EP1236793A2 - Washing agent and laundry treatment agent comprising one or more dye transfer inhibiting dye fixatives - Google Patents

Washing agent and laundry treatment agent comprising one or more dye transfer inhibiting dye fixatives Download PDF

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Publication number
EP1236793A2
EP1236793A2 EP02004064A EP02004064A EP1236793A2 EP 1236793 A2 EP1236793 A2 EP 1236793A2 EP 02004064 A EP02004064 A EP 02004064A EP 02004064 A EP02004064 A EP 02004064A EP 1236793 A2 EP1236793 A2 EP 1236793A2
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EP
European Patent Office
Prior art keywords
alkyl
color
acid
dye
detergent
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EP02004064A
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German (de)
French (fr)
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EP1236793A3 (en
EP1236793B1 (en
Inventor
Frank-Petre Di. Lang
Helmut Dr. Berenbold
Michael Dr. Wessling
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
Clariant GmbH
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-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
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • the amines used can be primary, secondary and tertiary amines. These can be aliphatic amines, alicyclic amines such as cyclohexylamine and aromatic amines such as aniline. However, the amines used can also have aliphatic, alicyclic and aromatic substituents at the same time. Heterocyclic compounds such as pyridine can also be used.
  • polyamines here includes, for example, diamines, triamines, tetraamines, etc. Examples include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine and higher polyamines.
  • the ammonium salts can be salts of ammonia or the amines or polyamines mentioned above with various inorganic or organic acids or else quaternary ammonium salts.
  • the cyanamides can be cyanamide or dicyandiamide.
  • Aldehydes which can be used for the synthesis of the color transfer-inhibiting color fixing agents are, for example, aliphatic aldehydes such as, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; Dialdehydes such as
  • glyoxal unsaturated aldehydes such as e.g. Acrolein, crotonaldehyde and aromatic Aldehydes such as Benzaldehyde.
  • unsaturated aldehydes such as e.g. Acrolein, crotonaldehyde and aromatic Aldehydes such as Benzaldehyde.
  • aromatic Aldehydes such as Benzaldehyde.
  • the aliphatic ones are particularly preferred Aldehydes.
  • color fixatives are added to the detergents according to the invention in order to improve the wash fastness of the textile dyes by reducing their bleeding. At the same time, these color fixatives also inhibit color transfer by binding residual amounts of bleeding-out dye in the wash liquor in the case of very poor fastness to washing of the dyed textiles and thus preventing deposition on washed-off white or differently colored fabric.
  • the detergent formulations in which the dye transfer-inhibiting color fixatives described can be used are powder, granule, paste, gel or liquid. Examples of these are heavy-duty detergents, mild detergents, color detergents, wool detergents, curtain detergents, modular detergents, washing tablets, bar soaps, detergent formulations packed in water-soluble films and stain salts.
  • Laundry treatment agents are, for example, laundry starches and stiffeners and ironing aids.
  • the dye-transfer-inhibiting dye-fixing agents mentioned can be used in laundry pretreatment or laundry aftertreatment agents which can be used before or after the actual wash cycle and which are used exclusively for laundry care and laundry conditioning, but not for cleaning the laundry.
  • the detergents according to the invention contain at least 0.1%, preferably between 0.1 and 10% and particularly preferably 0.5 to 5% of the dye transfer-inhibiting dye fixatives described.
  • Formulations that are used as laundry pretreatment and / or laundry post-treatment agents can contain between 1 and 99% of the color fixing agents. Depending on their intended use, the formulation of the formulations must be adapted to the type of textiles to be washed.
  • washing and Detergent ingredients are described below.
  • the total concentration of the surfactants in the finished detergent formulation can be from 1 to 99% and preferably from 5 to 80% (all% by weight).
  • the surfactants used can be anionic, nonionic, amphoteric and cationic. Mixtures of the surfactants mentioned can also be used.
  • Preferred detergent formulations contain anionic and / or nonionic surfactants and their mixtures with other surfactants.
  • Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof.
  • Suitable cations are alkali metals, such as sodium or potassium, or alkaline earth metals, such as calcium or magnesium, and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof.
  • the following types of anionic surfactants are particularly preferred: alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkane sulfonates and soaps, as described below.
  • Alkyl ester sulfonates include linear esters of C 8 -C 20 carboxylic acids (ie fatty acids) which are sulfonated using gaseous SO 3 , as described in "The Journal of the American Oil Chemists Society” 52 (1975), pp. 323-329.
  • Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but can also be synthetic in nature.
  • Preferred alkyl ester sulfonates are compounds of the formula wherein R 1 is a C 8 -C 20 hydrocarbon radical, preferably alkyl, and R is a C 1 -C 6 hydrocarbon radical, preferably alkyl.
  • M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine.
  • R 1 is preferably C 10 -C 16 alkyl and R is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R 1 is C 10 -C 16 alkyl are particularly preferred.
  • Alkyl sulfates are here water-soluble salts or acids of the formula ROSO 3 M, in which R is a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with a C 10 -C 20 alkyl component, particularly preferably a C 12 -C 18 alkyl or Is hydroxyalkyl.
  • M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine , Diethylamine, triethylamine and mixtures thereof.
  • Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below approx. 50 ° C) and alkyl chains with C 16 -C 18 for higher washing temperatures (eg above approx. 50 ° C).
  • Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, in which R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 alkyl or hydroxyalkyl radical, particularly preferably C 12 -C 18 represents alkyl or hydroxyalkyl.
  • A is an ethoxy or propoxy unit
  • m is a number greater than 0, preferably between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3
  • M is a hydrogen atom or a cation such as, for example Sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
  • alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
  • Examples include C 12 to C 18 fatty alcohol ether sulfates, the content of EO being 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate, and in which M is sodium or potassium.
  • the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted.
  • the sulfo group can be at any position on the C chain, with the primary methyl groups at the beginning and end of the chain none Possess sulfonate groups.
  • the preferred secondary alkanesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably about 10 to about 20 Carbon atoms and particularly preferably about 13 to 17 carbon atoms.
  • the Cation is, for example, sodium, potassium, ammonium, mono-, di- or Triethanolammonium, calcium or magnesium, and mixtures thereof. sodium is preferred as the cation.
  • primary alkanesulfonates can also be used in the detergents according to the invention are used.
  • the preferred alkyl chains and cations correspond to those of the secondary alkane sulfonates.
  • the preparation of primary alkanesulfonic acid, from which the corresponding sulfonates which are effective as surfactants are obtained, is described, for example, in EP 854 136-A1.
  • alkenyl or alkylbenzenesulfonates are alkenyl or alkylbenzenesulfonates.
  • the alkenyl or alkyl group can be branched or linear and optionally substituted with a hydroxyl group.
  • the preferred alkylbenzenesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Magnesium is preferred as the cation for mild surfactant systems, while sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.
  • anionic surfactants also includes olefin sulfonates which are obtained by sulfonating C 8 -C 24 -, preferably C 14 -C 16 - ⁇ -olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these olefin sulfonates can contain smaller amounts of hydroxyalkanesulfonates and alkane disulfonates. Special mixtures of ⁇ -olefin sulfonates are described in US 3,332,880.
  • Suitable anionic surfactants are carboxylates, e.g. Fatty acid soaps and comparable surfactants.
  • the soaps can be saturated or unsaturated and can have various substituents, such as hydroxyl groups or ⁇ -sulfonate groups contain.
  • Linear saturated or unsaturated hydrocarbon radicals are preferred as a hydrophobic portion with about 6 to about 30, preferably about 10 to about 18 Carbon atoms.
  • Suitable anionic surfactants are salts of acylaminocarboxylic acids, the acyl sarcosinates formed in the alkaline medium by reaction of fatty acid chlorides with sodium sarcosinate; Fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkyl sulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis products of alkaline earth metal citrates as described, for example, in GB-1,082,179; Alkyl and alkenyl glycerol sulfates such as oleyl glycerol sulfates, alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates, such as acyl isethionates, N-acy
  • the alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • the condensation products of C 10 to C 20 alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol are particularly preferred.
  • the alkyl chain can be saturated or unsaturated.
  • the alcohol ethoxylates can have a narrow (“narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates").
  • nonionic surfactants of this type are Tergitol® 15-S-9 (condensation product of a linear secondary C 11 -C 15 alcohol with 9 mol ethylene oxide), Tergitol® 24-L-NMW (condensation product of a linear primary C 12 -C 14 -alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution).
  • Genapol® brands from Clariant GmbH also fall under this product class.
  • the hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800.
  • the attachment of ethylene oxide to this Hydrophobic part leads to an improvement in water solubility.
  • the product is liquid up to a polyoxyethylene content of approx. 50% of the total weight of the Condensation product, which is a condensation with up to about 40 mol of ethylene oxide equivalent.
  • Commercially available examples of this product class are the Pluronic® brands from BASF and the ®Genapol PF brands from Clariant GmbH.
  • the hydrophobic unit of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a Molecular weight from about 2500 to 3000. At this hydrophobic unit Ethylene oxide up to a content of approx. 40 to approx. 80% by weight of polyoxyethylene and a molecular weight of about 5000 to 11000 added.
  • Ethylene oxide up to a content of approx. 40 to approx. 80% by weight of polyoxyethylene and a molecular weight of about 5000 to 11000 added.
  • Commercially available Examples of this class of compounds are the ®Tetronic brands from BASF and the ®Genapol PN brands from Clariant GmbH.
  • This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each with an alkyl radical of approximately 10 to approximately 18 carbon atoms.
  • Semipolar nonionic surfactants are also amine oxides of the formula R is an alkyl, hydroxyalkyl or alkylphenol group with a chain length of about 8 to about 22 carbon atoms, R 2 is an alkylene or hydroxyalkylene group with about 2 to 3 carbon atoms or mixtures thereof, each R 1 is an alkyl - Or hydroxyalkyl group with approx. 1 to approx. 3 carbon atoms or a polyethylene oxide group with approx. 1 to approx.
  • ethylene oxide units and x means a number from 0 to approx. 10.
  • the R 1 groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring.
  • Amine oxides of this type are especially C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy diethyl dihydroxyethyl amine oxides.
  • Fatty acid amides have the formula wherein R is an alkyl group with about 7 to about 21, preferably about 9 to about 17 carbon atoms and each radical R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x means H, where x varies from about 1 to about 3.
  • R is an alkyl group with about 7 to about 21, preferably about 9 to about 17 carbon atoms and each radical R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x means H, where x varies from about 1 to about 3.
  • C 8 -C 20 amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.
