EP0715647B1 - Liquid washing product - Google Patents

Liquid washing product Download PDF

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Publication number
EP0715647B1
EP0715647B1 EP94926859A EP94926859A EP0715647B1 EP 0715647 B1 EP0715647 B1 EP 0715647B1 EP 94926859 A EP94926859 A EP 94926859A EP 94926859 A EP94926859 A EP 94926859A EP 0715647 B1 EP0715647 B1 EP 0715647B1
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EP
European Patent Office
Prior art keywords
protein
weight
protein hydrolyzates
fatty acid
hydrolyzates
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EP94926859A
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German (de)
French (fr)
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EP0715647B2 (en
EP0715647A1 (en
Inventor
Hans Jürgen RIEBE
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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
    • 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
    • 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
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/384—Animal products
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—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
    • C11D1/02—Anionic compounds
    • C11D1/32—Protein hydrolysates; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to a storage-stable, discoloration-inhibiting Liquid textile detergent with a viscosity (at 20 ° C) of 100 up to 2000 mPa ⁇ s containing water-soluble protein derivatives.
  • Liquid textile detergents have recently been enjoying the consumer increasing in popularity as they have some handling advantages over powdered ones Own detergents and greasy or oily soiling are easier to remove. This advantage is due to the fact that liquid detergents have larger amounts compared to greasy or oily ones Contaminants contain particularly effective nonionic surfactants. A frequently occurring in the development of liquid detergent formulations The problem is the setting of the desired viscosity.
  • the viscosity is often comparatively high sought, since the customer is hereby generally a particularly effective and rich wording associated.
  • various connections have been proposed in the past been.
  • Polymers e.g. polyurethanes
  • ethanolamides are often used as viscosity regulators.
  • these substances are usually not or only poorly biodegradable or can under May contain or form nitrosamines.
  • solvent-based e.g. ethanol, propylene glycol
  • German Offenlegungsschrift 28 14 287 is as a discoloration-inhibiting active ingredient polyvinylimidazole and from the German Offenlegungsschrift 28 14 329 known polyvinyloxazolidone.
  • the Use of protein-fatty acid condensates, protein hydrolyzates and cationic derivatized protein hydrolyzates as dye inhibitors in textile detergents is not yet known. Even the use of these substances as viscosity and consistency regulators in liquid detergents has not yet been described.
  • CA paper 91: 212922f describes the use of cationically modified hydrolyzed protein in liquid dishwashing detergents to prevent water stains the washed dishes.
  • U.S. Patent No. 5,073,292 discloses the use of protein hydrolyzates and quaternized proteins as enzyme stabilizers in liquid detergents.
  • the present invention relates to textile liquid detergents, which, in addition to a certain combination of surfactants, protein-fatty acid condensates, Protein hydrolyzates or cationically derivatized protein hydrolyzates as readily biodegradable dye transfer inhibitors and viscosity regulators contain.
  • soaps used in the agents according to the invention are alkali or alkanolamine salts of saturated fatty acids or mixtures of substantially saturated fatty acids.
  • potassium salts and sodium salts of fatty acids with 10 up to 20 carbon atoms used.
  • the fatty alcohol ethoxylates used are adducts of 1 to 15 moles of ethylene oxide with primary C 10 to C 18 fatty alcohols and their mixtures such as coconut oil, tallow fat or oleyl alcohol or adducts of 1 to 15 moles of ethylene oxide with oxo alcohols. To achieve particularly balanced properties, it is often advisable to use a combination of alcohol ethoxylates with different degrees of ethoxylation.
  • alkyl glucosides are glucosides having a C 8 to C 18 alkyl radical which is derived from lauryl, myristyl, cetyl and stearyl and from technical fractions which preferably contain saturated alcohols.
  • the use of alkyl glucosides is particularly preferred, the alkyl radicals of which contain 50 to 70% by weight of C 12 and 18 to 30% by weight of C 14 .
  • the index number x is a number between 1 and 4, which indicates the degree of oligomerization. It represents an average for a specific product, which takes into account the fact that industrially produced alkyl glucosides are generally mixtures of monoglucosides and oligoglucosides of various degrees of oligomerization. Alkyl glucosides in which x has a value between 1.1 and 1.4 are particularly preferred.
  • the water-soluble protein derivatives used in the liquid detergents according to the invention can, for. B. derived from the following proteins or their hydrolyzates: collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.
  • protein-fatty acid condensates are the condensation products and their salts, e.g. B. Alkali, ammonium or alkanolamine salts, which are formed from protein or protein hydrolyzate and C 12 - to C 18 fatty acids to understand.
  • the C 12 - to C 18 fatty acid residues can be made from technical mixtures, e.g. B. coconut or valley remains.
  • Cationically derivatized protein hydrolyzates are protein hydrolyzates that are substituted with a quaternized nitrogen-containing radical; suitable residues are e.g. B. lauryldimonium hydroxypropyl or stearyltrimonium.
  • suitable residues are e.g. B. lauryldimonium hydroxypropyl or stearyltrimonium.
  • halide ions can be used as counterions.
  • Suitable Protein fatty acid condensates are e.g. B. under the trade name Lamepon from the Grünau company or those under the trade name Maypon from the company Stepan distributed protein-fatty acid condensates.
  • Lamepon S a protein fatty acid condensate potassium salt with an average Molecular weight from 700 to 800, which is a cocoyl substituted Collagen hydrolyzate with four amino acid monomer units.
  • Lamepon S-TR and Lamepon ST 40 the corresponding triethanolamine salts, to call.
  • Suitable protein hydrolyzates are e.g. B. by the company Grünau under the Trade names Nutrilan distributed protein hydrolysates, the hydrolysates of Represent collagen and an average molecular weight of 500 to 2000 exhibit.
  • Suitable cationically derivatized proteins or protein hydrolyzates are e.g. B. those sold by the Grünau company under the trade name Lamequat cationized protein hydrolyzates, e.g. B. Lauryldimonium hydroxypropylamino substituted Medium molecular weight collagen hydrolyzate from 600 to 700.
  • surfactants are amphoteric or zwitterionic Surfactants, e.g. Betaine.
  • Preferred additionally contained surfactants are anionic surfactants, e.g. Alkylbenzenesulfonates, but especially fatty alcohol sulfates.
  • liquid detergents described in more detail above which additionally contain up to 30% by weight of a fatty alcohol sulfate of the general formula R 3 OSO 3 (-) M (+) , where R 3 is a straight-chain or branched alkyl or alkenyl group with 12 to 18 carbon atoms and M (+) represents an alkali metal or ammonium cation.
  • the fatty alcohol sulfates contained in the liquid detergents according to the invention are sulfuric acid monoesters of C 12 to C 18 fatty alcohols such as lauryl, myristyl or cetyl alcohol and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil and tallow, which additionally contain proportions of unsaturated alcohols, e.g. B. oleyl alcohol.
  • Mixtures in which the proportions of the alkyl radicals are 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed.
  • the liquid detergents according to the invention can be water, contain monohydric alcohols and / or polyhydric alcohols.
  • a monovalent Alcohol is primarily used as ethanol; as multivalued Alcohols, 1,2-propanediol or preferably glycerin can be used.
  • the pH of the liquid detergents according to the invention is 7 to 10.5, preferably 7 to 9.5.
  • the agents can be known in detergents Additives usually used, for example salts of Citric acid, salts of polyphosphonic acids, optical brighteners, enzymes, Enzyme stabilizers, defoamers, pearlescent agents, preservatives as well as dyes and fragrances.
  • salts of polyphosphonic acids the neutral reacting sodium salts of z.
  • enzymes the class of proteases, lipases, amylases and cellulases in question.
  • your Proportion can be 0.2 to 5% by weight; as an enzyme stabilizer e.g. 0.5 up to 1.5% by weight sodium formate can be used.
  • Suitable defoamers are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, Waxes, microcrystalline waxes or their mixtures with silanated Silica. As pearlescent z. B. Ethyl glycol distearate.
  • the liquid detergents according to the invention are preferably free of biological poorly degradable viscosity regulators such.
  • B. Polyurethanes and discoloration inhibitors such as e.g. B. homo- and copolymers based on N-vinylimidazole, N-vinyloxazolidone or N-vinylpyrrolidone.
  • B. homo- and copolymers based on N-vinylimidazole, N-vinyloxazolidone or N-vinylpyrrolidone instead of such poorly degradable polymer compounds contain the inventive Liquid detergents, the water-soluble ones already characterized in more detail above Protein derivatives. These water soluble protein derivatives work on the one hand an increase in viscosity; they give the liquid detergent that is, the consistency desired by the consumer. On the other hand, prevent it they the when washing colored textiles, e.g. B. acetyl cellulose, Cotton, polyamide, polyester, polyacrylic or wool fibers undesirable Dye transfer.
  • Another subject of the invention is therefore the use of protein-fatty acid condensates, Protein hydrolyzates and / or cationically derivatized Protein hydrolyzates to increase the viscosity of liquid laundry detergents.
  • Another object of the invention is the use of protein-fatty acid condensates, protein hydrolyzates and / or cationically derivatized protein hydrolyzates as dye transfer inhibitors in textile detergents, preferably liquid textile detergents.
  • the water-soluble protein derivatives mentioned naturally also exert their dye transfer-inhibiting action in granulated or extruded powdered textile detergents.
  • the use of the above-mentioned protein derivatives in powdered laundry detergents is therefore also part of the invention; however, the above-mentioned protein derivatives are preferably used in liquid laundry detergents. Cationically derivatized protein hydrolyzates are particularly preferred.
  • Another object of the invention is a method for washing discoloration-sensitive textiles in aqueous wash liquors, the soap, nonionic surfactant selected from the group of the C 10 -C 18 alcohol ethoxylates described above and the group of the C 8 -C 18 alkyl glucosides described above and contain a dye transfer inhibitor, the dye transfer inhibitor being a water-soluble protein derivative selected from protein-fatty acid condensates, protein hydrolyzates or cationically derivatized protein hydrolyzates and mixtures thereof.
  • liquid detergents listed in Table I under numbers 2 to 4 contain collagen hydrolyzate. Comparative example 1 is free of Collagen hydrolyzate.
  • liquid detergents 6 to 9 listed in Table II contain one Collagen hydrolyzate coconut fatty acid condensate potassium salt. Comparative example 5 does not contain collagen hydrolyzate fatty acid condensate.
  • liquid detergents 11, 12 and 14 to 16 listed in Table III contain a cationically derivatized protein hydrolyzate (lauryldimonium hydroxypropyl substituted Collagen hydrolyzate).
  • the comparative examples 10 and 13 are free of it.
  • the increase in the amount of water-soluble protein derivative results in a sharp increase in the viscosity of the respective liquid detergent.
  • Lamequat L-containing formulations B and C are better color transfer inhibiting effects show as that not according to the invention Agent A; with increasing lamequat L content, the color transfer inhibiting decreases Effect too.

