EP0068232A2 - Liquid detergent containing dye transfer inhibition additives - Google Patents

Liquid detergent containing dye transfer inhibition additives Download PDF

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Publication number
EP0068232A2
EP0068232A2 EP19820105121 EP82105121A EP0068232A2 EP 0068232 A2 EP0068232 A2 EP 0068232A2 EP 19820105121 EP19820105121 EP 19820105121 EP 82105121 A EP82105121 A EP 82105121A EP 0068232 A2 EP0068232 A2 EP 0068232A2
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EP
European Patent Office
Prior art keywords
weight
water
polyglycol ether
ethylene oxide
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP19820105121
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German (de)
French (fr)
Inventor
Rudolf Weber
Winfried Pochandke
Hans Dr. Andree
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0068232A2 publication Critical patent/EP0068232A2/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719Polyamides or polyimides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the present invention relates to a liquid detergent based on nonionic surfactants, which additionally contains certain water-soluble, synthetically produced, ionic polymeric compounds which counteract dye transfer from colored textiles to white or light-colored textiles during washing together.
  • Dye transfer when washing colored and white or light-colored textiles together has been a problem that has been known for a long time, for which there have already been some proposed solutions, but which are not entirely satisfactory because they are only marginal compared to a number of colors or textiles Have effect.
  • an agent is known whose discoloration-inhibiting additive is polyvinylpyrrolidone.
  • DE-OS 24 20 561 describes a detergent with a combination of alkali metal percarbonate and polyethylene glycol of a certain molecular weight and / or Pclyvinylpyrrolidor ,.
  • DE-OS 23 09 099 relates to an agent with proportions of two different organic compounds that contain basic nitrogen atoms in the molecule.
  • US Pat. Nos. 4,005,029 and 4,006,092 agents are described which contain per compounds which have an anti-discoloring effect.
  • DE-OS 28 28 619 describes a discoloration-inhibiting detergent composed of three different types of surfactants, namely 1. nonionic surfactants, 2. zwitterionic or semipolar and 3. cationic surfactants, which must be present in certain proportions.
  • a liquid detergent containing nonionic or zwitterionic surfactants in combination with synthetic, water-soluble, amino and / or amido group-containing polymers from the group of polyethyleneimines, polyamines, polyaminamides and polyacrylamides, the detergent containing no quaternary ammonium compounds which soften the textile and is essentially phosphate-free, has an improved discoloration-inhibiting effect not only on textiles made of cotton but also of synthetic fibers and mixtures of synthetic and natural fibers.
  • Such polymers which can be used individually or optionally in combination with other water-soluble polymeric compounds in the detergents according to the invention, are known, synthetically produced compounds which are used, for example, in the paper industry as retention agents for better separation of the paper fiber raw materials and fillers. According to their structural structure, these polymers can be divided into four groups: polyethyleneimines, polyamines, polyaminamides and polyacrylamides.
  • Suitable polyethyleneimines are obtained by acid-catalyzed polymerization of ethyleneimine and can be modified by urea and epichlorohydrin or dichloroethane.
  • Polyethyleneimines can contain primary, secondary and tertiary amino groups as well as quaternary ammonium groups.
  • Aqueous solutions of polyethyleneimines react basicly. The molecular weight can be up to 100,000.
  • Polyamines are addition or condensation products from polyvalent aliphatic amines and substances with several reactive groups, e.g. Epichlorohydrin or alkylene dihalides. They therefore always contain several secondary, tertiary or quaternary nitrogen atoms, and possibly also hydroxyl groups in the molecule. Accordingly, they are hydrophilic, polar compounds that behave like polyelectrolytes and are water-soluble; unless they contain large hydrophobic groups in the molecule. The polyamines react basicly in aqueous solution. Suitable compounds are described, for example, in US Pat. No. 2,969,302.
  • Polyaminamides contain amino and amide at the same time. groups in the molecule. They are produced, for example, by condensation of polybasic acids, for example dibasic, saturated, aliphatic C 3 - to C 8 acids, and polyamines, and also with substances which contain several reactive groups, such as epichlorohydrin. These compounds also react basicly in aqueous solution. Suitable polyaminamides are described, for example, in US Pat. No. 2,926,154.
  • Suitable polyacrylamides are high molecular weight polymers with molecular weights of several million.
  • carboxyl groups which are formed, for example, by partial hydrolysis, in addition to amide groups, anionic polyacrylamides are obtained, while polyacrylamides containing amino groups react in a basic manner in aqueous solution.
  • Amino groups can be introduced, for example, by reaction with alkali and hypobromite or hypochlorite.
  • polymers mentioned have in common that they are water-soluble.
  • Such polymers are commercially available products.
  • Particularly suitable as an additive to the detergents according to the invention are the polyethyleneimines and polyamines which react strongly in water.
  • Particularly suitable polyethyleneimines are "Retaminol E” and for polyamines, e.g. "Retaminol K”, from Bayer AG, Leverkusen, Federal Republic of Germany.
  • These polymers can be added to the detergents according to the invention either alone or in combination with other water-soluble polymers.
  • These are, for example, water-soluble resins made from melamine or urea and formaldehyde, e.g.
  • the concentration of the polymers mentioned in a detergent according to the invention based on nonioni African, zwitterionic or amphoteric surfactants are in the range from about 1 to 1.5% by weight, preferably 5 to 5% by weight, based on the amount of surfactant in the detergent.
  • the application concentration of the detergent is. in the range from 1 to 10 g / 1 wash liquor, preferably in the range from 3 to 6 g / l.
  • the detergents according to the invention are preferably phosphate-free; however, they can also contain small amounts of phosphate, which corresponds to about 3% by weight of phosphorus.
  • Addition products of 2-40, preferably 2-20, moles of ethylene oxide with 1 mole of fatty alcohol or oxo alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants.
  • the addition products of 5-16 mol of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18, carbon atoms, and with mono- or dialkylphenols with 6-14 carbon atoms in, are particularly important the alkyl residues.
  • non-fully or not fully water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • Amine oxide or sulfoxide type surfactants can be used.
  • the zwitterionic or amphoteric surfactants contain both acidic groups, such as the carboxyl, sulfo, sulfuric acid half-ester, phosphono or phosphoric acid partial ester groups, as well as basic groups, such as amino, imino or ammonium groups, in the molecule.
  • Zwitterionic compounds with a tetrasubstituted, ie quaternary ammonium group are called betaines if they also have a covalently bound acid group in the molecule and the positive and negative charge is balanced intramolecularly.
  • the betaines also include the correspondingly substituted quaternary phosphonium and tertiary sulfonium compounds.
  • the surface-active betaines generally have a higher molecular weight aliphatic hydrocarbon radical with a hydrophobic character and two lower alkyl radicals with 1-3 carbon atoms, which can be substituted by one or two hydroxyl groups or linked directly or via a hetero atom.
  • the water-solubilizing carboxylate, sulfonate or sulfate group is linked to the ammonium nitrogen via the fourth substituent, which usually consists of a short-chain aliphatic radical which may have a double bond or a hydroxyl group.
  • sulfonate betaines in which the anionic, water-solubilizing group is bonded directly to the long-chain, hydrophobic hydrocarbon residue responsible for capillary activity.
  • Such sulfobetaines can be obtained, for example, from the sultones which can be prepared from C 8 -C 20 - ⁇ -olefins with S0 3 and a tertiary amine with three chain aliphatic radicals obtained.
  • Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylanmonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonio) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethylammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.
  • the quantitative ratio of a): b) is preferably 2: 1 to 1: 2.
  • alkyl polyglycol ethers of the formula I which are suitable as component a) are derived from alcohols which are prepared by reacting linear olefins with carbon monoxide and hydrogen by the known oxo process by hydroformylation and subsequent hydrogenation.
  • Commercially available oxo alcohol mixtures which are suitable for the preparation of the surfactant component a) are, for example, the oxo alcohols available from Deutsche under the trade name "Dobanol”. Shell Chemie Deutschen, which have about 25 wt .-% of 2-alkyl branches, other suitable oxo-alcohols are among the. Name "Synprol" of Inperial Chemical Industries Ltd.
  • alkyl polyglycol ethers which represent ethylene oxide condensates of the aforementioned oxo alcohols with 13 to 15 carbon atoms and an average ethylene oxide content of approximately 55 to 65% by weight.
  • Typical preferred products are, for example, "Dobanol 45-7”, which consists of at least 95% C 14 / C 15 oxo alcohol with an average of 7 moles of ethylene oxide, and "Lutensol AO-8", which is a C 13 / C 15 oxo Alcohol represents ethoxylate with an average of 8 moles of ethylene oxide.
  • alkyl polyglycol ethers whose alcohol base is natural or synthetic primary fatty alcohols or oxo alcohols which contain 9 to 12 carbon atoms and have an ethylene oxide content of approximately 60 to 70% by weight.
  • Typical preferred products are, for example, the commercial product "Marlipal KF” (Chemische Werke Huls), which is a C 10 / C 12 fatty alcohol ethoxylate with an average of 6 moles of ethylene oxide, and the "Lutensol ON-70", which is a C 9 / C 11 -Oxo alcohol ethoxylate with an average of 7 moles of ethylene oxide.
  • Suitable fatty alcohols as the basis for preferred alkyl polyglycol ethers are also the commercial products "Lorol C-8 to 12" (Henkel).
  • the ratio of the amount of component a) used to the amount of component b) essentially determines the parameters of washing power, foaming behavior and softening effect. Optimal results are obtained when the ratio of a): b) is between about 2: 1 and 1: 2.
  • component a) and component b) of 10 to 30% by weight, based on the total weight of the detergent, are used, an amount of 15 to 30% by weight being preferred.
  • Pasty and in particular liquid detergents containing the discoloration-inhibiting polymers described are particularly preferred.
  • Water is preferably used as the solvent for the preferred liquid detergents.
  • organic solvents can also be used in amounts of up to 20, preferably up to 16% by weight of the total liquid detergent.
  • additional solvents are either lower alkanols or lower diols or polyols such as ethanol, isopropyl alcohol, ethylene glycol, propylene glycol or glycerin.
  • polyols with ether linkages such as methyl, ethyl, butyl or diethylene glycol or their acetates (for example products of the "Cellosolve" type from Union Carbide Corp.) can also be used.
  • solubilizers so-called hydrotropes
  • hydrotropes are non-surfactant organic sulfonates, such as C 6 -C 12 alkanesulfonates, and the salts of toluene, xylene and cumene sulfonic acid, preferably their alkanolamine and alkali salts, especially their potassium salts.
  • Urea is also suitable as a hydrotrope.
  • Hydrotropes are added in amounts of 2 to 12, preferably 3 to 9% by weight, based on the total liquid detergent.
  • auxiliaries which are likewise usually effective in small amounts, can be added to the detergents according to the invention;
  • opacifiers and viscosity regulators which are usually contained in the detergent at about 0.05 to 2% by weight.
  • esters of alkanols or partial esters of polyols with longer-chain fatty acids such as palmitic or stearic acid.
  • a typical product is ethylene glycol stearate.
  • Formalin is usually used as a preservative in an amount of 0.05 to 1% by weight.
  • complexing agents for heavy metal ions are added.
  • Common complexing agents are the sodium, potassium or triethanolamine salts of aminopolycarboxylic acids, such as, for example, ethylenediaminetetraacetic acid or nitrilostriacetic acid. They are used in amounts of 0.1 to 1% by weight.
  • Suitable fragrances are substances with a floral / fresh or fruity fragrance or those designated as cosmetic or creamy.
  • the detergents contained the following substances in the stated amounts as water-soluble polymers:

Abstract

The detergent based on nonionic or zwitterionic surfactants contains synthetically prepared water-soluble amines and/or polymers having amino groups, from the class of polyethyleneimines, polyamines, polyaminoamides and polyacrylamides. A preferred composition contains a) 5 to 18 (7.5 to 12.5) per cent by weight of a certain fatty alcohol polyglycol ether having an ethylene oxide content of 55 to 65%, b) 5 to 18 (7.5 to 12.5) per cent by weight of a fatty alcohol polyglycol ether or oxo alcohol polyglycol ether having an ethylene oxide content of 60 to 70% in a relative ratio of a) to b) of 2 : 1 to 1 : 2, c) 0.2 to 2 per cent by weight of water-soluble polymers from the group comprising polyethyleneimines and polyamines, d) 2.5 to 4.0 per cent by weight of other water-soluble polymers. The remainder is made up of conventional additives for liquid detergents. The detergents are free of textile-softening quaternary ammonium compounds and substantially phosphate-free. Detergents of such a composition counteract staining of white or pale-coloured textiles by coloured textiles during joint washing.

Description

Die vorliegende Erfindung betrifft ein flüssiges Waschmittel auf Basis von nichtionischen Tensiden, das zusätzlich bestimmte wasserlösliche.synthetisch hergestellte, ionische polymere Verbindungen enthält, durch die einer Farbstoffübertragung von farbigen Textilien auf weiße oder hellfarbige Textilien während des gemeinsamen Waschens entgegengewirkt wird.The present invention relates to a liquid detergent based on nonionic surfactants, which additionally contains certain water-soluble, synthetically produced, ionic polymeric compounds which counteract dye transfer from colored textiles to white or light-colored textiles during washing together.

Die Farbstoffübertragung bei der gemeinsamen Wäsche von farbigen und weißen bzw. hellfarbigen Textilien ist ein seit langem bekanntes Problem, für das es bereits einige Lösungsvorschläge gibt, die aber alle nicht voll befriedigen können, weil sie gegenüber einer Reihe von Ausfärbungen bzw. Textilien nur eine geringe Wirkung aufweisen. So ist z.B. aus der DE-AS 22 32 353 ein Mittel bekannt, dessen verfärbungsinhibierender Zusatz Polyvinylpyrrolidon ist. Die DE-OS 24 20 561 beschreibt ein Waschmittel mit einer Kombination aus Alkalimetall-Percarbonat und Polyethylenglykol eines bestimmten Molekulargewichts und/oder Pclyvinylpyrrolidor,. Die DE-OS 23 09 099 betrifft ein Mittel mit Anteilen an zwei verschiedenen organischen Verbindungen, die basische Stickstoffatome im Molekül enthalten. In den US-PS 4 005 029 und 4 006 092 sind Mittel beschrieben, die verfärbunrsinhibierend wirkende Perverbindungen enthalten.Dye transfer when washing colored and white or light-colored textiles together has been a problem that has been known for a long time, for which there have already been some proposed solutions, but which are not entirely satisfactory because they are only marginal compared to a number of colors or textiles Have effect. For example, from DE-AS 22 32 353 an agent is known whose discoloration-inhibiting additive is polyvinylpyrrolidone. DE-OS 24 20 561 describes a detergent with a combination of alkali metal percarbonate and polyethylene glycol of a certain molecular weight and / or Pclyvinylpyrrolidor ,. DE-OS 23 09 099 relates to an agent with proportions of two different organic compounds that contain basic nitrogen atoms in the molecule. In US Pat. Nos. 4,005,029 and 4,006,092 agents are described which contain per compounds which have an anti-discoloring effect.

In der deutschen Patentanmeldung P 30 26 090.3 wurde vorgeschlagen, zur Verhinderung der Farbstoffübertragung flüssigen Waschmitteln auf Basis von bestimmten nichtionischen Tensiden und textilweichmachenden quartären Ammoniumverbindungen kationische Stärkeether zuzusetzen. In der DE-OS 28 28 619 ist ein verfärbungsinhibierendes Waschmittel aus drei verschiedenen Tensid-Typen beschrieben, nämlich 1. nichtionischen Tensiden, 2. zwitterionischen oder semipolaren und 3. kationischen Tensiden, die in bestimmten Mengenverhältnissen vorhanden sein müssen.In German patent application P 30 26 090.3 it was proposed to add cationic starch ethers to prevent liquid transfer to liquid detergents based on certain nonionic surfactants and quaternary ammonium textile softening agents. DE-OS 28 28 619 describes a discoloration-inhibiting detergent composed of three different types of surfactants, namely 1. nonionic surfactants, 2. zwitterionic or semipolar and 3. cationic surfactants, which must be present in certain proportions.

Es wurde nun gefunden, daß ein flüssiges Waschmittel, enthaltend nichtionische oder zwitterionische Tenside in Kombination mit synthetischen, wasserlöslichen, amino-und/oder amidogruppenhaltigen Polymeren aus der Gruppe der Polyethylenimine, Polyamine, Polyaminamide und Polyacrylamide, wobei das Waschmittel keine textilweichmachenden quartären Ammoniumverbindungen enthält und im wesentlichen phosphatfrei ist, eine verbesserte verfärbungsinhibierende Wirkung nicht nur auf Textilien aus Baumwolle sondern auch aus synthetischen Fasern und Gemischen aus synthetischen und natürlichen Fasern aufweist.It has now been found that a liquid detergent containing nonionic or zwitterionic surfactants in combination with synthetic, water-soluble, amino and / or amido group-containing polymers from the group of polyethyleneimines, polyamines, polyaminamides and polyacrylamides, the detergent containing no quaternary ammonium compounds which soften the textile and is essentially phosphate-free, has an improved discoloration-inhibiting effect not only on textiles made of cotton but also of synthetic fibers and mixtures of synthetic and natural fibers.

Derartige Polymere, die einzeln oder gegebenenfalls in Kombination mit sonstigen wasserlöslichen polymeren Verbindungen in den erfindungsgemäßen Waschmitteln eingesetzt werden können, sind bekannte, synthetisch hergestellte Verbindungen, die beispielsweise in der Papierindustrie als Retentionsmittel zur besseren Abscheidung der Papierfaser-Rohstoffe und Füllstoffe verwendet werden. Nach ihrem strukturellen Aufbau lassen sich diese Polymere in vier Gruppen einteilen: Polyethylenimine, Polyamine, Polyaminamide und Polyacrylamide.Such polymers, which can be used individually or optionally in combination with other water-soluble polymeric compounds in the detergents according to the invention, are known, synthetically produced compounds which are used, for example, in the paper industry as retention agents for better separation of the paper fiber raw materials and fillers. According to their structural structure, these polymers can be divided into four groups: polyethyleneimines, polyamines, polyaminamides and polyacrylamides.