  • nonionic surfactants are alkyl and alkenyl oligoglycosides as well Fatty acid polyglycol esters or fatty amine polyglycol esters each with 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, Mixed ethers or mixed formals, alkyl oligoglycosides, alkenyl oligoglycosides, fatty acid N-alkyl glucamides, Phosphine oxides, dialkyl sulfoxides and protein hydrolyzates.
  • Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.
  • These compounds include the condensation products of alkylphenols with a C 6 to C 20 alkyl group, which can be either linear or branched, with alkene oxides. Compounds with about 5 to 25 mol of alkene oxide per mol of alkylphenol are preferred.
  • Commercially available surfactants of this type are, for example, Igepal® CO-630, Triton® X-45, X-114, X-100 and X102, and the ®Arkopal-N brands from Clariant GmbH. These surfactants are referred to as alkylphenol alkoxylates, for example alkylphenol ethoxylates.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula wherein R 1 is C 8 -C 22 alkyl or alkenyl, R 2 is hydrogen or CH 2 CO 2 M, R 3 CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CH 2 CO 2 M, R 4 is hydrogen, CH 2 CH 2 OH or CH 2 CH 2 COOM, Z CO 2 M or CH 2 CO 2 M, n 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonium or alkanolammonium.
  • Preferred amphoteric surfactants of this formula are monocarboxylates and Dicarboxylates. Examples include cocoamphocarboxypropionate, Cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinat (or also as Cocoamphodiacetate) and Cocoamphoacetat.
  • amphoteric surfactants are alkyldimethylbetaines and Alkyldipolyethoxybetaines with an alkyl radical having about 8 to about 22 carbon atoms, which can be linear or branched, preferably having 8 to 18 carbon atoms and particularly preferably having about 12 to about 18 carbon atoms. These connections e.g. from Clariant GmbH under the trade name ®Genagen LAB marketed.
  • Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R 1 N (CH 3 ) 3 ⁇ X ⁇ , R 1 R 2 N (CH 3 ) 2 ⁇ X ⁇ , R 1 R 2 R 3 N (CH 3 ) ⁇ X ⁇ or R 1 R 2 R 3 R 4 N ⁇ X ⁇ .
  • the radicals R 1 , R 2 , R 3 and R 4 can preferably independently of one another unsubstituted alkyl with a chain length between 8 and 24 carbon atoms, in particular between 10 and 18 carbon atoms, hydroxyalkyl with about 1 to about 4 carbon atoms.
  • X is a suitable anion.
  • detergent ingredients included in the present invention may include inorganic and / or organic builders to the To reduce the hardness of the water.
  • inorganic Builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.
  • silicate builders are the alkali metal silicates, in particular those with an SiO 2 : Na 2 O ratio between 1.6: 1 and 3.2: 1, and sheet silicates, for example sodium sheet silicates, as described in US Pat. No. 4,664,839, available from Clariant GmbH under the SKS® brand.
  • SKS-6® is a particularly preferred layered silicate builder.
  • Aluminosilicate builders are particularly preferred for the present invention. These are in particular zeolites with the formula Na z [(AlO 2 ) z (SiO 2 ) y ] .xH 2 O, where z and y are integers of at least 6, the ratio of z to y is between 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • Suitable ion exchangers based on aluminosilicate are commercially available. This Aluminosilicates can be crystalline or amorphous in structure and can naturally occurring or synthetically produced. Procedure for the Manufacture of ion exchangers based on aluminosilicate are described in U.S. 3,985,669 and U.S. 4,605,509. Preferred ion exchangers based Synthetic crystalline aluminosilicates are available under the name Zeolite A, Zeolite P (B) (including those disclosed in EP-A-0 384 070) and Zeolite X. Preferred are aluminosilicates with a particle diameter between 0.1 and 10 ⁇ m.
  • Suitable organic builders include polycarboxyl compounds, such as ether polycarboxylates and oxydisuccinates, such as for example, described in US-3,128,287 and US-3,635,830. Also on “TMS / TDS" builders can be found in US 4,663,071.
  • Suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitric acid and also polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.
  • Important organic builders are also polycarboxylates based on acrylic acid and maleic acid, such as the Sokalan CP brands from BASF.
  • Citric acid and its soluble salts, especially the sodium salt are preferred polycarboxylic acid builders that also in granulated formulations, especially together with zeolites and / or layered silicates can be used.
  • phosphorus-based builders can be used, and especially if soap bars for laundry are to be formulated by hand, various alkali metal phosphates such as sodium tripolyphosphate, Sodium pyrophosphate and sodium orthophosphate can be used.
  • alkali metal phosphates such as sodium tripolyphosphate, Sodium pyrophosphate and sodium orthophosphate can be used.
  • phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and others known phosphonates as described, for example, in US Pat. No. 3,159,581, US Pat. No. 3,213,030, U.S. 3,422,021, U.S. 3,400,148 and U.S. 3,422,137 are used.
  • the detergents and laundry treatment agents according to the invention can be conventional Contain auxiliaries or other materials that enhance the cleaning effect, to treat or care for the textile material to be washed or the Change the usage properties of the detergent composition.
  • auxiliaries include the substances mentioned in US Pat. No. 3,936,537, for example enzymes, in particular proteases, lipases, cellulases and Amylases, mannanases, enzyme stabilizers, foam boosters, foam brakes, Anti-tarnish and / or anti-corrosion agents, suspending agents, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropic compounds, Antioxidants, perfumes, solvents, solubilizers, Redeposition inhibitors, dispersants, processing aids, Plasticizers, anti-static agents and soil release polymers such as the TexCare brands / Clariant, the Repel-O-Tex brands / Rhodia or Sokalan SR-100 / company BASF.
  • enzymes in particular proteases, lipases, cellulases and Amylases, mannanases, enzyme stabilizers, foam boosters, foam brakes, Anti-tarnish and / or anti-corrosion agents, suspending agents, dyes, fillers, optical
  • the washing and cleaning agents according to the invention containing color transfer-inhibiting color fixatives can additionally also contain the known and commercially available color transfer inhibitors.
  • these color transfer inhibitors are polyamine N-oxides such as poly- (4-vinylpyridine-N-oxide), for example Chromabond S-400, from ISP; Polyvinylpyrrolidone, for example Sokalan HP 50 / BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
  • a major disadvantage of the dye transfer inhibitors commercially available hitherto is that they not only bind the dye detached from the textiles and contained in the wash liquor, but can also detach dyes from the textiles and thus promote fading of the washed dye fabric.
  • the combination with the dye-transfer-inhibiting dye fixatives not only improves the dye-transfer-inhibiting effect of the known dye-transfer inhibitors, but also counteracts the fading of the color fabrics promoted by these products.
  • the detergent compositions of the present invention can optionally contain one or more conventional bleaches, and Bleach activators, bleach catalysts and suitable stabilizers. In general it must be ensured that the bleach used with the detergent ingredients are tolerated. Conventional test methods, such as the Determination of the bleaching activity of the formulated cleaning agent in Depending on the storage time can be used for this purpose.
  • the peroxy acid can either be a free peroxy acid or a combination from an inorganic persalt, for example sodium perborate or Sodium percarbonate and an organic peroxyacid precursor that leads to a Peroxyacid is converted when the combination of persalt and Peroxyacid precursor is dissolved in water.
  • the organic peroxyacid precursors are often referred to as bleach activators in the prior art. Examples of suitable organic peroxyacids are disclosed in US 4,374,035, U.S. 4,681,592, U.S. 4,634,551, U.S. 4,686,063, U.S. 4,606,838 and U.S. 4,671,891.
  • compositions suitable for bleaching laundry and containing perborate bleaches and activators are described in U.S. 4,412,934, U.S. 4,536,314, U.S. 4,681,695 and U.S. 4,539,130.
  • peroxyacids preferred for use in this invention include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA).
  • DPDA peroxydodecanedioic acid
  • NAPSA nonylamide of peroxysuccinic acid
  • NAPAA nonylamide of peroxyadipic acid
  • DDPSA decyldiperoxysuccinic acid
  • the color fixatives described can also be found in commercially available Fabric softeners are used for household applications. This essentially contain plasticizing components, co-plasticizers, Emulsifiers, perfumes, dyes and electrolytes, and are at an acidic pH from below 7, preferably between 3 and 5.
  • Examples include distearyldimethylammonium chloride, ditallow alkyldimethylammonium chloride, Ditalgalkylmethylhydroxypropylammoniumchlorid, Cetyltrimethylammonium chloride or the corresponding benzyl derivatives such as such as dodecyldimethylbenzylammonium chloride. Cyclic quaternary ammonium salts, such as alkyl morpholine derivatives can also be used.
  • Triethanolamine and methyldiethanolamine are particularly preferred.
  • esterquats are Aminoglycerol derivatives, e.g. Dimethylaminopropanediol.
  • Alkylation or hydroxyalkylation agents are preferred, preferably alkyl halides Methyl chloride, dimethyl sulfate, ethylene oxide and propylene oxide.
  • ester quats are compounds of the formulas: where RCO is derived from C 8 -C 24 fatty acids, which can be saturated or unsaturated. Examples include caproic acid, caprylic acid, hydrogenated or not or only partially hydrogenated tallow fatty acids, stearic acid, oleic acid, linolenic acid, behenic acid, palminstearic acid, myristic acid and elaidic acid. n is in the range from 0 to 10, preferably 0 to 3, particularly preferably 0 to 1.
  • a radical R 3 which can be C 1 -C 4 -alkyl, preferably methyl
  • a counterion X which can be chloride, bromide, iodide or methyl sulfate
  • Amidoaminooxethylates and their quaternized secondary products are offered under the trade names ®Varisoft 510, ®Varisoft 512, ®Rewopal V 3340 and ®Rewoquat W 222 LM.
  • the preferred application concentrations of the color fixative in the Fabric softener formulations correspond to those for detergent formulations are mentioned.
  • the color transfer inhibiting color fixatives were used in combination with Standard detergents on different color fabrics on their color-preserving Effect examined. At the same time, the test was carried out for an ink transfer inhibitor Effect.
  • the tissues were then rinsed with clear water, dried and the dL, da, determines db values from which the color differences delta E result.
  • the fabrics with the test detergents were added without the Color fixative washed.
  • the washing conditions are given in Table 3. A total of five wash cycles were carried out.
  • the values obtained on the white fabric after the first wash serve to quantify the color transfer inhibiting effect.
  • the values measured on the colored fabric quantify the color retention achieved.
  • the average dE value obtained on five different color fabrics was calculated. Standard phosphate-free washing powder IEC-A.
  • Tables 7 to 11 show the average delta E values obtained on red, blue, green, violet and black colored fabrics. The lower these values are, the better the color retention achieved with the color fixing agents in the detergents according to the invention.
  • Detergent / additive ⁇ delta E values Color differences to the unwashed fabric after five washes IEC-A without additive 7.6 + Ex. 1 5.3 + Ex. 2 3.9 + Ex. 3 4.7 Color-preserving effect in combination with the phosphate-free test washing powder IEC-A with bleach additive
  • Detergent / additive ⁇ delta E values Color differences to the unwashed fabric after five washes IEC-A without additive 7.4 + Ex. 1 6.4 + Ex.
  • the following examples show the color transfer-inhibiting effect of the detergents according to the invention containing the color transfer-inhibiting color fixatives on the white fabrics washed together with the color fabrics.
  • Detergent / additive delta E values of the white test fabric washed together with violet color fabric after a wash IEC-A without additive 36.9 + Ex. 1 12.7 + Ex. 2 15.2 + Ex. 3 14.6 Color transfer inhibiting effect in combination with the phosphate-free test washing powder IEC-A on blue test fabric.
  • Detergent / additive delta E values of the white test fabric washed together with blue color fabric after a wash IEC-A without additive 32.6 + Ex. 1 8.7 + Ex. 2 18.9 + Ex. 3 14.7 Color transfer inhibiting effect of Example 1 in combination with the phosphate-free test washing powder IEC-A on other color test fabrics.
  • Detergent / additive delta E values of the white test fabric washed together with other color fabrics after a wash. black green red IEC-A without additive 35.1 22.0 37.5 + Ex. 1 15.1 10.9 28.3