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

Abstract

A storage stable, colour change-inhibiting, liquid textile washing product has 100 to 2000 mPa.s viscosity (at 20 DEG C) and contains water-soluble protein derivatives selected among protein-fatty acid condensates, protein hydrolysates and cationically derived protein hydrolysates. Also disclosed is the use of said protein derivatives as colour-transfer-inhibitors in textile washing products, preferably liquid textile washing products, and as viscosity regulators in liquid textile washing products.

Description

Die vorliegende Erfindung betrifft ein lagerstabiles, verfärbungsinhibierendes Textil-Flüssigwaschmittel mit einer Viskosität (bei 20°C) von 100 bis 2000 mPa·s enthaltend wasserlösliche Proteinderivate.The present invention relates to a storage-stable, discoloration-inhibiting Liquid textile detergent with a viscosity (at 20 ° C) of 100 up to 2000 mPa · s containing water-soluble protein derivatives.

Flüssige Textilwaschmittel erfreuen sich in letzter Zeit beim Verbraucher zunehmender Beliebtheit, da sie einige Handhabungsvorteile gegenüber pulverförmigen Waschmitteln besitzen und fettige bzw. ölige Verschmutzungen besser zu entfernen imstande sind. Dieser Vorteil beruht auf der Tatsache, daß flüssige Waschmittel größere Mengen der gegenüber fettigen oder öligen Verschmutzungen besonders wirksamen nichtionischen Tenside enthalten. Ein häufig bei der Entwicklung von Flüssigwaschmittelrezepturen auftretendes Problem ist die Einstellung der gewünschten Viskosität.Liquid textile detergents have recently been enjoying the consumer increasing in popularity as they have some handling advantages over powdered ones Own detergents and greasy or oily soiling are easier to remove. This advantage is due to the fact that liquid detergents have larger amounts compared to greasy or oily ones Contaminants contain particularly effective nonionic surfactants. A frequently occurring in the development of liquid detergent formulations The problem is the setting of the desired viscosity.

Aus konzeptionellen Gründen wird oft eine vergleichsweise hohe Viskosität angestrebt, da der Kunde im allgemeinen hiermit eine besonders wirksame und gehaltvolle Formulierung assoziiert. Zur Erzielung der gewünschten Verdickung sind in der Vergangenheit verschiedene Verbindungen vorgeschlagen worden. So werden vielfach Polymere (z. B.: Polyurethane) oder Ethanolamide als Viskositätsregulatoren eingesetzt. Diese Stoffe sind jedoch in der Regel nicht oder nur schlecht biologisch abbaubar oder können unter Umständen Nitrosamine enthalten bzw. bilden. Oft sind die Substanzen auch nicht in der Lage, lösungsmittelhaltige (z. B. Ethanol, Propylenglycol) Tensidsysteme ausreichend zu verdicken. Es galt daher, geeignete Stoffe aufzufinden, die nicht mit derartigen Makeln behaftet sind.For conceptual reasons, the viscosity is often comparatively high sought, since the customer is hereby generally a particularly effective and rich wording associated. To achieve the desired Thickening, various connections have been proposed in the past been. Polymers (e.g. polyurethanes) or ethanolamides are often used used as viscosity regulators. However, these substances are usually not or only poorly biodegradable or can under May contain or form nitrosamines. Often the substances are too unable to use solvent-based (e.g. ethanol, propylene glycol) Thicken surfactant systems sufficiently. It was therefore necessary to use suitable substances to find that are not affected by such flaws.