Geeignete Polyethylenimine werden durch säurekatalysierte Polymerisation von Ethylenimin erhalten und können durch Harnstoff und Epichlorhydrin bzw. Dichlorethan modifiziert werden. Polyethylenimine können primäre, sekundäre und tertiäre Aminogruppen sowie quartäre Ammoniumgruppen enthalten. Wäßrige Lösungen von Polyethyleniminen reagieren basisch. Das Molekulargewicht kann bis zu 100000 betragen.Suitable polyethyleneimines are obtained by acid-catalyzed polymerization of ethyleneimine and can be modified by urea and epichlorohydrin or dichloroethane. Polyethyleneimines can contain primary, secondary and tertiary amino groups as well as quaternary ammonium groups. Aqueous solutions of polyethyleneimines react basicly. The molecular weight can be up to 100,000.

Polyamine sind Additions- oder Kondensationsprodukte aus mehrwertigen aliphatischen Aminen und Substanzen mit mehreren reaktionsfähigen Gruppen, z.B. Epichlorhydrin oder Alkylendihalogeniden. Sie enthalten daher stets mehrere sekundäre, tertiäre oder auch quartäre Stickstoffatome, sowie evtl. auch Hydroxylgruppen im Molekül. Sie sind dementsprechend hydrophile, polare Verbindungen, die sich wie Polyelektrolyte verhalten und wasserlöslich sind; soweit sie nicht große hydrophobe Gruppen im Molekül enthalten. In wäßriger Lösung reagieren die Polyamine basisch. Geeignete Verbindungen sind beispielsweise in der US-Patentschrift 2,969,302 beschrieben.Polyamines are addition or condensation products from polyvalent aliphatic amines and substances with several reactive groups, e.g. Epichlorohydrin or alkylene dihalides. They therefore always contain several secondary, tertiary or quaternary nitrogen atoms, and possibly also hydroxyl groups in the molecule. Accordingly, they are hydrophilic, polar compounds that behave like polyelectrolytes and are water-soluble; unless they contain large hydrophobic groups in the molecule. The polyamines react basicly in aqueous solution. Suitable compounds are described, for example, in US Pat. No. 2,969,302.

Polyaminamide enthalten gleichzeitig Amino- und Amid- . gruppen im Molekül. Sie werden beispielsweise hergestellt durch Kondensation von mehrbasischen Säuren, z.B. zweibasischen, gesättigten, aliphatischen C3- bis C8-Säuren, und Polyaminen, sowie mit Substanzen, die mehrere reaktionsfähige Gruppen enthalten, wie beispielsweise Epichlorhydrin. Auch diese Verbindungen reagieren in wäßriger Lösung basisch. Geeignete Polyaminamide sind z.B. in der US-Patentschrift Nr. 2,926,154 beschrieben.Polyaminamides contain amino and amide at the same time. groups in the molecule. They are produced, for example, by condensation of polybasic acids, for example dibasic, saturated, aliphatic C 3 - to C 8 acids, and polyamines, and also with substances which contain several reactive groups, such as epichlorohydrin. These compounds also react basicly in aqueous solution. Suitable polyaminamides are described, for example, in US Pat. No. 2,926,154.

Geeignete Polyacrylamide sind hochmolekulare Polymere mit Molgewichten von mehreren Millionen. Durch Einbau von Carboxylgruppen, die beispielsweise durch partielle Hydrolyse gebildet werden, neben Amidgruppen erhält man anionische Polyacrylamide, während Aminogruppen enthaltende Polyacrylamide in wäßriger Lösung basisch reagieren. Aminogruppen lassen sich z.B. durch Reaktion mit Alkali und Hypobromit oder Hypochlorit einführen.Suitable polyacrylamides are high molecular weight polymers with molecular weights of several million. By installation of carboxyl groups, which are formed, for example, by partial hydrolysis, in addition to amide groups, anionic polyacrylamides are obtained, while polyacrylamides containing amino groups react in a basic manner in aqueous solution. Amino groups can be introduced, for example, by reaction with alkali and hypobromite or hypochlorite.

Allen genannten Polymeren ist gemeinsam, daß sie wasserlöslich sind. Derartige Polymere sind handelsübliche Produkte. Besonders geeignet als Zusatz zu den erfindungsgemäßen Waschmitteln sind die in Wasser stark basisch reagierenden Polyethylenimine und Polyamine. Beispiele für handelsübliche besonders geeignete Polyethylenimine sind "Retaminol E" und für Polyamine, z.B. "Retaminol K", der Firma Bayer AG, Leverkusen, Bundesrepublik Deutschland. Diese Polymere können entweder allein oder in Kombination mit sonstigen wasserlöslichen Polymeren den erfindungsgemäßen Waschmitteln zugesetzt werden. Hierbei handelt es sich beispielsweise um wasserlösliche Harze aus Melamin bzw. Harnstoff und Formaldehyd, z.B. um die Handelsprodukte "Pressal R 50" oder "Melan 125" der Firma Henkel, Düsseldorf, Bundesrepublik Deutschland. Weitere als Retentionsmittel bei der Papierherstellung einsetzbare und für die erfindungsgemäßen Waschmittel geeignete Polymere sind beispielsweise in "Encyclopedia of Polymer Science and Technology", Vol 9, S. 762 , John Wiley & Sons, Inc., New York, 1968, beschrieben. Ein Zusatz dieser Polymeren zu den erfindungsgemäßen Waschmitteln bewirkt in Kombination mit den genannten amino- und/oder amidogruppenhaltigen Polymeren eine Verstärkung des verfärbungsinhibierenden Effekts.All of the polymers mentioned have in common that they are water-soluble. Such polymers are commercially available products. Particularly suitable as an additive to the detergents according to the invention are the polyethyleneimines and polyamines which react strongly in water. Examples of commercially available particularly suitable polyethyleneimines are "Retaminol E" and for polyamines, e.g. "Retaminol K", from Bayer AG, Leverkusen, Federal Republic of Germany. These polymers can be added to the detergents according to the invention either alone or in combination with other water-soluble polymers. These are, for example, water-soluble resins made from melamine or urea and formaldehyde, e.g. the commercial products "Pressal R 50" or "Melan 125" from Henkel, Düsseldorf, Federal Republic of Germany. Further polymers which can be used as retention aids in papermaking and are suitable for the detergents according to the invention are described, for example, in "Encyclopedia of Polymer Science and Technology", Vol 9, p. 762, John Wiley & Sons, Inc., New York, 1968. The addition of these polymers to the detergents according to the invention, in combination with the abovementioned polymers containing amino and / or amido groups, enhances the discoloration-inhibiting effect.

Die Konzentration der genannten Polymere in einem erfindungsgemaßen Waschmittel auf Basis von nichtionischen, zwitterionischen oder amphoteren Tensiden liegt im Bereich von etwa 1 bis 1;5 Gew.-%, vorzugsweise 5 bis 5 Gew.-%, bezogen auf die Tensidmenge des Waschmittels. Die Anwendungskonzentration des Waschmittels liegt . im Bereich von 1 bis 10 g/1 Waschlauge, vorzugsweise im Bereich von 3 bis 6 g/l.The concentration of the polymers mentioned in a detergent according to the invention based on nonioni African, zwitterionic or amphoteric surfactants are in the range from about 1 to 1.5% by weight, preferably 5 to 5% by weight, based on the amount of surfactant in the detergent. The application concentration of the detergent is. in the range from 1 to 10 g / 1 wash liquor, preferably in the range from 3 to 6 g / l.

Die erfindungsgemäßen Waschmittel sind vorzugsweise phosphatfrei; jedoch können sie auch in geringen Mengen Phosphat enthalten, der etwa 3 Gew.-% Phosphor entspricht.The detergents according to the invention are preferably phosphate-free; however, they can also contain small amounts of phosphate, which corresponds to about 3% by weight of phosphorus.

Als nichtionische Tenside sind Anlagerungsprodukte von 2-40, vorzugsweise 2-20 Mol Ethylenoxid an 1 Mol Fettalkohol oder Oxoalkohol, Alkylphenol, Fettsäure, Fettamin, Fettsäureamid oder Alkansulfonamid verwendbar. Besonders wichtig sind die Anlagerungsprodukte von 5-16 Mol Ethylenoxid an Kokos- oder Talgfettalkohole, an Oleylalkohol oder an sekundäre Alkohole mit 8 - 18, vorzugsweise 12 - 18 C-Atomen, sowie an Mono- oder Dialkylphenole mit 6 - 14 C-Atomen in den Alkylresten. Neben diesen wasserlöslichen Nonionics sind aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykolether mit 1 - 4 Ethylenglykoletherresten im Molekül von Interesse, insbesondere wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden.Addition products of 2-40, preferably 2-20, moles of ethylene oxide with 1 mole of fatty alcohol or oxo alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants. The addition products of 5-16 mol of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18, carbon atoms, and with mono- or dialkylphenols with 6-14 carbon atoms in, are particularly important the alkyl residues. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.