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Abstract

Washing agents contain transfer-inhibiting dye fixing agents. Washing agents contain transfer-inhibiting dye fixing agents obtained by reaction of: (i) polyamines with cyanamides and amidosulfuric acid; (ii) cyanamides with aldehydes and ammonium salts; or (iii) amines with epichlorhydrin.

Description

Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende FarbfixiermittelDetergents and laundry treatment compositions containing one or more dye transfer inhibiting dye fixatives

Gegenstand der Erfindung sind Waschmittel und Wäschebehandlungsmittel enthaltend farbübertragungsinhibierende Farbfixiermittel, wobei diese Farbfixiermittel erhalten werden durch Umsetzung von

  • a) Polyaminen mit Cyanamiden und Amidoschwefelsäure
    oder
  • b) Cyanamiden mit Aldehyden und Ammoniumsalzen
    oder
  • c) Aminen mit Epichlorhydrin.
    • The invention relates to detergents and laundry treatment compositions containing color transfer-inhibiting color fixing agents, these color fixing agents being obtained by reacting
  • a) Polyamines with cyanamides and amidosulfuric acid
    or
  • b) cyanamides with aldehydes and ammonium salts
    or
  • c) amines with epichlorohydrin.

    • Die eingesetzten Amine können primäre, sekundäre und tertiäre Amine sein. Dabei kann es sich um aliphatische Amine, alicyclische Amine wie z.B. Cyclohexylamin und aromatische Amine wie z.B. Anilin handeln. Die verwendeten Amine können aber auch gleichzeitig aliphatische, alicyclische und aromatische Substituenten besitzen. Ferner können auch heterocyclische Verbindungen wie z.B. Pyridin eingesetzt werden.
    Der Begriff Polyamine umfasst hierbei z.B. Diamine, Triamine, Tetraamine usw. Beispiele hierfür sind Ethylendiamin, Propylendiamin, Butylendiamin, Pentylendiamin, Hexylendiamin, Diethylentriamin, Triethylentetramin und höhere Polyamine.
    Besonders bevorzugt ist Diethylentriamin.
    Bei den Ammoniumsalzen kann es sich um Salze des Ammoniaks oder der oben erwähnten Amine bzw. Polyamine mit verschiedenen anorganischen oder organischen Säuren oder auch um quartäre Ammoniumsalze handeln.
    Bei den Cyanamiden kann es sich um Cyanamid oder um Dicyandiamid handeln. Aldehyde, die zur Synthese der farbübertragungsinhibierenden Farbfixiermittel eingesetzt werden können, sind zum Beispiel aliphatische Aldehyde wie z.B. Formaldehyd, Acetaldehyd, Propionaldehyd, Butyraldehyd; Dialdehyde wie z.B.     The amines used can be primary, secondary and tertiary amines. These can be aliphatic amines, alicyclic amines such as cyclohexylamine and aromatic amines such as aniline. However, the amines used can also have aliphatic, alicyclic and aromatic substituents at the same time. Heterocyclic compounds such as pyridine can also be used.
    The term polyamines here includes, for example, diamines, triamines, tetraamines, etc. Examples include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine and higher polyamines.
    Diethylene triamine is particularly preferred.
    The ammonium salts can be salts of ammonia or the amines or polyamines mentioned above with various inorganic or organic acids or else quaternary ammonium salts.
    The cyanamides can be cyanamide or dicyandiamide. Aldehydes which can be used for the synthesis of the color transfer-inhibiting color fixing agents are, for example, aliphatic aldehydes such as, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; Dialdehydes such as

    Glyoxal; ungesättigte Aldehyde wie z.B. Acrolein, Crotonaldehyd und aromatische Aldehyde wie z.B. Benzaldehyd. Besonders bevorzugt sind die aliphatischen Aldehyde.glyoxal; unsaturated aldehydes such as e.g. Acrolein, crotonaldehyde and aromatic Aldehydes such as Benzaldehyde. The aliphatic ones are particularly preferred Aldehydes.

    Diese Farbfixiermittel werden den erfindungsgemäßen Waschmitteln zugesetzt um die Waschechtheit der Textilfarbstoffe zu verbessern, indem sie deren Ausbluten reduzieren.
    Gleichzeitig wirken diese Farbfixiermittel auch farbübertragungsinhibierend, indem sie bei sehr schlechten Waschechtheiten der gefärbten Textilien Restmengen von ausblutendem Farbstoff in der Waschlauge binden und so eine Ablagerung auf mitgewaschenem weißen oder andersfarbigen Gewebe verhindern.    These color fixatives are added to the detergents according to the invention in order to improve the wash fastness of the textile dyes by reducing their bleeding.
    At the same time, these color fixatives also inhibit color transfer by binding residual amounts of bleeding-out dye in the wash liquor in the case of very poor fastness to washing of the dyed textiles and thus preventing deposition on washed-off white or differently colored fabric.