Ein weiteres Problem, das sich beim Waschen von Textilien, insbesondere bei der gemeinsamen Wäsche von farbigen und weißen bzw. hellfarbigen Textilien stellt, ist die Übertragung von Farbstoffen von einem Wäschestück auf das andere. Zur Lösung dieses Problems gibt es bereits einige Lösungsvorschläge. Aus der deutschen Auslegeschrift DE 22 32 353 ist ein Waschmittel bekannt, dessen verfärbungsinhibierender Zusatz Polymerbestandteile auf Basis von Polyvinylpyrrolidon sind. Aus der deutschen Auslegeschrift DE 12 24 698 ist bekannt, daß man durch eine Behandlung von Textilien, die durch Aufhellerübertragung eine Farbtonverschiebung erfahren haben, mit Lösungen von tertiären und quartären organischen Stickstoffbasen oder deren Salzen eine Farbtonregenerierung bewirken kann. Gegenstand der deutschen Offenlegungsschrift 35 19 012 sind Waschmittel mit einem Gehalt an Polymerbestandteilen auf Basis von Polyvinylpyrrolidon und wasserlöslichen kationischen Verbindungen. Aus der deutschen Offenlegungsschrift 28 14 287 ist als verfärbungsinhibierender Wirkstoff Polyvinylimidazol und aus der deutschen Offenlegungsschrift 28 14 329 Polyvinyloxazolidon bekannt. Die Verwendung von Eiweiß-Fettsäure-Kondensaten, Eiweißhydrolysaten und kationisch derivatisierten Eiweißhydrolysaten als Farbstoffinhibitoren in Textilwaschmitteln ist bislang nicht bekannt. Auch die Verwendung dieser Substanzen als Viskositäts- und Konsistenzregulatoren in Flüssigwaschmitteln ist bisher noch nicht beschrieben worden. Das CA-Referat 91:212922f beschreibt den Einsatz von kationisch modifiziertem hydrolysierten Protein in flüssigen Geschirrspülmitteln zur Verhinderung von Wasserflecken auf dem gewaschenen Geschirrgut. Die US-Patentschrift US 5,073,292 offenbart den Einsatz von Proteinhydrolysaten und quaternierten Proteinen als Enzymstabilisatoren in Flüssigwaschmitteln.Another problem that arises when washing textiles, in particular when washing colored and white or light-colored textiles together represents the transfer of dyes from a laundry to the other. There are already some solutions to solve this problem. A detergent is known from German specification DE 22 32 353 known, the discoloration-inhibiting addition of polymer components are based on polyvinylpyrrolidone. From the German interpretation DE 12 24 698 is known that by treating textiles, the have experienced a color shift due to brightener transfer with Solutions of tertiary and quaternary organic nitrogen bases or their Salt can cause a color regeneration. Subject of the German Laid-open specification 35 19 012 are detergents containing Polymer components based on polyvinylpyrrolidone and water-soluble cationic compounds. From German Offenlegungsschrift 28 14 287 is as a discoloration-inhibiting active ingredient polyvinylimidazole and from the German Offenlegungsschrift 28 14 329 known polyvinyloxazolidone. The Use of protein-fatty acid condensates, protein hydrolyzates and cationic derivatized protein hydrolyzates as dye inhibitors in textile detergents is not yet known. Even the use of these substances as viscosity and consistency regulators in liquid detergents has not yet been described. CA paper 91: 212922f describes the use of cationically modified hydrolyzed protein in liquid dishwashing detergents to prevent water stains the washed dishes. U.S. Patent No. 5,073,292 discloses the use of protein hydrolyzates and quaternized proteins as enzyme stabilizers in liquid detergents.

Die vorliegende Erfindung betrifft demgegenüber Textil-Flüssigwaschmittel, die neben einer bestimmten Tensidkombination Eiweiß-Fettsäure-Kondensate, Eiweißhydrolysate oder kationisch derivatisierte Eiweißhydrolysate als biologisch gut abbaubare Farbstoffübertragungsinhibitoren und Viskositätsregulatoren enthalten.In contrast, the present invention relates to textile liquid detergents, which, in addition to a certain combination of surfactants, protein-fatty acid condensates, Protein hydrolyzates or cationically derivatized protein hydrolyzates as readily biodegradable dye transfer inhibitors and viscosity regulators contain.

Gegenstand der Erfindung sind Flüssigwaschmittel zum Waschen von Textilien, die bei 20°C eine Viskosität von 100 bis 2000 mPa·s, vorzugsweise 200 bis 1000 mPa·s aufweisen, enthaltend

  • 0,1 - 30 Gew.-% Seife,
  • 0,1 - 50 Gew.-% eines nichtionischen Tensids ausgewählt aus der Gruppe der Alkoholethoxylate der allgemeinen Formel R1O(C2H4O)nH, wobei R1 eine geradkettige oder verzweigte Alkyl- oder Alkenylgruppe mit 10 bis 18 C-Atomen, und n eine Zahl von 1 bis 15 ist und der Alkylglucoside der allgemeinen Formel R2O(G)x, wobei R2 eine geradkettige oder verzweigte Alkyl- oder Alkenylgruppe mit 8 bis 18 C-Atomen darstellt, G eine Glucoseeinheit und x eine Zahl von 1 bis 4, vorzugsweise 1,1 bis 1,4, ist, bzw. deren Mischungen, und
  • 0,1 - 10 Gew.-% eines wasserlöslichen Proteinderivats mit einem mittleren Molekulargewicht von 400 bis 4000 ausgewählt aus Eiweiß-Fettsäure-Kondensaten, Eiweißhydrolysaten und kationisch derivatisierten Eiweißhydrolysaten.
The invention relates to liquid detergents for washing textiles which, at 20 ° C., have a viscosity of 100 to 2000 mPa · s, preferably 200 to 1000 mPa · s
  • 0.1-30% by weight of soap,
  • 0.1-50% by weight of a nonionic surfactant selected from the group of alcohol ethoxylates of the general formula R 1 O (C 2 H 4 O) n H, where R 1 is a straight-chain or branched alkyl or alkenyl group with 10 to 18 C. -Atoms, and n is a number from 1 to 15 and the alkyl glucosides of the general formula R 2 O (G) x , where R 2 is a straight-chain or branched alkyl or alkenyl group having 8 to 18 carbon atoms, G is a glucose unit and x is a number from 1 to 4, preferably 1.1 to 1.4, or mixtures thereof, and
  • 0.1-10% by weight of a water-soluble protein derivative with an average molecular weight of 400 to 4000 selected from protein-fatty acid condensates, protein hydrolyzates and cationically derivatized protein hydrolyzates.

