to 4 mol ethylene oxide and having low degrees of ethoxylation,
    b) aliphatic C₁₂₋₂₀ alcohols containing 8 to 20 mol ethylene oxide and/or c₆₋₁₅ alkyl phenols containing 6 to 20 mol ethylene oxide and having relatively high degrees of ethoxylation,
    the ratio of a) to b) being from 1 : 0.5 to 1 : 5,
    1 to 10% by weight   of a reaction product of triglycerides of higher fatty alcohols containing 10 to 22 carbon atoms in the fatty acid residue with hydroxyalkyl polyamines containing at least one hydroxyethyl, hydroxypropyl or dihydroxypropyl group and at least two hydrogen atoms attached to nitrogen,
    5 to 60% by weight   of other typical detergent constituents except anionic surfactants,
    0 to 30% by weight   of anionic surfactants, but not more anionic surfactants than nonionic surfactants.
  2. A detergent as claimed in claim 1 containing a condensation product in which 1.3 to 4 and preferably 1.5 to 3 mol fatty acid residues are used per mol hydroxyalkyl polyamine and which has the following composition:
    2 to 20 and preferably 5 to 15% by weight diamide ester,
    20 to 60 and preferably 25 to 45% by weight diamides,
    5 to 40 and preferably 10 to 35% by weight monoamides,
    5 to 40 and preferably 10 to 30% by weight fatty acid triglycerides,
    balance to 100% by weight: free fatty acids, free amine, glycerol.
  3. A detergent as claimed in claim 1 containing a condensation product of a fatty acid triglyceride, preferably of 1 mol hydrogenated tallow, corresponding to 3 mol fatty acids residues and 1 mol hydroxyethyl ethylenediamine.
  4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains as other detergent constituents up to 50% by weight water-soluble organic phosphates and/or sodium alumosilicates of the zeolite A4 type and/or alkali metal salts of aminopolycarboxylic acids, preferably nitrilotriacetic acid, ethylenediamine tetraacetic acid and/or alkali metal salts of organic phosphonic acids, preferably ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid.
  5. A detergent as claimed in any of claims 1 to 4, characterized in that it additionally contains up to 5% by weight sodium salts of polymeric carboxylic acids, such as for example polyacrylic acid, polyhydroxyacrylic acid, and copolymers of carboxylic acids, such as maleic acid (anhydride), with methyl vinyl ether or acrylic acid.
  6. A detergent as claimed in any of claims 1 to 5, characterized in that it additionally contains up to 4% by weight foam inhibitors based on sodium salts of C₁₂₋₂₂ fatty acids and/or silicone oils and/or paraffin.
  7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains 10 to 25% by weight of a bleach component, bleach stabilizers and bleach activators.
  8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains proteases corresponding to a protease activity of 100 to 2,500 LVE per gram and/or amylases corresponding to an amylase activity of 20 to 2,000 SKBE per gram end product.
EP19850106659 1984-06-06 1985-05-30 Washing agent with intensified washing power Expired - Lifetime EP0164072B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT1859/84 1984-06-06
AT185984A AT384435B (en) 1984-06-06 1984-06-06 WASH-ACTIVATED TEXTILE DETERGENT

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EP0164072A3 EP0164072A3 (en) 1989-10-18
EP0164072B1 true EP0164072B1 (en) 1992-02-12

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WO1995019955A1 (en) * 1994-01-25 1995-07-27 The Procter & Gamble Company Gemini polyether fatty acid amides and their use in detergent compositions
US5534197A (en) * 1994-01-25 1996-07-09 The Procter & Gamble Company Gemini polyhydroxy fatty acid amides
DE19756680A1 (en) * 1997-12-19 1999-06-24 Henkel Kgaa Production of fatty acid aminoamide
GB0030669D0 (en) 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0030671D0 (en) 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0124308D0 (en) 2001-10-10 2001-11-28 Unilever Plc Detergent compositions
GB0124307D0 (en) 2001-10-10 2001-11-28 Unilever Plc Detergent compositions
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AT384435B (en) 1987-11-10
ES543944A0 (en) 1986-01-16
DE3585375D1 (en) 1992-03-26
EP0164072A3 (en) 1989-10-18
ES8604297A1 (en) 1986-01-16
ATA185984A (en) 1987-04-15

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