    Die Waschmittelformulierungen, in denen die beschriebenen farbübertragungsinhibierenden Farbfixiermittel eingesetzt werden können, sind pulver-, granulat-, pasten-, gelförmig oder flüssig. Beispiele hierfür sind Vollwaschmittel, Feinwaschmittel, Colorwaschmittel, Wollwaschmittel, Gardinenwaschmittel, Baukastenwaschmittel, Waschtabletten, bar soaps, Waschmittelformulierungen in wasserlöslichen Folien verpackt und Fleckensalze. Wäschebehandlungsmittel sind z.B. Wäschestärken und -steifen sowie Bügelhilfen.
    Außerdem können die genannten farbübertragungsinhibierenden Farbfixiermittel in Wäschevor- bzw. Wäschenachbehandlungsmitteln eingesetzt werden, die vor bzw. nach dem eigentlichen Waschgang zur Anwendung kommen können und die ausschließlich der Wäschepflege und der Wäschekonditionierung, aber nicht der Reinigung der Wäsche dienen.    The detergent formulations in which the dye transfer-inhibiting color fixatives described can be used are powder, granule, paste, gel or liquid. Examples of these are heavy-duty detergents, mild detergents, color detergents, wool detergents, curtain detergents, modular detergents, washing tablets, bar soaps, detergent formulations packed in water-soluble films and stain salts. Laundry treatment agents are, for example, laundry starches and stiffeners and ironing aids.
    In addition, the dye-transfer-inhibiting dye-fixing agents mentioned can be used in laundry pretreatment or laundry aftertreatment agents which can be used before or after the actual wash cycle and which are used exclusively for laundry care and laundry conditioning, but not for cleaning the laundry.

    Die erfindungsgemäßen Waschmittel enthalten mindestens 0,1 %, bevorzugt zwischen 0,1 und 10 % und besonders bevorzugt 0,5 bis 5 % der beschriebenen farbübertragungsinhibierenden Farbfixiermittel.
    Formulierungen die als Wäschevor- und/oder Wäschenachbehandlungsmittel eingesetzt werden, können zwischen 1 und 99 % der Farbfixiermittel enthalten.
    Die Formulierungen sind je nach ihrer vorgesehenen Anwendung in ihrer Zusammensetzung der Art der zu waschenden Textilien anzupassen.     The detergents according to the invention contain at least 0.1%, preferably between 0.1 and 10% and particularly preferably 0.5 to 5% of the dye transfer-inhibiting dye fixatives described.
    Formulations that are used as laundry pretreatment and / or laundry post-treatment agents can contain between 1 and 99% of the color fixing agents.
    Depending on their intended use, the formulation of the formulations must be adapted to the type of textiles to be washed.

    Sie enthalten konventionelle Wasch- und Reinigungsmittelinhaltsstoffe, wie sie dem Stand der Technik entsprechen. Repräsentative Beispiele für solche Wasch- und Reinigungsmittelinhaltsstoffe werden im folgenden beschrieben.They contain conventional detergent and cleaning agent ingredients such as the State of the art. Representative examples of such washing and Detergent ingredients are described below.

    Die Gesamtkonzentration der Tenside in der fertigen Waschmittelformulierung kann von 1 bis 99 % und bevorzugt von 5 bis 80 % (alles Gew.-%) betragen.
    Die verwendeten Tenside können anionisch, nichtionisch, amphoter und kationisch sein. Es können auch Mischungen der genannten Tenside verwendet werden. Bevorzugte Waschmittelformulierungen enthalten anionische und/oder nichtionische Tenside und deren Mischungen mit weiteren Tensiden.    The total concentration of the surfactants in the finished detergent formulation can be from 1 to 99% and preferably from 5 to 80% (all% by weight).
    The surfactants used can be anionic, nonionic, amphoteric and cationic. Mixtures of the surfactants mentioned can also be used. Preferred detergent formulations contain anionic and / or nonionic surfactants and their mixtures with other surfactants.

    Als anionische Tenside kommen Sulfate, Sulfonate, Carboxylate, Phosphate und Mischungen daraus in Betracht. Geeignete Kationen sind hierbei Alkalimetalle, wie z.B. Natrium oder Kalium oder Erdalkalimetalle, wie z.B. Calcium oder Magnesium sowie Ammonium, substituierte Ammoniumverbindungen, einschließlich Mono-, Dioder Triethanolammoniumkationen, und Mischungen daraus.
    Folgende Typen von anionischen Tensiden sind besonders bevorzugt: Alkylestersulfonate, Alkylsulfate, Alkylethersulfate, Alkylbenzolsulfonate, Alkansulfonate und Seifen, wie im folgenden beschrieben.    Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof. Suitable cations are alkali metals, such as sodium or potassium, or alkaline earth metals, such as calcium or magnesium, and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof.
    The following types of anionic surfactants are particularly preferred: alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkane sulfonates and soaps, as described below.

    Alkylestersulfonate sind unter anderem lineare Ester von C8-C20-Carboxylsäuren (d.h. Fettsäuren), welche mittels gasförmigem SO3 sulfoniert werden, wie in "The Journal of the American Oil Chemists Society" 52 (1975), pp. 323-329 beschrieben wird. Geeignete Ausgangsmaterialien sind natürliche Fette wie z.B. Talg, Kokosöl und Palmöl, können aber auch synthetischer Natur sein.Alkyl ester sulfonates include linear esters of C 8 -C 20 carboxylic acids (ie fatty acids) which are sulfonated using gaseous SO 3 , as described in "The Journal of the American Oil Chemists Society" 52 (1975), pp. 323-329. Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but can also be synthetic in nature.

    Bevorzugte Alkylestersulfonate, speziell für Waschmittelanwendungen, sind Verbindungen der Formel

    Figure 00030001
    worin R1 einen C8-C20-Kohlenwasserstoffrest, bevorzugt Alkyl, und R einen C1-C6 Kohlenwasserstoffrest, bevorzugt Alkyl, darstellt. M steht für ein Kation, das ein wasserlösliches Salz mit dem Alkylestersulfonat bildet. Geeignete Kationen sind Natrium, Kalium, Lithium oder Ammoniumkationen, wie Monoethanolamin, Diethanolamin und Triethanolamin. Bevorzugt bedeuten R1 C10-C16-Alkyl und R Methyl, Ethyl oder Isopropyl. Besonders bevorzugt sind Methylestersulfonate, in denen R1 C10-C16-Alkyl bedeutet.Preferred alkyl ester sulfonates, especially for detergent applications, are compounds of the formula
    Figure 00030001
    wherein R 1 is a C 8 -C 20 hydrocarbon radical, preferably alkyl, and R is a C 1 -C 6 hydrocarbon radical, preferably alkyl. M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. R 1 is preferably C 10 -C 16 alkyl and R is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R 1 is C 10 -C 16 alkyl are particularly preferred.

    Alkylsulfate sind hier wasserlösliche Salze oder Säuren der Formel ROSO3M, worin R ein C10-C24-Kohlenwasserstoffrest, bevorzugt ein Alkyl- oder Hydroxyalkylrest mit C10-C20-Alkylkomponente, besonders bevorzugt ein C12-C18 Alkyl- oder Hydroxyalkylrest ist. M ist Wasserstoff oder ein Kation, z.B. ein Alkalimetallkation (z.B. Natrium, Kalium, Lithium) oder Ammonium oder substituiertes Ammonium, z.B. Methyl-, Dimethyl- und Trimethylammoniumkationen und quaternäre Ammoniumkationen, wie Tetramethylammonium- und Dimethylpiperidiniumkationen und quartäre Ammoniumkationen, abgeleitet von Alkylaminen wie Ethylamin, Diethylamin, Triethylamin und Mischungen davon. Alkylketten mit C12-C16 sind für niedrige Waschtemperaturen (z.B. unter ca. 50°C) und Alkylketten mit C16-C18 für höhere Waschtemperaturen (z.B. oberhalb ca. 50°C) bevorzugt.Alkyl sulfates are here water-soluble salts or acids of the formula ROSO 3 M, in which R is a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with a C 10 -C 20 alkyl component, particularly preferably a C 12 -C 18 alkyl or Is hydroxyalkyl. M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine , Diethylamine, triethylamine and mixtures thereof. Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below approx. 50 ° C) and alkyl chains with C 16 -C 18 for higher washing temperatures (eg above approx. 50 ° C).

    Alkylethersulfate sind wasserlösliche Salze oder Säuren der Formel RO(A)m SO3M, worin R einen unsubstituierten C10-C24-Alkyl- oder Hydroxyalkylrest, bevorzugt einen C12-C20 Alkyl- oder Hydroxyalkylrest, besonders bevorzugt C12-C18-Alkyl- oder Hydroxyalkylrest darstellt. A ist eine Ethoxy- oder Propoxyeinheit, m ist eine Zahl größer als 0, vorzugsweise zwischen ca. 0,5 und ca. 6, besonders bevorzugt zwischen ca. 0,5 und ca. 3 und M ist ein Wasserstoffatom oder ein Kation wie z.B. Natrium, Kalium, Lithium, Calcium, Magnesium, Ammonium oder ein substituiertes Ammoniumkation. Spezifische Beispiele von substituierten Ammoniumkationen sind Methyl-, Dimethyl-, Trimethylammonium- und quarternäre Ammoniumkationen wie Tetramethylammonium und Dimethylpiperidiniumkationen sowie solche, die von Alkylaminen, wie Ethylamin, Diethylamin, Triethylamin oder Mischungen davon abgeleitet sind. Als Beispiele seien C12- bis C18-Fettalkoholethersulfate genannt wobei der Gehalt an EO 1, 2, 2.5, 3 oder 4 mol pro mol des Fettalkoholethersulfats beträgt, und in denen M Natrium oder Kalium ist. Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, in which R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 alkyl or hydroxyalkyl radical, particularly preferably C 12 -C 18 represents alkyl or hydroxyalkyl. A is an ethoxy or propoxy unit, m is a number greater than 0, preferably between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as, for example Sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples include C 12 to C 18 fatty alcohol ether sulfates, the content of EO being 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate, and in which M is sodium or potassium.