Bei den in den erfindungsgemäßen Mitteln zur Verwendung kommenden Seifen handelt es sich um Alkali- oder Alkanolaminsalze von gesättigten Fettsäuren oder von Gemischen von im wesentlichen gesättigten Fettsäuren. Vorzugsweise werden die Kaliumsalze und Natriumsalze von Fettsäuren mit 10 bis 20 Kohlenstoffatomen verwendet. Dabei kann die Seife als solche oder aber auch ein Seife bildendes Gemisch aus Fettsäure und KOH bzw. NaOH eingesetzt werden.In the soaps used in the agents according to the invention are alkali or alkanolamine salts of saturated fatty acids or mixtures of substantially saturated fatty acids. Preferably the potassium salts and sodium salts of fatty acids with 10 up to 20 carbon atoms used. The soap as such or but also a soap-forming mixture of fatty acid and KOH or NaOH is used will.

Die eingesetzten Fettalkoholethoxylate sind Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an primäre C10 bis C18-Fettalkohole und deren Gemische wie Kokos-, Talgfett- oder Oleylalkohol oder Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an Oxoalkohole. Zur Einstellung besonders ausgewogener Eigenschaften ist es oft empfehlenswert, eine Kombination von Alkoholethoxylaten mit unterschiedlich hohen Ethoxylierungsgraden zu verwenden.The fatty alcohol ethoxylates used are adducts of 1 to 15 moles of ethylene oxide with primary C 10 to C 18 fatty alcohols and their mixtures such as coconut oil, tallow fat or oleyl alcohol or adducts of 1 to 15 moles of ethylene oxide with oxo alcohols. To achieve particularly balanced properties, it is often advisable to use a combination of alcohol ethoxylates with different degrees of ethoxylation.

Als Alkylglucoside eignen sich insbesondere Glucoside mit einem C8 bis C18-Alkylrest, der sich von Lauryl, Myristyl, Cetyl und Stearyl sowie von technischen Fraktionen, die vorzugsweise gesättigte Alkohole enthalten, ableitet. Besonders bevorzugt ist der Einsatz von Alkylglucosiden, deren Alkylreste zu 50 bis 70 Gew.-% C12, und 18 bis 30 Gew.-% C14 enthält. Die Indexzahl x ist eine Zahl zwischen 1 und 4, die den Oligomerisierungsgrad angibt. Sie stellt für ein spezielles Produkt einen Mittelwert dar, womit der Tatsache Rechnung getragen wird, daß technisch hergestellte Alkylglucoside im allgemeinen Mischungen von Monoglucosiden und Oligoglucosiden verschiedener Oligomerisierungsgrade darstellen. Besonders bevorzugt sind Alkylglucoside, in denen x einen Wert zwischen 1,1 und 1,4 hat.Particularly suitable alkyl glucosides are glucosides having a C 8 to C 18 alkyl radical which is derived from lauryl, myristyl, cetyl and stearyl and from technical fractions which preferably contain saturated alcohols. The use of alkyl glucosides is particularly preferred, the alkyl radicals of which contain 50 to 70% by weight of C 12 and 18 to 30% by weight of C 14 . The index number x is a number between 1 and 4, which indicates the degree of oligomerization. It represents an average for a specific product, which takes into account the fact that industrially produced alkyl glucosides are generally mixtures of monoglucosides and oligoglucosides of various degrees of oligomerization. Alkyl glucosides in which x has a value between 1.1 and 1.4 are particularly preferred.

Die in den erfindungsgemäßen Flüssigwaschmitteln eingesetzten wasserlöslichen Proteinderivate können sich z. B. von folgenden Eiweißen bzw. deren Hydrolysaten ableiten: Kollagen, Keratin, Casein, Elastin, Sojaprotein, Weizengluten oder Mandelprotein. Unter Eiweiß-Fettsäure-Kondensaten sind die Kondensationsprodukte und deren Salze, z. B. Alkali-, Ammonium- oder Alkanolaminsalze, die aus Eiweiß bzw. Eiweißhydrolysat und C12- bis C18-Fettsäuren gebildet werden, zu verstehen. Die C12- bis C18-Fettsäurereste können dabei aus technischen Gemischen, z. B. Kokos- oder Talgresten stammen. Unter kationisch derivatisierten Eiweißhydrolysaten sind solche Eiweißhydroiysate zu verstehen, die mit einem quaternierten Stickstoff enthaltenden Rest substituiert sind; geeignete Reste sind z. B. Lauryldimoniumhydroxypropyl oder Stearyltrimonium. Als Gegenionen kommen hierbei z.B. Halogenidionen in Betracht.The water-soluble protein derivatives used in the liquid detergents according to the invention can, for. B. derived from the following proteins or their hydrolyzates: collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Among protein-fatty acid condensates are the condensation products and their salts, e.g. B. Alkali, ammonium or alkanolamine salts, which are formed from protein or protein hydrolyzate and C 12 - to C 18 fatty acids to understand. The C 12 - to C 18 fatty acid residues can be made from technical mixtures, e.g. B. coconut or valley remains. Cationically derivatized protein hydrolyzates are protein hydrolyzates that are substituted with a quaternized nitrogen-containing radical; suitable residues are e.g. B. lauryldimonium hydroxypropyl or stearyltrimonium. For example, halide ions can be used as counterions.

Dabei kommen alle handelsüblichen Eiweiß-Fettsäure-Kondensate, Eiweißhydrolysate und kationisch derivatisierten Eiweiße oder Eiweißhydrolysate mit einem mittleren Molekulargewicht von 400 bis 4000 in Frage. Geeignete Eiweiß-Fettsäure-Kondensate sind z. B. die unter dem Handelsnamen Lamepon von der Firma Grünau oder die unter dem Handelsnamen Maypon von der Firma Stepan vertriebenen Eiweiß-Fettsäure-Kondensate. Zu erwähnen sind z. B. das Lamepon S, ein Eiweiß-Fettsäurekondensat-Kaliumsalz mit einem durchschnittlichen Molekulargewicht von 700 bis 800, das ein cocoylsubstituiertes Kollagenhydrolysat mit vier Aminosäuremonomereinheiten ist. Desweiteren sind Lamepon S-TR und Lamepon ST 40, die entsprechenden Triethanolaminsalze, zu nennen.All commercially available protein-fatty acid condensates, protein hydrolyzates and cationically derivatized proteins or protein hydrolyzates with an average molecular weight of 400 to 4000 in question. Suitable Protein fatty acid condensates are e.g. B. under the trade name Lamepon from the Grünau company or those under the trade name Maypon from the company Stepan distributed protein-fatty acid condensates. To mention are z. B. the Lamepon S, a protein fatty acid condensate potassium salt with an average Molecular weight from 700 to 800, which is a cocoyl substituted Collagen hydrolyzate with four amino acid monomer units. Furthermore are Lamepon S-TR and Lamepon ST 40, the corresponding triethanolamine salts, to call.