Weiterhin sind als nichtionische Tenside die wasserlöslichen, 20 - 250 Ethylenglykolethergruppen und 10 - 100 Propylenglykolethergruppen enthaltenden Anlagerungsprodukte von Ethylenoxid an Polypropylenglykol ( = Pluro- nics(R)), Alkylendiamin-polypropylenglykol ( = Tetronics (R)) und Alkylpolypropylenglykole mit 1 - 10 C-Atomen in der Alkylkette brauchbar, in denen die Polypropylenglykolkette als hydrophober Rest fungiert.Other suitable nonionic surfactants are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing adducts of ethylene oxide with polypropylene glycol (= Pluro- nics (R)), alkylenediamine polypropylene glycol (= Tetronics (R)) and A lkylpolypropylenglykole with 1 - 10 Carbon atoms useful in the alkyl chain in which the polypropylene glycol chain acts as a hydrophobic residue.

Auch nichtionische. Tenside vom Typ der Aminoxide oder Sulfoxide sind verwendbar.Also non-ionic. Amine oxide or sulfoxide type surfactants can be used.

Die zwitterionischen oder amphoteren Tenside enthalten im Molekül sowohl saure Gruppen, wie z.B. die Carboxyl-, Sulfo-, Schwefelsäurehalbester-, Phosphono- oder Phosphorsäureteilestergruppen, als auch basische Gruppen, wie z.B. Amino-, Imino- oder Ammoniumgruppierungen. Zwitterionische Verbindungen mit einer vierfach substituierten, d.h. quartären Ammoniumgruppe werden als Betaine bezeichnet, wenn sie im Molekül auch eine kovalent gebundene Säuregruppe besitzen und die positive und negative Ladung intramolekular ausgeglichen ist. Im weiteren Sinne gehören zur Klasse der Betaine auch die entsprechend substituierten quartären Phosphonium- und tertiären Sulfoniumverbindungen. Die oberflächenaktiven Betaine besitzen am Stickstoff im allgemeinen einen höhermolekularen aliphatischen Kohlenwasserstoffrest mit hydrophobem Charakter und zwei niedere Alkylreste mit 1 - 3 Kohlenstoffatomen, die durch eine oder zwei Hydroxylgruppen substituiert oder direkt oder über ein Heteroatom miteinander verbunden sein können. Die wasserlöslichmachende Carboxylat-, Sulfonat- oder Sulfatgruppe ist über den vierten Substituenten, der meist aus einem kurzkettigen, gegebenenfalls eine Doppelbindung oder eine Hydroxylgruppe aufweisenden aliphatischen Rest besteht, mit dem Ammoniumstickstoff verbunden. Als Tenside sind auch solche Sulfonatbetaine geeignet, bei denen die anionische, wasserlöslich-machende Gruppe direkt an den langkettigen, für die Kapillaraktivität verantwortlichen hydrophoben Kohlenwasserstoffrest gebunden ist. Derartige Sulfobetaine lassen sich beispielsweise aus den aus C8-C20-α-Olefinen mit S03 herstellbaren Sultonen und einem tertiären Amin mit drei kurzkettigen aliphatischen Resten erhalten. Typische Vertreter derartiger oberflächenaktiver Betaine sind beispielsweise die Verbindungen 3-(N-Hexadecyl-N,N-di- methylammonio)-propansulfonat; 3-(N-Talgalkyl-N,N-di- methylanmonio) -2-hydroxypropansulfonat; 3-(N-Hexadecyl-N,N-bis (2-hydroxyethyl)-ammonio)-2-hydroxypropyl- sulfat; 3-(N-Cocosalkyl-N,N-bis(2,3-dihydroxypropyl)-ammonio)-propansulfonat; N-Tetradecyl-N,N-dimethyl- ammonioacetat; N-Hexadecyl-N,N-bis(2,3-dihydroxypropyl)-ammonioacetat.The zwitterionic or amphoteric surfactants contain both acidic groups, such as the carboxyl, sulfo, sulfuric acid half-ester, phosphono or phosphoric acid partial ester groups, as well as basic groups, such as amino, imino or ammonium groups, in the molecule. Zwitterionic compounds with a tetrasubstituted, ie quaternary ammonium group are called betaines if they also have a covalently bound acid group in the molecule and the positive and negative charge is balanced intramolecularly. In a broader sense, the betaines also include the correspondingly substituted quaternary phosphonium and tertiary sulfonium compounds. On the nitrogen, the surface-active betaines generally have a higher molecular weight aliphatic hydrocarbon radical with a hydrophobic character and two lower alkyl radicals with 1-3 carbon atoms, which can be substituted by one or two hydroxyl groups or linked directly or via a hetero atom. The water-solubilizing carboxylate, sulfonate or sulfate group is linked to the ammonium nitrogen via the fourth substituent, which usually consists of a short-chain aliphatic radical which may have a double bond or a hydroxyl group. Also suitable as surfactants are sulfonate betaines in which the anionic, water-solubilizing group is bonded directly to the long-chain, hydrophobic hydrocarbon residue responsible for capillary activity. Such sulfobetaines can be obtained, for example, from the sultones which can be prepared from C 8 -C 20 -α-olefins with S0 3 and a tertiary amine with three chain aliphatic radicals obtained. Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylanmonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonio) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethylammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.

Insbesondere besteht die Tensidkomponente des erfindungsgemäßen Waschmittels aus einer Kombination aus zwei verschiedenen nichtionischen Tensiden, wie sie in der DE-OS 28 17 834 beschrieben ist. Dieses besonders bevorzugte erfindungsgemäße Waschmittel enthält als nichtionisches Tensid ein Gemisch aus:

  • a) 5 - 18 Gew.-% eines Alkylpolyglykolethers der Formel
    Figure imgb0001
    in der R1 eine geradkettige Alkylgruppe und R2 zu 20 bis 75 Gew.-% - bezogen auf den den Alkylpolyglykolether zugrunde liegenden Alkohol - eine C1 - C4 - Alkylgruppe und in übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R1 und R2 11 bis 15 beträgt, und n einen Wert von 5 bis 9 bedeutet, und wobei n so ausgewählt ist, daß der Ethylenoxidanteil des Alkylpolyglykolethers etwa 50 bis 65 Gew.-% beträgt,
  • b) 5 - 18 Gew.-% eines Alkylpolyglykolethers der Formel I, in der R1 eine geradkettige Alkylgruppe und R2 entweder Wasserstoff, oder zu 20 bis 75 Gew.-% - bezogen auf den dem Alkylpolyglykol - ether zugrunde liegenden Alkohol - eine C1-C4 Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R1 und R2 6 bis 10 beträgt und n einen Wert von 3 bis 8 bedeutet, und wobei n so ausgewählt ist, daß der Ethylenoxidanteil des Alkylpolyglykolethers etwa 55 bis 70 Gew.-% beträgt.
In particular, the surfactant component of the detergent according to the invention consists of a combination of two different nonionic surfactants, as described in DE-OS 28 17 834. This particularly preferred detergent according to the invention contains, as a nonionic surfactant, a mixture of:
  • a) 5 - 18 wt .-% of an alkyl polyglycol ether of the formula
    Figure imgb0001
    in which R 1 is a straight - chain alkyl group and R 2 is 20 to 75% by weight, based on the alcohol on which the alkyl polyglycol ether is based, a C 1 - C 4 alkyl group and in the rest hydrogen, the total number of carbon atoms in R 1 and R 2 is 11 to 15, and n is a value of 5 to 9, and where n is selected so that the ethylene oxide content of the alkyl polyglycol ether is about 50 to 65% by weight,
  • b) 5-18% by weight of an alkyl polyglycol ether of the formula I in which R 1 is a straight-chain alkyl group and R 2 is either hydrogen or 20 to 75% by weight, based on that of the alkyl polyglycol alcohol on which ether is based - is a C 1 -C 4 alkyl group and hydrogen in the rest, where the total number of carbon atoms in R 1 and R 2 is 6 to 10 and n is a value from 3 to 8, and where n is selected that the ethylene oxide content of the alkyl polyglycol ether is about 55 to 70% by weight.

Das Mengenverhältnis von a) : b) beträgt vorzugsweise 2 : 1 bis 1 : 2.The quantitative ratio of a): b) is preferably 2: 1 to 1: 2.

Die als Bestandteil a) geeigneten Alkylpolyglykolether der Formel I leiten sich von Alkoholen ab, die durch Umsetzung linearer Olefine mit Kohlenstoffmonoxid und Wasserstoff nach dem bekannten Oxo-Verfahren durch Hydroformylierung und anschließende Hydrierung hergestellt werden. Handelsübliche Oxo-Alkohol-Gemische, die sich für die Herstellung der Tensidkomponente a) eignen, sind beispielsweise die unter der Handelsbezeichnung "Dobanol" erhältlichen Oxo-Alkohole der Deutsche. Shell Chemie Gesellschaft, die ca. 25 Gew.-% an 2-Alkylverzweigungen aufweisen, Andere geeignete Oxo-Alkohole sind unter der. Bezeichnung "Synprol" der Inperial Chemical Industries Ltd. erhältliche Alkoholgemische mit ca. 50 bis 70 Gew.-% 2-Alkylverzweigunger. Weitere geeignete Produkte auf Basis von Oxo-Alkoholen sind z.B. verschiedene "Lutensol"-Typen der BASF mit ca. 30 bis 35 Gew.-% verzweigten Alko- holen und einige "Lial"-Typen der Liquichimica S.p.A. mit ca. 60 Gew.-% verzweigten Alkoholen.The alkyl polyglycol ethers of the formula I which are suitable as component a) are derived from alcohols which are prepared by reacting linear olefins with carbon monoxide and hydrogen by the known oxo process by hydroformylation and subsequent hydrogenation. Commercially available oxo alcohol mixtures which are suitable for the preparation of the surfactant component a) are, for example, the oxo alcohols available from Deutsche under the trade name "Dobanol". Shell Chemie Gesellschaft, which have about 25 wt .-% of 2-alkyl branches, other suitable oxo-alcohols are among the. Name "Synprol" of Inperial Chemical Industries Ltd. available alcohol mixtures with about 50 to 70 wt .-% 2-alkyl branching. Other suitable products based on oxo alcohols are e.g. Various "Lutensol" types from BASF with approx. 30 to 35% by weight of branched alcohols and some "Lial" types from Liquichimica S.p.A. with about 60 wt .-% branched alcohols.