    In sekundären Alkansulfonaten kann die Alkylgruppe entweder gesättigt oder ungesättigt, verzweigt oder linear und gegebenenfalls mit einer Hydroxylgruppe substituiert sein. Die Sulfogruppe kann an einer beliebigen Position der C-Kette sein, wobei die primären Methylgruppen am Kettenanfang und Kettenende keine Sulfonatgruppen besitzen. Die bevorzugten sekundären Alkansulfonate enthalten lineare Alkylketten mit ca. 9 bis 25 Kohlenstoffatomen, bevorzugt ca. 10 bis ca. 20 Kohlenstoffatome und besonders bevorzugt ca. 13 bis 17 Kohlenstoffatome. Das Kation ist beispielsweise Natrium, Kalium, Ammonium, Mono-, Di- oder Triethanolammonium, Calcium oder Magnesium, und Mischungen davon. Natrium als Kation ist bevorzugt.In secondary alkanesulfonates, the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted. The sulfo group can be at any position on the C chain, with the primary methyl groups at the beginning and end of the chain none Possess sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably about 10 to about 20 Carbon atoms and particularly preferably about 13 to 17 carbon atoms. The Cation is, for example, sodium, potassium, ammonium, mono-, di- or Triethanolammonium, calcium or magnesium, and mixtures thereof. sodium is preferred as the cation.

    Neben sekundären Alkansulfonaten können auch primäre Alkansulfonate in den erfindungsgemäßen Waschmitteln eingesetzt werden.In addition to secondary alkanesulfonates, primary alkanesulfonates can also be used in the detergents according to the invention are used.

    Die bevorzugten Alkylketten und Kationen entsprechen denen der sekundären Alkansulfonaten.
    Die Herstellung von primärer Alkansulfonsäure, aus der die als Tensid wirksamen entsprechenden Sulfonate erhalten werden, ist z.B. in EP 854 136-A1 beschrieben.    The preferred alkyl chains and cations correspond to those of the secondary alkane sulfonates.
    The preparation of primary alkanesulfonic acid, from which the corresponding sulfonates which are effective as surfactants are obtained, is described, for example, in EP 854 136-A1.

    Weitere geeignete anionische Tenside sind Alkenyl- oder Alkylbenzolsulfonate. Die Alkenyl- oder Alkylgruppe kann verzweigt oder linear und gegebenenfalls mit einer Hydroxylgruppe substituiert sein. Die bevorzugten Alkylbenzolsulfonate enthalten lineare Alkylketten mit ca. 9 bis 25 Kohlenstoffatomen, bevorzugt von ca. 10 bis ca. 13 Kohlenstoffatome, das Kation ist Natrium, Kalium, Ammonium, Mono-, Di- oder Triethanolammonium, Calcium oder Magnesium und Mischungen davon.
    Für milde Tensidsysteme ist Magnesium als Kation bevorzugt, für Standardwaschanwendungen dagegen Natrium. Gleiches gilt für Alkenylbenzolsulfonate.    Other suitable anionic surfactants are alkenyl or alkylbenzenesulfonates. The alkenyl or alkyl group can be branched or linear and optionally substituted with a hydroxyl group. The preferred alkylbenzenesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof.
    Magnesium is preferred as the cation for mild surfactant systems, while sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.

    Der Begriff anionische Tenside schließt auch Olefinsulfonate mit ein, die durch Sulfonierung von C8-C24-, vorzugsweise C14-C16-α-Olefinen mit Schwefeltrioxid und anschließende Neutralisation erhalten werden. Bedingt durch das Herstellverfahren, können diese Olefinsulfonate kleinere Mengen an Hydroxyalkansulfonaten und Alkandisulfonaten enthalten. Spezielle Mischungen von α-Olefinsulfonaten sind in US-3,332,880 beschrieben.The term anionic surfactants also includes olefin sulfonates which are obtained by sulfonating C 8 -C 24 -, preferably C 14 -C 16 -α-olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these olefin sulfonates can contain smaller amounts of hydroxyalkanesulfonates and alkane disulfonates. Special mixtures of α-olefin sulfonates are described in US 3,332,880.

    Weitere bevorzugte anionische Tenside sind Carboxylate, z.B. Fettsäureseifen und vergleichbare Tenside. Die Seifen können gesättigt oder ungesättigt sein und können verschiedene Substituenten, wie Hydroxylgruppen oder α-Sulfonatgruppen enthalten. Bevorzugt sind lineare gesättigte oder ungesättigte Kohlenwasserstoffreste als hydrophober Anteil mit ca. 6 bis ca. 30, bevorzugt ca. 10 bis ca. 18 Kohlenstoffatomen.Other preferred anionic surfactants are carboxylates, e.g. Fatty acid soaps and comparable surfactants. The soaps can be saturated or unsaturated and can have various substituents, such as hydroxyl groups or α-sulfonate groups contain. Linear saturated or unsaturated hydrocarbon radicals are preferred as a hydrophobic portion with about 6 to about 30, preferably about 10 to about 18 Carbon atoms.

    Als anionische Tenside kommen weiterhin Salze von Acylaminocarbonsäuren in Frage, die durch Umsetzung von Fettsäurechloriden mit Natriumsarkosinat im alkalischen Medium entstehenden Acylsarcosinate; Fettsäure-Eiweiß-Kondensationsprodukte, die durch Umsetzung von Fettsäurechloriden mit Oligopeptiden erhalten werden; Salze von Alkylsulfamidocarbonsäuren; Salze von Alkyl- und Alkylarylethercarbonsäuren; sulfonierte Polycarboxylsäuren, hergestellt durch Sulfonierung der Pyrolyseprodukte von Erdalkalimetallcitraten, wie z.B. beschrieben in GB-1,082,179; Alkyl- und Alkenylglycerinsulfate wie Oleylglycerinsulfate, Alkylphenolethersulfate, Alkylphosphate, Alkyletherphosphate, Isethionate, wie Acylisethionate, N-Acyltauride, Alkylsuccinate, Sulfosuccinate, Monoester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Monoester) und Diester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Diester), Acylsarcosinate, Sulfate von Alkylpolysacchariden wie Sulfate von Alkylpolyglycosiden, verzweigte primäre Alkylsulfate und Alkylpolyethoxycarboxylate wie die der Formel RO(CH2CH2)kCH2COO-M+, worin R C8 bis C22-Alkyl, k eine Zahl von 0 bis 10 und M ein Kation ist.
    Weitere Beispiele sind in "Surface Active Agents and Detergents" (Vol. I und II, Schwartz, Perry und Berch) beschrieben.    Other suitable anionic surfactants are salts of acylaminocarboxylic acids, the acyl sarcosinates formed in the alkaline medium by reaction of fatty acid chlorides with sodium sarcosinate; Fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkyl sulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis products of alkaline earth metal citrates as described, for example, in GB-1,082,179; Alkyl and alkenyl glycerol sulfates such as oleyl glycerol sulfates, alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates, such as acyl isethionates, N-acyl taurides, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 -monter sulfates), in particular saturated and unsaturated C 12 -C 18 monoesters unsaturated C 12 -C 18 diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxy carboxylates such as those of the formula RO (CH 2 CH 2 ) k CH 2 COO - M + , where RC 8 to C 22 -Alkyl, k is a number from 0 to 10 and M is a cation.
    Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch).

    Als nichtionische Tenside kommen beispielsweise folgende Verbindungen in Frage: Kondensationsprodukte von aliphatischen Alkoholen mit ca. 1 bis ca. 25 mol Ethylenoxid. The following compounds, for example, are suitable as nonionic surfactants: Condensation products of aliphatic alcohols with approx. 1 to approx. 25 mol Ethylene oxide.

    Die Alkylkette der aliphatischen Alkohole kann linear oder verzweigt, primär oder sekundär sein, und enthält im allgemeinen ca. 8 bis ca. 22 Kohlenstoffatome. Besonders bevorzugt sind die Kondensationsprodukte von C10- bis C20-Alkoholen mit ca. 2 bis ca. 18 mol Ethylenoxid pro mol Alkohol. Die Alkylkette kann gesättigt oder auch ungesättigt sein. Die Alkoholethoxylate können eine enge ("Narrow Range Ethoxylates") oder eine breite Homologenverteilung des Ethylenoxides ("Broad Range Ethoxylates") aufweisen. Beispiele von kommerziell erhältlichen nichtionischen Tensiden dieses Types sind Tergitol® 15-S-9 (Kondensationsprodukt eines linearen sekundären C11-C15-Alkohols mit 9 mol Ethylenoxid), Tergitol® 24-L-NMW (Kondensationsprodukt eines linearen primären C12-C14-Alkohols mit 6 mol Ethylenoxid bei enger Molgewichtsverteilung). Ebenfalls unter diese Produktklasse fallen die Genapol®-Marken der Clariant GmbH.The alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. The condensation products of C 10 to C 20 alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol are particularly preferred. The alkyl chain can be saturated or unsaturated. The alcohol ethoxylates can have a narrow ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates"). Examples of commercially available nonionic surfactants of this type are Tergitol® 15-S-9 (condensation product of a linear secondary C 11 -C 15 alcohol with 9 mol ethylene oxide), Tergitol® 24-L-NMW (condensation product of a linear primary C 12 -C 14 -alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution). The Genapol® brands from Clariant GmbH also fall under this product class.