Geeignete Eiweißhydrolysate sind z. B. die von der Firma Grünau unter dem Handelsnamen Nutrilan vertriebenen Eiweißhydrolysate, die Hydrolysate des Kollagens darstellen und ein mittleres Molekulargewicht von 500 bis 2000 aufweisen.Suitable protein hydrolyzates are e.g. B. by the company Grünau under the Trade names Nutrilan distributed protein hydrolysates, the hydrolysates of Represent collagen and an average molecular weight of 500 to 2000 exhibit.

Geeignete kationisch derivatisierte Eiweiße oder Eiweißhydrolysate sind z. B. die von der Firma Grünau unter dem Handelsnamen Lamequat vertriebenen kationisierten Eiweißhydrolysate, z. B. Lauryldimoniumhydroxypropylamino-substituiertes Kollagenhydrolysat mit einem mittleren Molekulargewicht von 600 bis 700.Suitable cationically derivatized proteins or protein hydrolyzates are e.g. B. those sold by the Grünau company under the trade name Lamequat cationized protein hydrolyzates, e.g. B. Lauryldimonium hydroxypropylamino substituted Medium molecular weight collagen hydrolyzate from 600 to 700.

Weitere fakultativ enthaltene Tenside sind amphotere Tenside oder zwitterionische Tenside, z.B. Betaine. Bevorzugte zusätzlich enthaltene Tenside sind Aniontenside, z.B. Alkylbenzolsulfonate, insbesondere jedoch Fettalkoholsulfate.Other optional surfactants are amphoteric or zwitterionic Surfactants, e.g. Betaine. Preferred additionally contained surfactants are anionic surfactants, e.g. Alkylbenzenesulfonates, but especially fatty alcohol sulfates.

Ein weiterer Erfindungsgegenstand sind daher oben näher beschriebene Flüssigwaschmittel, die zusätzlich bis zu 30 Gew.-% eines Fettalkoholsulfats der allgemeinen Formel R3OSO3 (-) M(+) enthalten, wobei R3 eine geradkettige oder verzweigte Alkyl- oder Alkenylgruppe mit 12 bis 18 C-Atomen und M(+) ein Alkalimetall- oder Ammoniumkation darstellt. Another subject of the invention is therefore liquid detergents described in more detail above, which additionally contain up to 30% by weight of a fatty alcohol sulfate of the general formula R 3 OSO 3 (-) M (+) , where R 3 is a straight-chain or branched alkyl or alkenyl group with 12 to 18 carbon atoms and M (+) represents an alkali metal or ammonium cation.

Die in den erfindungsgemäßen Flüssigwaschmitteln enthaltenen Fettalkoholsulfate sind Schwefelsäuremonoester der C12- bis C18-Fettalkohole wie Lauryl-, Myristyl- oder Cetylalkohol und der aus Kokosöl, Palm- und Palmkernöl sowie Talg gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alkoholen, z. B. Oleylalkohol, enthalten können. Eine bevorzugte Verwendung finden dabei Gemische, in denen die Anteile der Alkylreste zu 50 bis 70 Gew.-% auf C12, zu 18 bis 30 Gew.-% auf C14, zu 5 bis 15 Gew.-% auf C16, unter 3 Gew.-% auf C10 und unter 10 Gew.-% auf C18 verteilt sind.The fatty alcohol sulfates contained in the liquid detergents according to the invention are sulfuric acid monoesters of C 12 to C 18 fatty alcohols such as lauryl, myristyl or cetyl alcohol and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil and tallow, which additionally contain proportions of unsaturated alcohols, e.g. B. oleyl alcohol. Mixtures in which the proportions of the alkyl radicals are 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed.

Als Lösungsmittel können die erfindungsgemäßen Flüssigwaschmittel Wasser, einwertige Alkohole und/oder mehrwertige Alkohole enthalten. Als einwertiger Alkohol kommt in erster Linie Ethanol zum Einsatz; als mehrwertige Alkohole können 1,2-Propandiol oder vorzugsweise Glycerin verwendet werden. Der pH-Wert der erfindungsgemäßen Flüssigwaschmittel beträgt 7 bis 10,5, vorzugsweise 7 bis 9,5.The liquid detergents according to the invention can be water, contain monohydric alcohols and / or polyhydric alcohols. As a monovalent Alcohol is primarily used as ethanol; as multivalued Alcohols, 1,2-propanediol or preferably glycerin can be used. The pH of the liquid detergents according to the invention is 7 to 10.5, preferably 7 to 9.5.

Außer den genannten Inhaltsstoffen können die Mittel bekannte, in Waschmitteln üblicherweise eingesetzte Zusatzstoffe, beispielsweise Salze der Citronensäure, Salze von Polyphosphonsäuren, optische Aufheller, Enzyme, Enzymstabilisatoren, Entschäumer, Perlglanzgeber, Konservierungsmittel sowie Farb- und Duftstoffe enthalten. Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagierenden Natriumsalze von z. B. 1-Hydroxyethan-1,1-diphosphonat und Diethylentriaminpentamethylenphosphonat in Mengen von 0,1 bis 1,5 Gew.-% verwendet. Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen und Cellulasen in Frage. Ihr Anteil kann 0,2 bis 5 Gew.-% betragen; als Enzymstabilisator kann z.B. 0,5 bis 1,5 Gew.-% Natriumformiat eingesetzt werden. Geeignete Entschäumer (Schauminhibitoren) sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure, sowie Paraffine, Wachse, Mikrokristallinwachse oder deren Gemische mit silanierter Kieselsäure. Als Perlglanzgeber dient z. B. Ethylglykoldistearat. In addition to the ingredients mentioned, the agents can be known in detergents Additives usually used, for example salts of Citric acid, salts of polyphosphonic acids, optical brighteners, enzymes, Enzyme stabilizers, defoamers, pearlescent agents, preservatives as well as dyes and fragrances. As salts of polyphosphonic acids the neutral reacting sodium salts of z. B. 1-Hydroxyethane-1,1-diphosphonate and diethylene triamine pentamethylene phosphonate used in amounts of 0.1 to 1.5 wt .-%. Such come out as enzymes the class of proteases, lipases, amylases and cellulases in question. your Proportion can be 0.2 to 5% by weight; as an enzyme stabilizer e.g. 0.5 up to 1.5% by weight sodium formate can be used. Suitable defoamers (Foam inhibitors) are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, Waxes, microcrystalline waxes or their mixtures with silanated Silica. As pearlescent z. B. Ethyl glycol distearate.