Als Bestandteil a) werden besonders Alkylpolyglykolether bevorzugt, die Ethylenoxid-Kondensate der erwähnten Oxo-Alkohole mit 13 bis 15 Kohlenstoffatomen bei einen durchschnittlichen Ethylenoxidgehalt von ca. 55 bis 65 Gew.-% darstellen. Typische bevorzugte Produkte sind beispielsweise "Dobanol 45-7", das zu mindestens 95 % aus C14/C15 Oxo-Alkohol mit durchschnittlich 7 Mol Ethylenoxid besteht, und "Lutensol AO-8", das ein C13/C15-Oxo-Alkohol Ethoxylat mit durchschnittlich 8 Mol Ethylenoxid darstellt.As component a), particular preference is given to alkyl polyglycol ethers which represent ethylene oxide condensates of the aforementioned oxo alcohols with 13 to 15 carbon atoms and an average ethylene oxide content of approximately 55 to 65% by weight. Typical preferred products are, for example, "Dobanol 45-7", which consists of at least 95% C 14 / C 15 oxo alcohol with an average of 7 moles of ethylene oxide, and "Lutensol AO-8", which is a C 13 / C 15 oxo Alcohol represents ethoxylate with an average of 8 moles of ethylene oxide.

Als Bestandteil b) werden Alkylpolyglykolether bevorzugt, deren Alkoholbasis natürliche oder synthetische primäre Fettalkohole oder Oxo-Alkohole darstellen, die 9 bis 12 Kohlenstoffatome enthalten und einen Ethylenoxidgehalt von ca. 60 bis 70 Gew.-% aufweisen. Typische bevorzugte Produkte sind z.B. das Handelsprodukt "Marlipal KF" (Chemische Werke Hüls), das ein C10/C12-Fettalkohol-Ethoxylat mit durchschnittlich 6 Mol Ethylenoxid darstellt, sowie das "Lutensol ON-70", das ein C9/C11-Oxo- Alkohol-Ethoxylat mit durchschnittlich 7 Mol Ethylenoxid darstellt. Geeignete Fettalkohole als Basis für bevorzugte Alkylpolyglykolether sind auch die Handelsprodukte "Lorol C - 8 bis 12" (Henkel).As component b), preference is given to alkyl polyglycol ethers whose alcohol base is natural or synthetic primary fatty alcohols or oxo alcohols which contain 9 to 12 carbon atoms and have an ethylene oxide content of approximately 60 to 70% by weight. Typical preferred products are, for example, the commercial product "Marlipal KF" (Chemische Werke Huls), which is a C 10 / C 12 fatty alcohol ethoxylate with an average of 6 moles of ethylene oxide, and the "Lutensol ON-70", which is a C 9 / C 11 -Oxo alcohol ethoxylate with an average of 7 moles of ethylene oxide. Suitable fatty alcohols as the basis for preferred alkyl polyglycol ethers are also the commercial products "Lorol C-8 to 12" (Henkel).

Das Verhältnis der eingesetzten Menge des Bestandteils a) zur eingesetzten Menge des Bestandteils b) bestimmt wesentlich die Parameter Waschkraft, Schäumverhalten und weichnachende Wirkung. Optimale Ergebnisse werden erhalten, wenn das Verhältnis von a) : b) zwischen etwa 2 : 1 und 1 : 2 liegt.The ratio of the amount of component a) used to the amount of component b) essentially determines the parameters of washing power, foaming behavior and softening effect. Optimal results are obtained when the ratio of a): b) is between about 2: 1 and 1: 2.

Im allgemeinen werden von Bestandteil a) und Bestandteil b) Mengen von zusammen 10 bis 30 Gew.-%, bezogen auf das Gesamtgewicht des Waschmittels, eingesetzt, wobei eine Menge von 15 bis 30 Gew.-% bevorzugt wird.In general, amounts of component a) and component b) of 10 to 30% by weight, based on the total weight of the detergent, are used, an amount of 15 to 30% by weight being preferred.

Pastöse und insbesondere flüssige Waschmittel mit einem Gehalt an den beschriebenen verfärbungsinhibierenden Polymeren sind besonders bevorzugt. Als Lösungsmittel für die bevorzugten flüssigen Waschmittel wird vorzugsweise Wasser verwendet. Es können aber auch organische Lösungsmittel in Mengen bis zu 20, vorzugsweise bis zu 16 Gew.-% des gesamten Flüssigwaschmittels mit verwendet werden. Derartige zusätzliche Lösungsmittel sind entweder niedere Alkanole oder niedere Diole oder Polyole wie beispielsweise Ethanol, Isopropylalkohol, Ethylenglykol, Propylenglykol oder Glycerin. Gegebenenfalls können auch Polyole mit Etherbindungen wie Methyl-, Ethyl-, Butyl- oder Diethylenglykol beziehungsweise deren Acetate (beispielsweise Produkte vom Typ der "Cellosolve" der Union Carbide Corp.) eingesetzt werden.Pasty and in particular liquid detergents containing the discoloration-inhibiting polymers described are particularly preferred. Water is preferably used as the solvent for the preferred liquid detergents. However, organic solvents can also be used in amounts of up to 20, preferably up to 16% by weight of the total liquid detergent. Such additional solvents are either lower alkanols or lower diols or polyols such as ethanol, isopropyl alcohol, ethylene glycol, propylene glycol or glycerin. Optionally, polyols with ether linkages such as methyl, ethyl, butyl or diethylene glycol or their acetates (for example products of the "Cellosolve" type from Union Carbide Corp.) can also be used.

Zur Verbesserung der Löslichkeit der Tenside ist es häufig zweckmäßig, zusätzlich oder anstelle der zuvor genannten organischen Lösungsmittel Lösungsvermittler, sogenannte Hydrotrope zu verwenden. Die bevorzugten Hydrotrope sind nichttensidische organische Sufonate, wie zum Beispiel C6-C12-Alkansulfonate, sowie die Salze der Toluol-, Xylol- und Cumolsulfonsäure, vorzugsweise deren Alkanolamin- und Alkalisalze, insbesondere deren Kaliumsalze. Auch Harnstoff ist als Hydrotrop geeignet. Hydrotrope werden in Mengen von 2 bis 12, vorzugsweise 3 bis 9 Gew.-%, bezogen auf das gesamte Flüssigwaschmittel, zugesetzt.To improve the solubility of the surfactants, it is often expedient to use solubilizers, so-called hydrotropes, in addition to or instead of the organic solvents mentioned above. The preferred hydrotropes are non-surfactant organic sulfonates, such as C 6 -C 12 alkanesulfonates, and the salts of toluene, xylene and cumene sulfonic acid, preferably their alkanolamine and alkali salts, especially their potassium salts. Urea is also suitable as a hydrotrope. Hydrotropes are added in amounts of 2 to 12, preferably 3 to 9% by weight, based on the total liquid detergent.

Zur Verbesserung bestimmter Eigenschaften können den erfindungsgemäßen Waschmitteln weitere, ebenfalls meist in gerignen Mengen wirksame Hilfsstoffe zugesetzt werden; dies sind beispielsweise Trübungs- und Viskositätsstellmittel, die meist zu etwa 0,05 bis 2 Gew.-% in dem Waschmittel enthalten sind. Hierbei handelt es sich zum Beispiel um Ester von Alkanolen oder Partialester von Polyolen mit längerkettigen Fettsäuren, wie zum Beispiel Palmitin- oder Stearinsäure. Ein typisches Produkt ist Ethylenglykolstearat.To improve certain properties, further auxiliaries, which are likewise usually effective in small amounts, can be added to the detergents according to the invention; These are, for example, opacifiers and viscosity regulators, which are usually contained in the detergent at about 0.05 to 2% by weight. These are, for example, esters of alkanols or partial esters of polyols with longer-chain fatty acids, such as palmitic or stearic acid. A typical product is ethylene glycol stearate.

Als Konservierungsmittel wird meist Formalin in einer Menge von 0,05 bis 1 Gew.-% verwendet.Formalin is usually used as a preservative in an amount of 0.05 to 1% by weight.