    Kondensationsprodukte von Ethylenoxid mit einer hydrophoben Basis, gebildet durch Kondensation von Propylenoxid mit Propylenglykol.Condensation products of ethylene oxide with a hydrophobic base by condensation of propylene oxide with propylene glycol.

    Der hydrophobe Teil dieser Verbindungen weist bevorzugt ein Molekulargewicht zwischen ca. 1500 und ca. 1800 auf. Die Anlagerung von Ethylenoxid an diesen hydrophoben Teil führt zu einer Verbesserung der Wasserlöslichkeit. Das Produkt ist flüssig bis zu einem Polyoxyethylengehalt von ca. 50 % des Gesamtgewichtes des Kondensationsproduktes, was einer Kondensation mit bis zu ca. 40 mol Ethylenoxid entspricht. Kommerziell erhältliche Beispiele dieser Produktklasse sind die Pluronic®-Marken der BASF und die ®Genapol PF-Marken der Clariant GmbH.The hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800. The attachment of ethylene oxide to this Hydrophobic part leads to an improvement in water solubility. The product is liquid up to a polyoxyethylene content of approx. 50% of the total weight of the Condensation product, which is a condensation with up to about 40 mol of ethylene oxide equivalent. Commercially available examples of this product class are the Pluronic® brands from BASF and the ®Genapol PF brands from Clariant GmbH.

    Kondensationsprodukte von Ethylenoxid mit einem Reaktionsprodukt von Propylenoxid und Ethylendiamin.Condensation products of ethylene oxide with a reaction product of Propylene oxide and ethylenediamine.

    Die hydrophobe Einheit dieser Verbindungen besteht aus dem Reaktionsprodukt von Ethylendiamin mit überschüssigem Propylenoxid und weist im allgemeinen ein Molekulargewicht von ca. 2500 bis 3000 auf. An diese hydrophobe Einheit wird Ethylenoxid bis zu einem Gehalt von ca. 40 bis ca. 80 Gew.-% Polyoxyethylen und einem Molekulargewicht von ca. 5000 bis 11000 addiert. Kommerziell erhältliche Beispiele dieser Verbindungsklasse sind die ®Tetronic-Marken der BASF und die ®Genapol PN-Marken der Clariant GmbH.The hydrophobic unit of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a Molecular weight from about 2500 to 3000. At this hydrophobic unit Ethylene oxide up to a content of approx. 40 to approx. 80% by weight of polyoxyethylene and a molecular weight of about 5000 to 11000 added. Commercially available Examples of this class of compounds are the ®Tetronic brands from BASF and the ®Genapol PN brands from Clariant GmbH.

    Semipolare nichtionische TensideSemipolar nonionic surfactants

    Diese Kategorie von nichtionischen Verbindungen umfasst wasserlösliche Aminoxide, wasserlösliche Phosphinoxide und wasserlösliche Sulfoxide, jeweils mit einem Alkylrest von ca. 10 bis ca. 18 Kohlenstoffatomen. Semipolare nichtionische Tenside sind auch Aminoxide der Formel

    Figure 00080001
    R ist hierbei eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe mit einer Kettenlänge von ca. 8 bis ca. 22 Kohlenstoffatomen, R2 ist eine Alkylen- oder Hydroxyalkylengruppe mit ca. 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon, jeder Rest R1 ist eine Alkyl- oder Hydroxyalkylgruppe mit ca. 1 bis ca. 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit ca. 1 bis ca. 3 Ethylenoxideinheiten und x bedeutet eine Zahl von 0 bis etwa 10. Die R1-Gruppen können miteinander über ein Sauerstoff- oder Stickstoffatom verbunden sein und somit einen Ring bilden. Aminoxide dieser Art sind besonders C10-C18-Alkyldimethylaminoxide und C8-C12-Alkoxiethyl-Dihydroxyethylaminoxide.This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each with an alkyl radical of approximately 10 to approximately 18 carbon atoms. Semipolar nonionic surfactants are also amine oxides of the formula
    Figure 00080001
    R is an alkyl, hydroxyalkyl or alkylphenol group with a chain length of about 8 to about 22 carbon atoms, R 2 is an alkylene or hydroxyalkylene group with about 2 to 3 carbon atoms or mixtures thereof, each R 1 is an alkyl - Or hydroxyalkyl group with approx. 1 to approx. 3 carbon atoms or a polyethylene oxide group with approx. 1 to approx. 3 ethylene oxide units and x means a number from 0 to approx. 10. The R 1 groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring. Amine oxides of this type are especially C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy diethyl dihydroxyethyl amine oxides.

    Fettsäureamidefatty acid amides

    Fettsäureamide besitzen die Formel

    Figure 00080002
    worin R eine Alkylgruppe mit ca. 7 bis ca. 21, bevorzugt ca. 9 bis ca. 17 Kohlenstoffatomen ist und jeder Rest R1 Wasserstoff, C1-C4-Alkyl, C1-C4-Hydroxyalkyl oder (C2H4O)xH bedeutet, wobei x von ca. 1 bis ca. 3 variiert. Bevorzugt sind C8-C20-Amide, -monoethanolamide, -diethanolamide und -isopropanolamide.Fatty acid amides have the formula
    Figure 00080002
    wherein R is an alkyl group with about 7 to about 21, preferably about 9 to about 17 carbon atoms and each radical R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x means H, where x varies from about 1 to about 3. C 8 -C 20 amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.

    Weitere geeignete nichtionische Tenside sind Alkyl- und Alkenyloligoglycoside sowie Fettsäurepolyglykolester oder Fettaminpolyglykolester mit jeweils 8 bis 20, vorzugsweise 12 bis 18 C-Atomen im Fettalkylrest, alkoxylierte Triglycamide, Mischether oder Mischformale, Alkyloligoglycoside, Alkenyloligoglycoside, Fettsäure-N-alkylglucamide, Phosphinoxide, Dialkylsulfoxide und Proteinhydrolysate.Other suitable nonionic surfactants are alkyl and alkenyl oligoglycosides as well Fatty acid polyglycol esters or fatty amine polyglycol esters each with 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, Mixed ethers or mixed formals, alkyl oligoglycosides, alkenyl oligoglycosides, fatty acid N-alkyl glucamides, Phosphine oxides, dialkyl sulfoxides and protein hydrolyzates.

    Polyethylen-, Polypropylen- und Polybutylenoxidkondensate von Alkylphenolen.Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.

    Diese Verbindungen umfassen die Kondensationsprodukte von Alkylphenolen mit einer C6- bis C20-Alkylgruppe, die entweder linear oder verzweigt sein kann, mit Alkenoxiden. Bevorzugt sind Verbindungen mit ca. 5 bis 25 mol Alkenoxid pro mol Alkylphenol. Kommerziell erhältliche Tenside diesen Typs sind z.B. Igepal® CO-630, Triton® X-45, X-114, X-100 und X102, und die ®Arkopal-N-Marken der Clariant GmbH. Diese Tenside werden als Alkylphenolalkoxilate, z.B. Alkylphenolethoxilate, bezeichnet.These compounds include the condensation products of alkylphenols with a C 6 to C 20 alkyl group, which can be either linear or branched, with alkene oxides. Compounds with about 5 to 25 mol of alkene oxide per mol of alkylphenol are preferred. Commercially available surfactants of this type are, for example, Igepal® CO-630, Triton® X-45, X-114, X-100 and X102, and the ®Arkopal-N brands from Clariant GmbH. These surfactants are referred to as alkylphenol alkoxylates, for example alkylphenol ethoxylates.

    Typische Beispiele für amphotere bzw. zwitterionische Tenside sind Alkylbetaine, Alkylamidbetaine, Aminopropionate, Aminoglycinate, oder amphotere Imidazolinium-Verbindungen der Formel

    Figure 00090001
    worin R1 C8-C22-Alkyl- oder -Alkenyl, R2 Wasserstoff oder CH2CO2M, R3 CH2CH2OH oder CH2CH2OCH2CH2CO2M, R4 Wasserstoff, CH2CH2OH oder CH2CH2COOM, Z CO2M oder CH2CO2M, n 2 oder 3, bevorzugt 2, M Wasserstoff oder ein Kation wie Alkalimetall, Erdalkalimetall, Ammonium oder Alkanolammonium bedeutet.Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula
    Figure 00090001
    wherein R 1 is C 8 -C 22 alkyl or alkenyl, R 2 is hydrogen or CH 2 CO 2 M, R 3 CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CH 2 CO 2 M, R 4 is hydrogen, CH 2 CH 2 OH or CH 2 CH 2 COOM, Z CO 2 M or CH 2 CO 2 M, n 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonium or alkanolammonium.