Die erfindungsgemäßen Flüssigwaschmittel sind vorzugsweise frei von biologisch schlecht abbaubaren Viskositätsregulatoren wie z. B. Polyurethanen und Verfärbungsinhibitoren wie z. B. Homo- und Copolymere auf Basis von N-Vinylimidazol, N-Vinyloxazolidon oder N-Vinylpyrrolidon. Anstelle solcher schlecht abbaubarer Polymerverbindungen enthalten die erfindungsgemäßen Flüssigwaschmittel die oben bereits näher charakterisierten wasserlöslichen Proteinderivate. Diese wasserlöslichen Proteinderivate bewirken einerseits eine Viskositätssteigerung; sie verleihen dem Flüssigwaschmittel also die vom Verbraucher gewünschte Konsistenz. Andererseits verhindern sie die beim Waschen von farbigen Textilien, z. B. Acetylcellulose, Baumwolle, Polyamid, Polyester, Polyacryl oder Wollfasern unerwünschte Farbstoffübertragung.The liquid detergents according to the invention are preferably free of biological poorly degradable viscosity regulators such. B. Polyurethanes and discoloration inhibitors such as e.g. B. homo- and copolymers based on N-vinylimidazole, N-vinyloxazolidone or N-vinylpyrrolidone. Instead of such poorly degradable polymer compounds contain the inventive Liquid detergents, the water-soluble ones already characterized in more detail above Protein derivatives. These water soluble protein derivatives work on the one hand an increase in viscosity; they give the liquid detergent that is, the consistency desired by the consumer. On the other hand, prevent it they the when washing colored textiles, e.g. B. acetyl cellulose, Cotton, polyamide, polyester, polyacrylic or wool fibers undesirable Dye transfer.

Ein weiterer Erfindungsgegenstand ist deshalb die Verwendung von Eiweiß-Fettsäure-Kondensaten, Eiweißhydrolysaten und/oder kationisch derivatisierten Eiweißhydrolysaten zur Erhöhung der Viskosität von flüssigen Textilwaschmitteln.Another subject of the invention is therefore the use of protein-fatty acid condensates, Protein hydrolyzates and / or cationically derivatized Protein hydrolyzates to increase the viscosity of liquid laundry detergents.

Ein weiterer Erfindungsgegenstand ist die Verwendung von Eiweiß-Fettsäure-Kondensaten, Eiweißhydrolysaten und/oder kationisch derivatisierten Eiweißhydrolysaten als Farbstoffübertragungsinhibitoren in Textilwaschmitteln, vorzugsweise flüssigen Textilwaschmitteln. Die genannten wasserlöslichen Proteinderivate entfalten ihre farbstoffübertragungsinhibierende Wirkung selbstverständlich auch in granulierten oder extrudierten pulverförmigen Textilwaschmitteln. Die Verwendung oben genannter Proteinderivate in pulverförmigen Textilwaschmitteln ist daher ebenfalls Teil der Erfindung; vorzugsweise werden die obengenannten Proteinderivate jedoch in flüssigen Textilwaschmitteln eingesetzt.
Dabei sind kationisch derivatisierte Eiweißhydrolysate besonders bevorzugt. Another object of the invention is the use of protein-fatty acid condensates, protein hydrolyzates and / or cationically derivatized protein hydrolyzates as dye transfer inhibitors in textile detergents, preferably liquid textile detergents. The water-soluble protein derivatives mentioned naturally also exert their dye transfer-inhibiting action in granulated or extruded powdered textile detergents. The use of the above-mentioned protein derivatives in powdered laundry detergents is therefore also part of the invention; however, the above-mentioned protein derivatives are preferably used in liquid laundry detergents.
Cationically derivatized protein hydrolyzates are particularly preferred.

Ein weiterer Erfindungsgegenstand ist ein Verfahren zum Waschen von verfärbungsempfindlichen Textilien in wäßrigen Waschlaugen, die Seife, nichtionisches Tensid ausgewählt aus der Gruppe der oben näher beschriebenen C10-C18-Alkoholethoxylate und der Gruppe der oben näher beschriebenen C8-C18-Alkylglucoside und einen Farbstoffübertragungsinhibitor enthalten, wobei der Farbstoffübertragungsinhibitor ein wasserlösliches Proteinderivat ausgewählt aus Eiweiß-Fettsäure-Kondensaten, Eiweißhydrolysaten oder kationisch derivatisierten Eiweißhydrolysaten sowie deren Mischungen ist.Another object of the invention is a method for washing discoloration-sensitive textiles in aqueous wash liquors, the soap, nonionic surfactant selected from the group of the C 10 -C 18 alcohol ethoxylates described above and the group of the C 8 -C 18 alkyl glucosides described above and contain a dye transfer inhibitor, the dye transfer inhibitor being a water-soluble protein derivative selected from protein-fatty acid condensates, protein hydrolyzates or cationically derivatized protein hydrolyzates and mixtures thereof.

Die folgenden Beispiele dienen der weiteren Erläuterung. The following examples are provided for further explanation.

BeispieleExamples ViskositätserhöhungViscosity increase

Zum Nachweis des erfindungsgemäßen Einflusses der wasserlöslichen Proteinderivate auf die Viskosität wurden die in Tabelle I, II und III aufgelisteten Flüssigwaschmittel hergestellt. Die Viskositätsmessungen wurden mit einem Brookfield-RVT-Viskosimeter bei 20°C durchgeführt. Die Drehzahl betrug 20 Umdrehungen pro Minute, wobei die Spindel so ausgewählt wurde, daß der Meßbereich im mittleren Skalenbereich des Gerätes liegt. Als Meßgefäße wurden Bechergläser mit einem Inhalt von ca. 750 ml gewählt.To demonstrate the influence of water-soluble protein derivatives according to the invention on viscosity were those listed in Tables I, II and III Liquid detergent made. The viscosity measurements were made with a Brookfield RVT viscometer at 20 ° C. The speed was 20 revolutions per minute, the spindle being selected so that the measuring range lies in the middle scale range of the device. As measuring vessels beakers with a content of approx. 750 ml were selected.

Die in Tabelle I unter den Nummern 2 bis 4 aufgelisteten Flüssigwaschmittel enthalten Kollagenhydrolysat. Das Vergleichsbeispiel 1 ist frei von Kollagenhydrolysat.The liquid detergents listed in Table I under numbers 2 to 4 contain collagen hydrolyzate. Comparative example 1 is free of Collagen hydrolyzate.

Die in Tabelle II aufgeführten Flüssigwaschmittel 6 bis 9 enthalten ein Kollagenhydrolysat-Kokosfettsäurekondensat-Kaliumsalz. Vergleichsbeispiel 5 enthält kein Kollagenhydrolysat-Fettsäurekondensat.The liquid detergents 6 to 9 listed in Table II contain one Collagen hydrolyzate coconut fatty acid condensate potassium salt. Comparative example 5 does not contain collagen hydrolyzate fatty acid condensate.

Die in Tabelle III aufgeführten Flüssigwaschmittel 11, 12 und 14 bis 16 enthalten ein kationisch derivatisiertes Eiweißhydrolysat (Lauryldimoniumhydroxypropylsubstituiertes Kollagenhydrolysat). Die Vergleichsbeispiele 10 und 13 sind frei davon.The liquid detergents 11, 12 and 14 to 16 listed in Table III contain a cationically derivatized protein hydrolyzate (lauryldimonium hydroxypropyl substituted Collagen hydrolyzate). The comparative examples 10 and 13 are free of it.