Zur Vermeidung von Verfärbungen der Waschmittel bei längerer Lagerung, die durch Verunreinigungen zum Beispiel mit Schwermetallionen bei der Herstellung hervorgerufen werden können, setzt man Komplexierungsmittel für Schwermetallionen zu. Gebräuchliche Komplexierungsmittel sind die Natrium-, Kalium- oder Triethanolaminsalze von Aminopolycarbonsäuren, wie beispielsweise Ethylendiamintetraessigsäure oder Nitrilostriessigsäure. Sie werden in Mengen von 0,1 bis 1 Gew.-% eingesetzt.In order to avoid discoloration of the detergents during prolonged storage, which can be caused by contamination with heavy metal ions during manufacture, for example, complexing agents for heavy metal ions are added. Common complexing agents are the sodium, potassium or triethanolamine salts of aminopolycarboxylic acids, such as, for example, ethylenediaminetetraacetic acid or nitrilostriacetic acid. They are used in amounts of 0.1 to 1% by weight.

Als Duftstoffe kommen beispielsweise Stoffe mit blumig/ frischer oder fruchtiger oder als kosmetisch oder cremig bezeichneter Duftnote in Frage.Examples of suitable fragrances are substances with a floral / fresh or fruity fragrance or those designated as cosmetic or creamy.

Ein hinsichtlich ausgewogener Produkteigenschaften besonders bevorzugtes Mittel hat die folgende Zusammensetzung:

  • a) 7,5 - 12,5 Gew.-% eines Alkylpolyglykolethers der Formel I, in der R1 und R2 zusammen 11 bis 13 Kohlenstoffatome aufweisen und wobei der durchschnittliche Ethylenoxidgehalt des Alkylpolyglykolethers 55 bis 65 Gew.-% beträgt;
  • b) 7,5 - 12,5 Gew.-% eines Alkylpolyglykolethers der Formel I, in der R1 7 bis 10 Kohlenstoffatome aufweist, R2 = H ist und wobei der durchschnittliche Ethylenoxidgehalt des Alkylpolyglykolethers 60 bis 70 Gew.-% beträgt;
  • c) 0,2 - 2,0 Gew.-% wasserlösliche synthetische Polymere aus der Gruppe Polyethyleninine und Polyamine
  • d) 2,5 - 4,0 Gew.-% sonstige wasserlösliche Polymere
    • Rest Wasser und organische Lösungsmittel sowie gegebenenfalls weitere übliche, in geringen Mengen anwesende Zusätze, wie zum Beispiel Farb- und Duftstoffe, hydrotrope Mittel, Komplexierungsmittel für Schwermetallspuren sowie Konservierungsmittel, Trübungs- und Viskositätsstellmittel
An agent which is particularly preferred with regard to balanced product properties has the following composition:
  • a) 7.5 to 12.5% by weight of an alkylpolyglycol ether of the formula I in which R 1 and R 2 together have 11 to 13 carbon atoms and the average ethylene oxide content of the alkylpolyglycol ether is 55 to 65% by weight;
  • b) 7.5-12.5% by weight of an alkylpolyglycol ether of the formula I in which R 1 has 7 to 10 carbon atoms, R 2 = H and the average ethylene oxide content of the alkylpolyglycol ether is 60 to 70% by weight;
  • c) 0.2-2.0% by weight of water-soluble synthetic polymers from the group of polyethyleneinins and polyamines
  • d) 2.5-4.0% by weight of other water-soluble polymers
    • Remainder water and organic solvents as well as, where appropriate, other customary additives present in small amounts, such as, for example, colorants and fragrances, hydrotropic agents, complexing agents for traces of heavy metals, and preservatives, opacifiers and viscosity regulators

BeispieleExamples Beispiele 1 bis 6Examples 1 to 6

Für die folgenden Beispiele der Erfindung wurde ein flüssiges Waschmittel der nachstehenden Zusammensetzung verwendet:

  • 11,0 Gew.-% C14/C15-0xo-Alkohol-Ethoxylat mit durchschnittlich 58 Gew.-% Ethylenoxid ("Dobanol 45-7", Shell);
  • 11,0 Gew.-% C10/C12-Fettalkohol-Ethoxylat mit durchschnittlich 60 Gew.-% Ethylenoxid ("Marlipal KF", Chemische Werke Hüls):
  • 7,0 Gew.-% Ethanol/1,2-Propylenglykol;

wasserlösliche, synthetische amino- und/oder amidogruppenhaltige Polymere aus der Gruppe Polyethylenimine, Polyamine, Polyaminamide, Polyacrylamide;
gegebenenfalls sonstige wasserlösliche Polymere;A liquid detergent of the following composition was used for the following examples of the invention:
  • 11.0% by weight of C 14 / C 15 -oxy alcohol ethoxylate with an average of 58% by weight of ethylene oxide ("Dobanol 45-7", Shell);
  • 11.0% by weight of C 10 / C 12 fatty alcohol ethoxylate with an average of 60% by weight of ethylene oxide ("Marlipal KF", Chemische Werke Hüls):
  • 7.0% by weight ethanol / 1,2-propylene glycol;

water-soluble, synthetic amino and / or amido group-containing polymers from the group polyethyleneimines, polyamines, polyaminamides, polyacrylamides;
optionally other water-soluble polymers;

Rest Wasser, geringe Mengen Konservierungsmittel, Farbstoff, Duftstoff.Balance water, small amounts of preservative, dye, fragrance.

Als wasserlösliche Polymere enthielten die Waschmittel die folgenden Stoffe in den angegebenen Mengen:The detergents contained the following substances in the stated amounts as water-soluble polymers:

Beispiel 1example 1

4,4 Gew.-% einer ca. 25 %igen wäßrigen Lösung eines in Wasser stark bis mäßig basisch reagierenden Polyethylenimins ("Retaminol E", BAYER AG, Leverkusen, Bundesrepublik Deutschland)4.4% by weight of an approx. 25% aqueous solution of a polyethyleneimine which reacts strongly to moderately basic in water ("Retaminol E", BAYER AG, Leverkusen, Federal Republic of Germany)

Beispiel 2Example 2

1,8 Gew.-% einer ca. 25 %igen wäßrigen Lösung eines in Wasser stark bis mäßig basisch reagierenden Polyethylenimins ("Retaminol E" , BAYER AG, Leverkusen, Bundesrepublik Deutschland)1.8% by weight of an approx. 25% aqueous solution of a polyethyleneimine which reacts strongly to moderately basic in water ("Retaminol E", BAYER AG, Leverkusen, Federal Republic of Germany)

0,9 Gew.-% eines niedermolekularen wasserlöslichen Melamin/Formaldehyd-Kondensationsproduktes (Molverhältnis 1 : 3), "Melan 125", HENKEL, Düsseldorf, Bundesrepublik Deutschland.0.9% by weight of a low molecular weight water-soluble melamine / formaldehyde condensation product (molar ratio 1: 3), "Melan 125", HENKEL, Düsseldorf, Federal Republic of Germany.

0,9 Gew.-% eines wasserlöslichen Kondensationsproduktes aus Melamin/Harnstoff/Formaldehyd, "Pressal R50", HENKEL, Düsseldorf, Bundesrepublik Deutschland.0.9% by weight of a water-soluble condensation product from melamine / urea / formaldehyde, "Pressal R50", HENKEL, Düsseldorf, Federal Republic of Germany.

Beispiel 3Example 3

2,5 Gew.-% einer ca. 25 %igen wäßrigen Lösung eines stark bis mäßig basisch reagierenden Polyethylenimins ("Retaminol E", BAYER AG, Leverkusen, Bundesrepublik Deutschland).2.5% by weight of an approximately 25% aqueous solution of a strongly to moderately basic-reacting polyethyleneimine ("Retaminol E", BAYER AG, Leverkusen, Federal Republic of Germany).

1,3 Gew.-% eines niedermolekularen wasserlöslichen Melamin/Formaldehyd-Kondensationsproduktes (Molverhältnis 1 : 3), "Melan 125", HENKEL, Düsseldorf, Bundesrepublik Deutschland.1.3% by weight of a low molecular weight water-soluble melamine / formaldehyde condensation product (molar ratio 1: 3), "Melan 125", HENKEL, Düsseldorf, Federal Republic of Germany.

1,3 Gew.-% eines wasserlöslichen Kondensationsproduktes aus Melamin/Formaldehyd, "Pressal R 50" HENKEL, Düsseldorf, Bundesrepublik Deutschland.1.3% by weight of a water-soluble condensation product made from melamine / formaldehyde, "Pressal R 50" HENKEL, Düsseldorf, Federal Republic of Germany.

Beispiel 4Example 4

1,8 Gew.-% einer ca..25 %igen wäßrigen Lösung eines stark basisch reagierenden Polyamins ("Retaminol K", Bayer AG, Leverkusen, Bundesrepublik Deutschland).1.8% by weight of an approximately 25% strength aqueous solution of a strongly basic polyamine ("Retaminol K", Bayer AG, Leverkusen, Federal Republic of Germany).

0,9 Gew.-% eines niedermolekularen wasserlöslichen Melamin/Formaldehyd/Kondensationsproduktes (Molverhältnis 1 : 3), "Melan 125", HENKEL, Düsseldorf, Bundesrepublik Deutschland0.9% by weight of a low molecular weight water-soluble melamine / formaldehyde / condensation product (molar ratio 1: 3), "Melan 125", HENKEL, Düsseldorf, Federal Republic of Germany

0,.9 Gew.-% eines wasserlöslichen Kondensationsproduktes aus Melamin/Harnstoff/Formaldehyd, "Pressal R50", HENKEL, Düsseldorf, Bundesrepublik Deutschland.0.9% by weight of a water-soluble condensation product of melamine / urea / formaldehyde, "Pressal R50", HENKEL, Düsseldorf, Federal Republic of Germany.