    Bevorzugte amphotere Tenside dieser Formel sind Monocarboxylate und Dicarboxylate. Beispiele hierfür sind Cocoamphocarboxypropionat, Cocoamidocarboxypropionsäure, Cocoamphocarboxyglycinat (oder auch als Cocoamphodiacetat bezeichnet) und Cocoamphoacetat.Preferred amphoteric surfactants of this formula are monocarboxylates and Dicarboxylates. Examples include cocoamphocarboxypropionate, Cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinat (or also as Cocoamphodiacetate) and Cocoamphoacetat.

    Weitere bevorzugte amphotere Tenside sind Alkyldimethylbetaine und Alkyldipolyethoxybetaine mit einem Alkylrest mit ca. 8 bis ca. 22 Kohlenstoffatomen, der linear oder verzweigt sein kann, bevorzugt mit 8 bis 18 Kohlenstoffatomen und besonders bevorzugt mit ca. 12 bis ca. 18 Kohlenstoffatomen. Diese Verbindungen werden z.B. von der Clariant GmbH unter dem Handelsnamen ®Genagen LAB vermarktet.Further preferred amphoteric surfactants are alkyldimethylbetaines and Alkyldipolyethoxybetaines with an alkyl radical having about 8 to about 22 carbon atoms, which can be linear or branched, preferably having 8 to 18 carbon atoms and particularly preferably having about 12 to about 18 carbon atoms. These connections e.g. from Clariant GmbH under the trade name ®Genagen LAB marketed.

    Geeignete kationische Tenside sind substituierte oder unsubstituierte geradkettige oder verzweigte quartäre Ammoniumsalze vom Typ R1N(CH3)3 ⊕X⊖, R1R2N(CH3)2 ⊕X⊖, R1R2R3N(CH3)⊕X⊖ oder R1R2R3R4N⊕X⊖. Die Reste R1, R2, R3 und R4 können vorzugsweise unabhängig voneinander unsubstituiertes Alkyl mit einer Kettenlänge zwischen 8 und 24 C-Atomen, insbesondere zwischen 10 und 18 C-Atomen, Hydroxyalkyl mit ca. 1 bis ca. 4 C-Atomen, Phenyl, C2- bis C18-Alkenyl, C7- bis C24-Aralkyl, (C2H4O)xH, wobei x von ca. 1 bis ca. 3 bedeutet, ein oder mehrere Estergruppen enthaltende Alkylreste oder cyclische quartäre Ammoniumsalze sein. X ist ein geeignetes Anion.Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R 1 N (CH 3 ) 3 ⊕ X ⊖ , R 1 R 2 N (CH 3 ) 2 ⊕ X ⊖ , R 1 R 2 R 3 N (CH 3 ) ⊕ X ⊖ or R 1 R 2 R 3 R 4 N ⊕ X ⊖ . The radicals R 1 , R 2 , R 3 and R 4 can preferably independently of one another unsubstituted alkyl with a chain length between 8 and 24 carbon atoms, in particular between 10 and 18 carbon atoms, hydroxyalkyl with about 1 to about 4 carbon atoms. Atoms, phenyl, C 2 to C 18 alkenyl, C 7 to C 24 aralkyl, (C 2 H 4 O) x H, where x is from about 1 to about 3, one or more alkyl groups containing ester groups or cyclic quaternary ammonium salts. X is a suitable anion.

    Weitere Waschmittelinhaltsstoffe, die in der vorliegenden Erfindung enthalten sein können, umfassen anorganische und/oder organische Gerüststoffe, um den Härtegrad des Wassers zu mindern.Other detergent ingredients included in the present invention may include inorganic and / or organic builders to the To reduce the hardness of the water.

    Diese Gerüststoffe können mit Gewichtsanteilen von etwa 5 % bis etwa 80 % in den Wasch- und Reinigungsmittelzusammensetzungen enthalten sein. Anorganische Gerüststoffe umfassen beispielsweise Alkali-, Ammonium- und Alkanolammoniumsalze von Polyphosphaten wie etwa Tripolyphosphate, Pyrophosphate und glasartige polymere Metaphosphate, Phosphonaten, Silikaten, Carbonaten einschließlich Bicarbonate und Sesquicarbonate, Sulfaten und Aluminosilikaten.These builders can range in weight from about 5% to about 80% Detergent and cleaning agent compositions may be included. inorganic Builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.

    Beispiele für Silikatgerüststoffe sind die Alkalimetallsilikate, insbesondere diejenigen mit einem SiO2:Na2O-Verhältnis zwischen 1,6:1 und 3,2:1 sowie Schichtsilikate, beispielsweise Natriumschichtsilikate, wie beschrieben in US-4,664,839, erhältlich von Clariant GmbH unter der Marke SKS®. SKS-6® ist ein besonders bevorzugter Schichtsilikatgerüststoff.Examples of silicate builders are the alkali metal silicates, in particular those with an SiO 2 : Na 2 O ratio between 1.6: 1 and 3.2: 1, and sheet silicates, for example sodium sheet silicates, as described in US Pat. No. 4,664,839, available from Clariant GmbH under the SKS® brand. SKS-6® is a particularly preferred layered silicate builder.

    Aluminosilikatgerüststoffe sind für die vorliegende Erfindung besonders bevorzugt. Es handelt sich dabei insbesondere um Zeolithe mit der Formel Naz[(AlO2)z(SiO2)y]·xH2O, worin z und y ganze Zahlen von mindestens 6 bedeuten, das Verhältnis von z zu y zwischen 1,0 bis etwa 0,5 liegt, und x eine ganze Zahl von etwa 15 bis etwa 264 bedeutet.Aluminosilicate builders are particularly preferred for the present invention. These are in particular zeolites with the formula Na z [(AlO 2 ) z (SiO 2 ) y ] .xH 2 O, where z and y are integers of at least 6, the ratio of z to y is between 1.0 to about 0.5, and x is an integer from about 15 to about 264.

    Geeignete lonentauscher auf Aluminosilikatbasis sind im Handel erhältlich. Diese Aluminosilikate können von kristalliner oder amorpher Struktur sein, und können natürlich vorkommend oder auch synthetisch hergestellt sein. Verfahren für die Herstellung von lonentauschern auf Aluminosilikatbasis werden beschrieben in US-3,985,669 und US-4,605,509. Bevorzugte lonentauscher auf der Basis synthetischer kristalliner Aluminosilikate sind erhältlich unter der Bezeichnung Zeolith A, Zeolith P(B) (einschließlich der in EP-A-0 384 070 offenbarten) und Zeolith X. Bevorzugt sind Aluminosilikate mit einem Partikeldurchmesser zwischen 0,1 und 10 µm.Suitable ion exchangers based on aluminosilicate are commercially available. This Aluminosilicates can be crystalline or amorphous in structure and can naturally occurring or synthetically produced. Procedure for the Manufacture of ion exchangers based on aluminosilicate are described in U.S. 3,985,669 and U.S. 4,605,509. Preferred ion exchangers based Synthetic crystalline aluminosilicates are available under the name Zeolite A, Zeolite P (B) (including those disclosed in EP-A-0 384 070) and Zeolite X. Preferred are aluminosilicates with a particle diameter between 0.1 and 10 µm.

    Geeignete organische Gerüststoffe (Co-Builder) umfassen Polycarboxylverbindungen, wie beispielsweise Etherpolycarboxylate und Oxydisuccinate, wie beispielsweise in US-3,128,287 und US-3,635,830 beschrieben. Ebenfalls soll auf "TMS/TDS"-Gerüststoffe aus US-4,663,071 verwiesen werden.Suitable organic builders (co-builders) include polycarboxyl compounds, such as ether polycarboxylates and oxydisuccinates, such as for example, described in US-3,128,287 and US-3,635,830. Also on "TMS / TDS" builders can be found in US 4,663,071.

    Andere geeignete Gerüststoffe umfassen die Etherhydroxypolycarboxylate, Copolymere von Maleinsäureanhydrid mit Ethylen oder Vinylmethylether, 1,3,5-Trihydroxybenzol-2,4,6-trisulfonsäure und Carboxymethyloxybernsteinsäure, die Alkali-, Ammonium- und substituierten Ammoniumsalze von Polyessigsäuren wie z.B. Ethylendiamintetraessigsäure und Nitrilotriessigsäure, sowie Polycarbonsäuren, wie Mellithsäure, Bernsteinsäure, Oxydibernsteinsäure, Polymaleinsäure, Benzol-1,3,5-tricarbonsäure, Carboxymethyloxybernsteinsäure, sowie deren lösliche Salze.
    Wichtige organische Gerüststoffe sind auch Polycarboxylate auf Basis von Acrylsäure und Maleinsäure, wie z.B. die Sokalan CP-Marken der BASF.    Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitric acid and also polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.
    Important organic builders are also polycarboxylates based on acrylic acid and maleic acid, such as the Sokalan CP brands from BASF.

    Gerüststoffe auf Citratbasis, z.B. Zitronensäure und ihre löslichen Salze, insbesondere das Natriumsalz, sind bevorzugte Polycarbonsäuregerüststoffe, die auch in granulierten Formulierungen, insbesondere zusammen mit Zeolithen und/oder Schichtsilikaten verwendet werden können.Citrate-based builders, e.g. Citric acid and its soluble salts, especially the sodium salt, are preferred polycarboxylic acid builders that also in granulated formulations, especially together with zeolites and / or layered silicates can be used.