In allen Beispielen hat die Erhöhung der Menge an wasserlöslichem Proteinderivat eine starke Erhöhung der Viskosität des jeweiligen Flüssigwaschmittels zur Folge.

Figure 00100001
Figure 00110001
Figure 00120001
In all examples, the increase in the amount of water-soluble protein derivative results in a sharp increase in the viscosity of the respective liquid detergent.
Figure 00100001
Figure 00110001
Figure 00120001

FarbstoffübertragungsinhibierungDye transfer inhibition

  • I.) Es wurde ein (nicht erfindungsgemäßes) Flüssigwaschmittel A folgender Zusammensetzung hergestellt. C12-C18-Fettsäure (Edenor K12-18) 5 Gew.-% Na-Laurylsulfat (Sulfopon K35) 5 Gew.-% C12-C18-Fettalkohol x 7 EO (Dehydol LT7) 12,5 Gew.-% C12-C16-Fettalkoholglucosid, x = 1,4 (APG 600) 2,5 Gew.-% Ethanol 5 Gew.-% Parfümöl 1 Gew.-% Ethylenglykoldistearat (Cutina AGS) 0,3 Gew.-% Dann wurde mit KOH ein pH-Wert von 8 eingestellt. Anschließend wurde mit Wasser auf 100 % aufgefüllt. Das so hergestellte, nicht erfindungsgemäße, Flüssigwaschmittel war frei von Proteinderivaten und hatte eine Viskosität von 250 mPa·s.Analog zu A wurde ein erfindungsgemäßes Flüssigwaschmittel C hergestellt, in dem anstelle der entsprechenden Menge Wasser zusätzlich 14,3 Gew.-% Lamequat L (Lauryldimoniumhydroxypropyl-substituiertes Kollagenhydrolysat, MG 600-700) als 35 Gew.-% wäßrige Lösung (entsprechend 5 Gew.-% Substanz absolut) enthalten waren.Das erfindungsgemäße Flüssigwaschmittel C und das nicht-erfindungsgemäße Flüssigwaschmittel A wurden bei 40°C in einem Linitest-Gerät und einer Dosierung von 6 g/l mit Wasser von 16°dH im Ein-Laugenwaschverfahren auf eine farbinhibierende Wirkung untersucht. Hierzu wurden im Handel gekaufte Textilien, die sehr stark zur Abgabe von Farbstoff neigten, zusammen mit jeweils gleichartigem, aber weißem Gewebe gewaschen. Außerdem wurden die Waschvorgänge ohne Waschmittel wiederholt (s. in der Tabelle unter "Wasser"). Das Beladungs/Flottenverhältnis lag jeweils bei 1:50. Das AusmaB der Anfärbung der weißen Textilien wurde durch Ermittlung des "Farbabstands" in %, bezogen auf dE max. ermittelt. Diese Prüfmethode ist beschrieben in der Zeitschrift "defazet", 31. Jahrgang (1977), Heft 8, Seiten 318 bis 324. Niedrige Prozent-Werte bedeuten geringe Verfärbung, 0 % bedeutet keine Verfärbung. Die Ergebnisse sind in Tabelle IV aufgeführt (Angaben in %). abfärbendes Textilgewebe: Wolle, schwarz Baumwolle, rot (Siriuslichtrot F4BL) Seide, grün Seide, rot (Siriuslichtrot F4BL) angefärbtes Textilgewebe: Wolle, weiß Baumwolle, weiß Seide, weiß Seide, weiß Flüssigwaschmittel A 27,0 37,3 14,1 17,4 Flüssigwaschmittel C 22,2 35,5 12,7 10,7 Wasser 24,9 31,7 8,0 3,0 Den Beispielen kann entnommen werden, daß beim Waschen mit dem erfindungsgemäßen Flüssigwaschmittel C die Farbstoffübertragungs-Inhibierung deutlich stärker ausgeprägt ist als beim Waschen mit dem Vergleichsmittel A und teilweise sogar die Werte von ohne Waschmittel "gewaschenen" Textilien erreicht.I.) A liquid detergent A (not according to the invention) with the following composition was produced. C 12 -C 18 fatty acid (Edenor K12-18) 5% by weight Na lauryl sulfate (Sulfopon K35) 5% by weight C 12 -C 18 fatty alcohol x 7 EO (Dehydol LT7) 12.5% by weight C 12 -C 16 fatty alcohol glucoside, x = 1.4 (APG 600) 2.5% by weight Ethanol 5% by weight Perfume oil 1% by weight Ethylene glycol distearate (Cutina AGS) 0.3% by weight Then a pH of 8 was adjusted with KOH. The mixture was then made up to 100% with water. The liquid detergent thus produced, not according to the invention, was free of protein derivatives and had a viscosity of 250 mPas. Analogous to A, a liquid detergent C according to the invention was produced, in which an additional 14.3% by weight of lamequat L ( Lauryldimonium hydroxypropyl-substituted collagen hydrolyzate, MW 600-700) were contained as 35% by weight aqueous solution (corresponding to 5% by weight absolute substance). The liquid detergent C according to the invention and the liquid detergent A not according to the invention were tested at 40 ° C. in a Linitest -Device and a dosage of 6 g / l with water of 16 ° dH in a one-lye washing process examined for a color-inhibiting effect. For this purpose, commercially purchased textiles that had a strong tendency to release dye were washed together with the same, but white fabric. In addition, the washing processes were repeated without detergent (see in the table under "water"). The load / liquor ratio was 1:50 in each case. The extent of the dyeing of the white textiles was determined by determining the "color difference" in%, based on the max. determined. This test method is described in the magazine "defazet", 31st year (1977), number 8, pages 318 to 324. Low percentages mean little discoloration, 0% means no discoloration. The results are shown in Table IV (in%). staining textile fabric: Wool, black Cotton, red (Sirius light red F4BL) Silk, green Silk, red (Sirius light red F4BL) dyed textile fabric: Wool, white Cotton white Silk, white Silk, white Liquid detergent A 27.0 37.3 14.1 17.4 Liquid detergent C 22.2 35.5 12.7 10.7 water 24.9 31.7 8.0 3.0 It can be seen from the examples that the dye transfer inhibition is markedly more pronounced when washing with the liquid detergent C according to the invention than when washing with the comparative agent A and in some cases even reaches the values of textiles "washed" without detergent.
  • II.) Es wurde ein weiteres erfindungsgemäßes Flüssigwaschmittel, B, hergestellt, das anstelle der in C verwendeten 5 Gew.-% (Substanz absolut) Lamequat L nur 1 Gew.-% (Substanz absolut) Lamequat L enthielt. Analog zu Beispiel I.) wurden im Handel gekaufte farbige Textilien (schwarzes Wollgewebe, türkisfarbene Seide, rote Seide) zusammen mit gleichartigen, nicht gefärbten Textilstreifen (also weißes Wollgewebe, weiße Seide) gewaschen. Alle Versuche wurden jeweils dreimal durchgeführt und anschließend der Mittelwert der erzielten Ergebnisse gebildet.Außerdem wurde während des Waschens ein weißer Streifen Multifasergewebe zugefügt. Das Multifasergewebe besteht aus aneinandergewebten Abschnitten verschiedener Textilien, nämlich Baumwolle, Polyamid, Polyacryl, Nylon. In dem Versuch wurden dabei jeweils der Baumwoll- und der Nylonstreifen ausgewertet. Außerdem wurden wie oben in Beispiel I.) die weiße Wolle und die weiße Seide beurteilt. Gemessen wurde wie in Beispiel I.) der durch das Waschen hervorgerufene Grad der Anfärbung der ehemals weißen Textilstücke im Vergleich zu den nicht angefärbten ursprünglichen Textilien. Die Ergebnisse sind Tabelle V zu entnehmen (Angaben in %).
    Figure 00160001
    Figure 00170001
    II.) A further liquid detergent according to the invention, B, was produced which, instead of the 5% by weight (absolute substance) Lamequat L used in C, contained only 1% by weight (absolute substance) Lamequat L. Analogously to Example I.), commercially purchased colored textiles (black woolen fabric, turquoise silk, red silk) were washed together with similar, non-dyed textile strips (i.e. white woolen fabric, white silk). All trials were run three times, then averaging the results obtained, and a white stripe of multifiber fabric was added during the wash. The multifiber fabric consists of sections of various textiles woven together, namely cotton, polyamide, polyacrylic, nylon. In the experiment, the cotton and nylon strips were evaluated. In addition, the white wool and white silk were evaluated as in Example I.) above. As in Example I.), the degree of staining caused by the washing of the formerly white textile pieces was measured in comparison to the non-dyed original textiles. The results are shown in Table V (in%).
    Figure 00160001
    Figure 00170001