Beispiel 5Example 5

2,5 Gew.-% einer ca. 25 %igen wäßrigen Lösung eines stark basisch reagierenden Polyamins ("Retaminol K", BAYER AG, Leverkusen, Bundesrepublik Deutschland)2.5% by weight of an approximately 25% aqueous solution of a strongly basic polyamine ("Retaminol K", BAYER AG, Leverkusen, Federal Republic of Germany)

1,3 Gew.-% eines niedermolekularen wasserlöslichen Melamin/Formaldehyd-Kondensationsproduktes (Molverhältnis 1 : 3), "Melan 125", HENKEL Düsseldorf, Bundesrepublik Deutschland1.3% by weight of a low molecular weight water-soluble melamine / formaldehyde condensation product (molar ratio 1: 3), "Melan 125", HENKEL Düsseldorf, Federal Republic of Germany

1,3 Gew.-% eines wasserlöslichen Kondensationsproduktes aus Melamin/Harnstoff/Formaldehyd, "Pressal R50", HENKEL Düsseldorf, Bundesrepublik Deutschland.1.3% by weight of a water-soluble condensation product from melamine / urea / formaldehyde, "Pressal R50", HENKEL Düsseldorf, Federal Republic of Germany.

Beispiel 6Example 6

4,4 Gew.-% einer ca. 25 %igen wäßrigen Lösung eines stark basisch reagierenden Polyamins ("Retamiol K", BAYER AG, Leverkusen, Bundesrepublik Deutschland).4.4% by weight of an approximately 25% aqueous solution of a strongly basic polyamine ("Retamiol K", BAYER AG, Leverkusen, Federal Republic of Germany).

Beispiel 7Example 7

Als Beispiel für ein weniger universell einsetzbares verfärbungsinhibierendes Buntwaschmittel wurde das Waschmittel von Beispiel 1 der Patentanmeldung P 30 26.090.3 mit der folgenden Zusammensetzung verwendet:

  • 11,0 Gew.-% C14/C15-Oxo-Ethoxylat mit durchschnittlich 58 Gew.-% Ethylenoxid ("Dobanol 45-7", Shell);
  • 11,0 Gew.-% C10/C12-Fettalkohol-Ethoxylat mit durchschnittlich 60 Gew.-% Ethylenoxid ("Marlipal KF", Chemische Werke, Hüls)
  • 3,0 Gew.-% Dimethylditalgalkylammoniumchlorid (100 %ig), eingesetzt als 75 %ige Paste, Rest Isopropylalkohol und Wasser, (Prägagen WK", HOECHST, Frankfurt, Bundesrepublik Deutschland
  • 1,2 Gew.-% Kationische Kartoffelstärkeether ("Empresol N" , Emsland Stärke GmbH, Emlichheim, Bundesrepublik Deutschland)
  • 7,0 Gew.-% Ethanol/Propylenglykol-1,2
The detergent from Example 1 of patent application P 30 26.090.3 with the following composition was used as an example of a less universally applicable discoloration-inhibiting colored detergent:
  • 11.0% by weight of C 14 / C 15 oxo-ethoxylate with an average of 58% by weight of ethylene oxide ("Dobanol 45-7", Shell);
  • 11.0% by weight of C 10 / C 12 fatty alcohol ethoxylate with an average of 60% by weight of ethylene oxide ("Marlipal KF", Chemische Werke, Hüls)
  • 3.0% by weight of dimethylditalgalkylammonium chloride (100%), used as a 75% paste, the remainder isopropyl alcohol and water, (Prägagen WK ", HOECHST, Frankfurt, Federal Republic of Germany
  • 1.2% by weight of cationic potato starch ether ("Empresol N", Emsland Starch GmbH, Emlichheim, Federal Republic of Germany)
  • 7.0 wt% ethanol / 1,2-propylene glycol

Rest Wasser, geringe Mengen Konservierungsmittel, Duftstoff, FarbstoffBalance water, small amounts of preservative, fragrance, dye

Mit den Waschmitteln der Beispiele 1 bis 7 wurden Waschversuche in einer handelsüblichen Trommelwaschmaschine bei 60° C durchgeführt. Dabei wurden weiße-Prüftextilien aus Baumwollbleichnessel (BL), Polyester/Baumwoll 63/35 (PES/BW), ein Baumwoll-Gewirke (BW), Polyurethan-Elastomehr-Gewirke (PU) bei einem Flottenverhältnis von 1 : 20, ohne Schmutzbelastung in Gegenwart eines Stoffabschnitts, der mit 3,5 % des stark ausblutenden Farbstoffs Siriuslichtrot F 4 BL, 154 % eingefärbt war, gewaschen. Auf eine Trommelfüllung wurden 84 g der Waschmittel der Beispiele 1 bis 7 gegeben und nach der Wäsche die Reflexionswerte mit einem Spektralphotometer vom Typ Zeiss Elrepho RFC3-18, Filter R 460 gemessen.With the detergents of Examples 1 to 7, washing tests were carried out in a commercial drum washing machine at 60 ° C. White test textiles made of cotton bleaching nettle (BL), polyester / cotton 63/35 (PES / BW), a knitted cotton fabric (BW), polyurethane-elastomeric multi-knitted fabric (PU) were used at a liquor ratio of 1:20, without contamination in In the presence of a section of fabric which was colored with 3.5% of the heavily bleeding-out dye Sirius light red F 4 BL, 154%. 84 g of the detergents from Examples 1 to 7 were placed on a drum filling and after washing the reflectance values were measured using a Zeiss Elrepho RFC3-18 type filter R 460.

Das Ergebnis ist in Tabelle I dargestellt.The result is shown in Table I.

Figure imgb0002
Diesen Versuchsergebnissen kann entnommen werden, daß der stark ausblutende Farbstoff auf die Prüftextilien in deutlich geringerem Ausmaß übertragen wird als bei Verwendung eines vergleichbaren Waschmittels mit einem anderen verfärbungsinhibierenden Wirkstoff.
Figure imgb0002
It can be seen from these test results that the heavily bleeding-out dye is transferred to the test textiles to a significantly lesser extent than when using a comparable detergent with another discoloration-inhibiting active ingredient.

Claims (7)