    • Es ist erkennbar, daß die Lamequat L-haltigen Rezepturen B und C bessere farbübertragungsinhibierende Wirkungen zeigen als das nicht erfindungsgemäße Mittel A; mit steigendem Lamequat L-Gehalt nimmt dabei die farbübertragungsinhibierende Wirkung zu.It can be seen that the Lamequat L-containing formulations B and C are better color transfer inhibiting effects show as that not according to the invention Agent A; with increasing lamequat L content, the color transfer inhibiting decreases Effect too.

    Claims (6)

    1. A liquid laundry detergent with a viscosity at 20°C of 100 to 2,000 mPa.s and preferably 200 to 1,000 mPa.s containing
      0.1 to 30% by weight of soap,
      0.1 to 50% by weight of a nonionic surfactant selected from the group of alcohol ethoxylates corresponding to the general formula R1O(C2H4O)nH, where R1 is a linear or branched alkyl or alkenyl group containing 10 to 18 carbon atoms and n is a number of 1 to 15, and alkyl glucosides corresponding to the general formula R2O(G)X, where R2 is a linear or branched alkyl or alkenyl group containing 8 to 18 carbon atoms, G is a glucose unit and x is a number of 1.1 to 1.4, and mixtures thereof and
      0.1 to 10% by weight of a water-soluble protein derivative with an average molecular weight of 400 to 4,000 selected from protein/fatty acid condensates, protein hydrolyzates and cationically derivatized protein hydrolyzates.
    2. A liquid detergent as claimed in claim 1 additionally containing up to 30% by weight of a fatty alcohol sulfate corresponding to the general formula R3OSO3 (-) M(+), where R3 is a linear or branched alkyl or alkenyl group containing 12 to 18 carbon atoms and M(+) is an alkali metal or ammonium cation.
    3. The use of protein/fatty acid condensates, protein hydrolyzates and/or cationically derivatized protein hydrolyzates for increasing the viscosity of liquid laundry detergents.
    4. The use of protein/fatty acid condensates, protein hydrolyzates and/or cationically derivatized protein hydrolyzates as dye transfer inhibitors in laundry detergents, preferably liquid laundry detergents.
    5. The use of cationically derivatized protein hydrolyzates as claimed in claim 4 as dye transfer inhibitors in laundry detergents, preferably liquid laundry detergents.
    6. A process for washing discoloration-sensitive fabrics in water-based wash liquors containing soap, nonionic surfactant selected from C10-18 alcohol ethoxylate and C8-18 alkyl glucoside and a dye transfer inhibitor, characterized in that a water-soluble protein derivative selected from protein/fatty acid condensates, protein hydrolyzates and cationically derivatized protein hydrolyzates is present as the dye transfer inhibitor.
    EP94926859A 1993-08-28 1994-08-20 Liquid washing product Expired - Lifetime EP0715647B2 (en)

    Applications Claiming Priority (3)

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    DE4329065 1993-08-28
    DE4329065A DE4329065A1 (en) 1993-08-28 1993-08-28 liquid detergent
    PCT/EP1994/002774 WO1995006703A1 (en) 1993-08-28 1994-08-20 Liquid washing product

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    EP0715647A1 EP0715647A1 (en) 1996-06-12
    EP0715647B1 true EP0715647B1 (en) 1998-01-07
    EP0715647B2 EP0715647B2 (en) 2004-06-02

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    FR2738835B1 (en) † 1995-09-18 1997-10-17 Oreal THICKNESS COMPOSITION IN AQUEOUS MEDIUM, PROCESS FOR THICKENING OF AN AQUEOUS MEDIUM AND USES IN COSMETICS
    FR2761702B1 (en) * 1997-04-08 1999-05-28 Bernard Jacques George Dubreux PROCESS FOR WASHING FABRICS IN AQUEOUS BATHS TO AVOID OR LIMIT DYE TRANSFER
    US6028046A (en) * 1997-08-11 2000-02-22 Witco Corporation Detergents with polyamine alkoxylates useful in cleaning dyed fabrics while inhibiting dye transfer
    DE19942538A1 (en) * 1999-09-07 2001-03-08 Cognis Deutschland Gmbh laundry detergent
    DE10253216A1 (en) * 2002-11-15 2004-05-27 Cognis Deutschland Gmbh & Co. Kg Use of low molecular weight protein hydrolyzates in washing and cleaning agents
    DE10317399A1 (en) * 2003-04-15 2004-11-11 Henkel Kgaa Damage-free machine washing of sensitive textiles in aqueous media, using flexible textile fixing device and detergent with specific foaming properties to reduce shrinkage and creasing
    DE102010001193A1 (en) * 2010-01-25 2011-07-28 Dahms, Gerd, 47138 Surfactant composition, useful e.g. in surface-active preparation, comprises protein-fatty acid-condensate and/or protein hydrolyzate quat, alkylpolyglucoside, water, and optionally further surfactants e.g. betaine, and further additives

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    EP0530418A1 (en) * 1991-08-26 1993-03-10 Protein Technologies International, Inc. Method of improving the soil anti-redeposition properties of washing detergents and products

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    WO1995006703A1 (en) 1995-03-09
    EP0715647B2 (en) 2004-06-02
    EP0715647A1 (en) 1996-06-12
    DE4329065A1 (en) 1995-03-02
    ATE161877T1 (en) 1998-01-15
    DE59404971D1 (en) 1998-02-12

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