1. Verfärbungsinhibierendes, flüssiges Waschmittel, enthaltend nichtionische oder zwitterionische Tenside, dadurch gekennzeichnet, daß es die genannten Tenside in Kombination mit synthetischen, wasserlöslichen, amino- und/oder amidogruppenhaltigen Polymeren aus der Gruppe der Polyethylenimine, Polyamine, Polyaminamide und Polyacrylamide enthält, daß es frei von textilweichmachenden quartären Ammoniumverbindungen sowie im wesentlichen phosphatfrei ist.1. Discoloration-inhibiting, liquid detergent, containing nonionic or zwitterionic surfactants, characterized in that it contains the surfactants mentioned in combination with synthetic, water-soluble, amino and / or amido group-containing polymers from the group of polyethyleneimines, polyamines, polyaminamides and polyacrylamides that it contains is free of textile-softening quaternary ammonium compounds and is essentially phosphate-free. 2. Mittel nach Anspruch 1,gekennzeichnet durch einen Gehalt an Polymeren aus der Gruppe Polyethylenimine und Polyamine.2. Composition according to claim 1, characterized by a content of polymers from the group of polyethyleneimines and polyamines. 3. Mittel nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß der Gehalt an Polymeren 1 bis 15 Gew.-%, vorzugsweise 5 bisl5 Gew.-% bezogen auf die Tensidmenge des Mittels beträgt.3. Composition according to claims 1 and 2, characterized in that the polymer content is 1 to 15 wt .-%, preferably 5 to 15 wt .-% based on the amount of surfactant of the agent. 4. Mittel nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß es zusätzliche sonstige wasserlösliche Polymere enthält.4. Composition according to claims 1 to 3, characterized in that it contains additional other water-soluble polymers. 5. Mittel nach den Ansprüchen 1 bis 4, enthaltend a) 5 - 18 Gew.-% eines Alkylpolyglykolethers der Formel I
Figure imgb0003
in der R1 eine geradkettige Alkylgruppe und R2 zu 20 bis 75 Gew.-% - bezogen auf den dem Alkylpolyglykolether zugrunde liegenden Alkohol - eine C1-C4-Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R1 und R2 11 bis 15 beträgt, und n einen Wert von 5 bis 9 bedeutet, und wobei n so ausgewählt ist, daß der Ethylenoxidanteil des Alkylpolyglykolethers etwa 50 bis 65 Gew.-% beträgt.
b) 5 - 18 Gew.-% eines Alkylpolyglykolethers der Formel I, in'der R1 eine geradkettige Alkylgruppe und R2 entweder Wasserstoff, oder zu 20 bis 75 Gew.-% - bezogen auf den dem Alkylpolyglykolether zugrunde liegenden Alkohol - eine C1-C4-Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R1 und R2 6 bis 10 beträgt und n einen Wert von 3 bis 8 bedeutet, und wobei n so ausgewählt ist, daß der Ethylenoxidanteil des Alkylpolyglykolethers etwa 55 bis 70 Gew.-% beträgt
als nichtionische Tenside in einem Mengenverhältnis a) : b) vorzugsweise von 2 : 1 bis 1 : 2.
5. Composition according to claims 1 to 4, containing a) 5-18% by weight of an alkyl polyglycol ether of the formula I.
Figure imgb0003
in which R 1 is a straight-chain alkyl group and R 2 is 20 to 75% by weight, based on the alcohol on which the alkyl polyglycol ether is based, a C 1 -C 4 -alkyl group and, moreover, hydrogen, the total number of carbon atoms in R 1 and R 2 is 11 to 15, and n is a value of 5 to 9, and where n is selected so that the ethylene oxide content of the alkyl polyglycol ether is about 50 to 65% by weight.
b) 5-18% by weight of an alkyl polyglycol ether of the formula I in which R 1 is a straight-chain alkyl group and R 2 is either hydrogen or 20 to 75% by weight, based on the alcohol on which the alkyl polyglycol ether is based, a C. 1 -C 4 alkyl group and hydrogen mean, where the total number of carbon atoms in R 1 and R 2 is 6 to 10 and n is a value from 3 to 8, and wherein n is selected so that the ethylene oxide portion of the alkyl polyglycol ether about 55 to 70 wt .-% is
as nonionic surfactants in a quantitative ratio a): b) preferably from 2: 1 to 1: 2.
6. Flüssiges Mittel nach den Ansprüchen 1 bis 5 enthaltend 10 bis 30 Gew.-% vorzugsweise 15 bis 30 Gew.-% Alkylpolyglykolether der Formel I.6. Liquid composition according to claims 1 to 5 containing 10 to 30 wt .-% preferably 15 to 30 wt .-% alkyl polyglycol ether of the formula I. 7. Flüssiges Mittel nach den Ansprüchen 1 bis 6, gekennzeichnet durch a) 7,5 - 12,5 Gew.-% eines Alkylpolyglykolethers der Formel I, in der R 1 und R2 zusammen 11 bis 13 Kohlenstoffatome aufweisen und wobei der durchschnittliche Ethylenoxidgehalt des Alkylpolyglykolethers 55 bis 65 Gew.-% beträgt; b) 7,5 - 12,5 Gew.-% eines Alkylpolyglykolethers der Formel I, in der R1 7 bis 10 Kohlenstoffatome aufweist, R 2 = H ist und wobei der durchschnittliche Ethylenoxidgehalt des Alkylpolyglykolethers 60 bis 70 Gew.-% beträgt; c) 0,2 - 2,0 Gew.-% wasserlösliche, synthetische Polymere aus der Gruppe Polyethylenimine und Polyamine d) 2,5 - 4,0 Gew.-% sonstige wasserlösliche Polymere Rest Wasser und organische Lösungsmittel sowie gegebenenfalls weitere übliche, in geringen Mengen anwesende Zusätze, wie zum Beispiel Farb- und Duftstoffe, hydrotrope Mittel, Komplexierungsmittel für Schwermetallspuren sowie Konservierungsmittel, Trübungs- und Viskositätsmittel. 7. Liquid agent according to claims 1 to 6, characterized by a) 7.5 to 12.5% by weight of an alkylpolyglycol ether of the formula I in which R 1 and R 2 together have 11 to 13 carbon atoms and the average ethylene oxide content of the alkylpolyglycol ether is 55 to 65% by weight; b) 7.5 to 12.5% by weight of an alkylpolyglycol ether of the formula I in which R 1 has 7 to 10 carbon atoms, R 2 = H and the average ethylene oxide content of the alkylpolyglycol ether is 60 to 70% by weight ; c) 0.2-2.0% by weight of water-soluble, synthetic polymers from the group of polyethyleneimines and polyamines d) 2.5-4.0% by weight of other water-soluble polymers Remainder water and organic solvents as well as any other usual additives present in small amounts, such as colorants and fragrances, Hydrotropic agents, complexing agents for traces of heavy metals as well as preservatives, opacifiers and viscosity agents.
EP19820105121 1981-06-19 1982-06-11 Liquid detergent containing dye transfer inhibition additives Withdrawn EP0068232A2 (en)

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EP0158260A2 (en) * 1984-04-09 1985-10-16 Henkel Kommanditgesellschaft auf Aktien Detergent for coloured textiles
EP0345946A2 (en) * 1988-06-10 1989-12-13 Milliken Research Corporation Cleaning composition for textiles containing sulfonated colorless dye site blocker
WO1994029422A1 (en) * 1993-06-16 1994-12-22 Basf Aktiengesellschaft Grafted polyamidoamines and grafted polyethylene imines, process for producing the same and their use as additives in washing agents
WO1995006100A1 (en) * 1993-08-23 1995-03-02 Henkel Kommanditgesellschaft Auf Aktien Fade inhibitors for detergents
EP0704523A1 (en) * 1994-09-30 1996-04-03 The Procter & Gamble Company Dye transfer inhibiting compositions containing betaines
EP0918089A1 (en) * 1997-11-24 1999-05-26 The Procter & Gamble Company Fabric care compositions
WO2000049124A1 (en) * 1999-02-19 2000-08-24 The Procter & Gamble Company Laundry detergent compositions comprising fabric enhancement polyamines
US6277810B2 (en) 1998-09-16 2001-08-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dryer-added fabric care compositions containing amide-epichlorohydrin resins
US6410503B1 (en) 1997-11-24 2002-06-25 The Procter & Gamble Company Fabric care compositions
US6846797B1 (en) 1999-10-01 2005-01-25 Unilever Home & Personal Care Usa A Division Of Conopco, Inc. Fabric care composition comprising an epichlorohydrin resin and anionic polymer
WO2008077952A1 (en) * 2006-12-22 2008-07-03 Basf Se Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors

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US5380447A (en) * 1993-07-12 1995-01-10 Rohm And Haas Company Process and fabric finishing compositions for preventing the deposition of dye in fabric finishing processes
DE4334368C2 (en) * 1993-10-08 1995-12-14 Henkel Kgaa Low-foaming, polymer-free cleaning agents
CA2180071A1 (en) * 1995-07-11 1997-01-12 Thomas Cleveland Kirk Fabric washing composition and method for inhibiting deposition of dye
CA2180070A1 (en) * 1995-07-11 1997-01-12 Thomas Cleveland Kirk Washing composition and use of polymer to clean and provide soil resistance to an article
BR9707836A (en) * 1996-03-06 1999-07-27 Novo Nordisk Processes to inhibit microorganisms present in washing clothes and microbial growth on a hard surface and to exterminate microbial cells present in the skin of humans or animals in the mucous membranes in the teeth in bruises or eye injuries or to inhibit their growth
DE19611977A1 (en) 1996-03-26 1997-10-02 Basf Ag Detergent booster for detergents
DE19643133A1 (en) * 1996-10-18 1998-04-23 Basf Ag Use of water-soluble or water-dispersible crosslinked nitrogen-containing compounds in washing and cleaning agents
US6777530B1 (en) 1996-10-18 2004-08-17 Basf Aktiengesellschaft Use of crosslinked nitrogenous compounds which are soluble or dispersible in water in detergents and cleaners
DE102010062286A1 (en) 2010-12-01 2012-06-06 Rudolf Gmbh Polycationic colloid particles, process for their preparation and their use for the modification of substrates

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158260A2 (en) * 1984-04-09 1985-10-16 Henkel Kommanditgesellschaft auf Aktien Detergent for coloured textiles
EP0158260A3 (en) * 1984-04-09 1987-11-25 Henkel Kommanditgesellschaft Auf Aktien Detergent for coloured textiles
EP0345946A2 (en) * 1988-06-10 1989-12-13 Milliken Research Corporation Cleaning composition for textiles containing sulfonated colorless dye site blocker
EP0345946A3 (en) * 1988-06-10 1991-03-20 Milliken Research Corporation Cleaning composition for textiles containing sulfonated colorless dye site blocker
WO1994029422A1 (en) * 1993-06-16 1994-12-22 Basf Aktiengesellschaft Grafted polyamidoamines and grafted polyethylene imines, process for producing the same and their use as additives in washing agents
WO1995006100A1 (en) * 1993-08-23 1995-03-02 Henkel Kommanditgesellschaft Auf Aktien Fade inhibitors for detergents
EP0704523A1 (en) * 1994-09-30 1996-04-03 The Procter & Gamble Company Dye transfer inhibiting compositions containing betaines
EP0918089A1 (en) * 1997-11-24 1999-05-26 The Procter & Gamble Company Fabric care compositions
WO1999027055A1 (en) * 1997-11-24 1999-06-03 The Procter & Gamble Company Fabric care compositions
US6410503B1 (en) 1997-11-24 2002-06-25 The Procter & Gamble Company Fabric care compositions
US6277810B2 (en) 1998-09-16 2001-08-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dryer-added fabric care compositions containing amide-epichlorohydrin resins
WO2000049124A1 (en) * 1999-02-19 2000-08-24 The Procter & Gamble Company Laundry detergent compositions comprising fabric enhancement polyamines
US6846797B1 (en) 1999-10-01 2005-01-25 Unilever Home & Personal Care Usa A Division Of Conopco, Inc. Fabric care composition comprising an epichlorohydrin resin and anionic polymer
WO2008077952A1 (en) * 2006-12-22 2008-07-03 Basf Se Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors

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