    Weitere geeignete Gerüststoffe sind die 3,3-Dicarboxy-4-oxa-1,6-hexandioate und die verwandten Verbindungen, die in US-4,566,984 offenbart sind.Other suitable builders are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in US 4,566,984.

    Wenn Gerüststoffe auf Phosphorbasis verwendet werden können, und insbesondere wenn Seifenstücke für die Wäsche von Hand formuliert werden sollen, können verschiedene Alkalimetallphosphate wie etwa Natriumtripolyphosphat, Natriumpyrophosphat und Natriumorthophosphat verwendet werden. Ebenfalls können Phosphonatgerüststoffe, wie Ethan-1-hydroxy-1,1-diphosphonat und andere bekannte Phosphonate wie sie beispielsweise in US-3,159,581, US-3,213,030, US-3,422,021, US-3,400,148 und US-3,422,137 offenbart sind, verwendet werden.If phosphorus-based builders can be used, and especially if soap bars for laundry are to be formulated by hand, various alkali metal phosphates such as sodium tripolyphosphate, Sodium pyrophosphate and sodium orthophosphate can be used. Likewise can phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and others known phosphonates as described, for example, in US Pat. No. 3,159,581, US Pat. No. 3,213,030, U.S. 3,422,021, U.S. 3,400,148 and U.S. 3,422,137 are used.

    Die erfindungsgemäßen Waschmittel und Wäschebehandlungsmittel können übliche Hilfsstoffe oder andere Materialien enthalten, die die Reinigungswirkung verstärken, zur Behandlung oder Pflege des zu waschenden Textilmaterials dienen oder die Gebrauchseigenschaften der Waschmittelzusammensetzung ändern.The detergents and laundry treatment agents according to the invention can be conventional Contain auxiliaries or other materials that enhance the cleaning effect, to treat or care for the textile material to be washed or the Change the usage properties of the detergent composition.

    Geeignete Hilfsmittel umfassen die in US-3,936,537 genannten Stoffe, beispielsweise Enzyme, insbesondere Proteasen, Lipasen, Cellulasen und Amylasen, Mannanasen, Enzymstabilisatoren, Schaumverstärker, Schaumbremsen, Anlauf- und/oder Korrosionsschutzmittel, Suspensionsmittel, Farbstoffe, Füllmittel, optische Aufheller, Desinfektionsmittel, Alkalien, hydrotrope Verbindungen, Antioxidantien, Parfüme, Lösungsmittel, Lösungsvermittler, Wiederablagerungsverhinderer, Dispergiermittel, Verarbeitungshilfsmittel, Weichmacher, Antistatikhilfsmittel und Soil Release Polymere wie z.B. die TexCare-Marken/ Fa. Clariant, die Repel-O-Tex Marken/ Fa. Rhodia oder Sokalan SR-100/Fa. BASF.Suitable auxiliaries include the substances mentioned in US Pat. No. 3,936,537, for example enzymes, in particular proteases, lipases, cellulases and Amylases, mannanases, enzyme stabilizers, foam boosters, foam brakes, Anti-tarnish and / or anti-corrosion agents, suspending agents, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropic compounds, Antioxidants, perfumes, solvents, solubilizers, Redeposition inhibitors, dispersants, processing aids, Plasticizers, anti-static agents and soil release polymers such as the TexCare brands / Clariant, the Repel-O-Tex brands / Rhodia or Sokalan SR-100 / company BASF.

    Die erfindungsgemäßen Wasch- und Reinigungsmittel enthaltend farbübertragungsinhibierende Farbfixiermittel können zusätzlich auch die bekannten und kommerziell erhältlichen Farbübertragungsinhibitoren enthalten.
    Beispiele für diese Farbübertragungsinhibitoren sind Polyamin-N-oxide wie etwa Poly-(4-vinylpyridin-N-oxid), z.B. Chromabond S-400, Fa. ISP; Polyvinylpyrrolidon, z.B. Sokalan HP 50/ Fa. BASF und Copolymere von N-Vinylpyrrolidon mit N-Vinylimidazol und gegebenenfalls anderen Monomeren.
    Ein wesentlicher Nachteil der bisher kommerziell erhältlichen Farbübertragungsinhibitoren ist, daß sie nicht nur den von den Textilien abgelösten und in der Waschlauge enthalten Farbstoff binden, sondern zusätzlich auch Farbstoffe von den Textilien ablösen können und damit eine Verblassung der gewaschenen Farbgewebe fördern.
    Durch die Kombination mit den farbübertragungsinhibierend wirkenden Farbfixiermitteln kann nicht nur der farbübertragungsinhibierende Effekt der bekannten Farbübertragungsinhibitoren verbessert werden, sondern es kann zusätzlich dem durch diese Produkte geförderten Verblassen der Farbgewebe entgegengewirkt werden.    The washing and cleaning agents according to the invention containing color transfer-inhibiting color fixatives can additionally also contain the known and commercially available color transfer inhibitors.
    Examples of these color transfer inhibitors are polyamine N-oxides such as poly- (4-vinylpyridine-N-oxide), for example Chromabond S-400, from ISP; Polyvinylpyrrolidone, for example Sokalan HP 50 / BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
    A major disadvantage of the dye transfer inhibitors commercially available hitherto is that they not only bind the dye detached from the textiles and contained in the wash liquor, but can also detach dyes from the textiles and thus promote fading of the washed dye fabric.
    The combination with the dye-transfer-inhibiting dye fixatives not only improves the dye-transfer-inhibiting effect of the known dye-transfer inhibitors, but also counteracts the fading of the color fabrics promoted by these products.

    Die Waschmittelzusammensetzungen der vorliegenden Erfindung können gegebenenfalls einen oder mehrere konventionelle Bleichmittel enthalten, sowie Bleichaktivatoren, Bleichkatalysatoren und geeignete Stabilisatoren. Im allgemeinen muß sichergestellt sein, daß die verwendeten Bleichmittel mit den Reinigungsmittelinhaltsstoffen verträglich sind. Konventionelle Prüfmethoden, wie etwa die Bestimmung der Bleichaktivität des fertig formulierten Reinigungsmittels in Abhängigkeit von der Lagerungszeit können für diesen Zweck verwendet werden. The detergent compositions of the present invention can optionally contain one or more conventional bleaches, and Bleach activators, bleach catalysts and suitable stabilizers. In general it must be ensured that the bleach used with the detergent ingredients are tolerated. Conventional test methods, such as the Determination of the bleaching activity of the formulated cleaning agent in Depending on the storage time can be used for this purpose.

    Die Peroxysäure kann entweder eine freie Peroxysäure sein, oder eine Kombination aus einem anorganischen Persalz, beispielsweise Natriumperborat oder Natriumpercarbonat und einem organischen Peroxysäure-Vorläufer, der zu einer Peroxysäure umgewandelt wird, wenn die Kombination des Persalzes und des Peroxysäure-Vorläufers in Wasser aufgelöst wird. Die organischen Peroxysäure-Vorläufer werden im Stand der Technik oft als Bleichaktivatoren bezeichnet. Beispiele geeigneter organischer Peroxysäuren sind offenbart in US-4,374,035, US-4,681,592, US-4,634,551, US-4,686,063, US-4,606,838 und US-4,671,891.The peroxy acid can either be a free peroxy acid or a combination from an inorganic persalt, for example sodium perborate or Sodium percarbonate and an organic peroxyacid precursor that leads to a Peroxyacid is converted when the combination of persalt and Peroxyacid precursor is dissolved in water. The organic peroxyacid precursors are often referred to as bleach activators in the prior art. Examples of suitable organic peroxyacids are disclosed in US 4,374,035, U.S. 4,681,592, U.S. 4,634,551, U.S. 4,686,063, U.S. 4,606,838 and U.S. 4,671,891.

    Beispiele für Zusammensetzungen, die zum Bleichen von Wäsche geeignet sind und die Perboratbleichmittel und Aktivatoren enthalten, werden beschrieben in US-4,412,934, US-4,536,314, US-4,681,695 und US-4,539,130.
    Beispiele für Peroxysäuren, die für die Verwendung in dieser Erfindung bevorzugt sind, umfassen die Peroxydodecandisäure (DPDA), das Nonylamid der Peroxybernsteinsäure (NAPSA), das Nonylamid der Peroxyadipinsäure (NAPAA) und Decyldiperoxybernsteinsäure (DDPSA).    Examples of compositions suitable for bleaching laundry and containing perborate bleaches and activators are described in U.S. 4,412,934, U.S. 4,536,314, U.S. 4,681,695 and U.S. 4,539,130.
    Examples of peroxyacids preferred for use in this invention include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA).

    Besonders bevorzugt werden in den erfindungsgemäßen Waschmitteln und Wäschebehandlungsmitteln Bleichsysteme auf Basis eines Persalzes wie Perboraten oder Pecarbonaten mit dem Bleichaktivator Tetraacetylethylendiamin (TAED) eingesetzt.Are particularly preferred in the detergents and Laundry treatment agents bleaching systems based on persalt such as Perborates or pecarbonates with the bleach activator tetraacetylethylenediamine (TAED) used.

    Es ist bekannt, daß viele der vorgenannten Bleichmittel, deren Zweck die oxidative Zerstörung farbiger Anschmutzungen ist, auch eine Schädigung der Textilfarbstoffe bunter Textilien bewirken.
    Durch die Verwendung der farbübertragungsinhibierenden Farbfixiermittel kann der schädigende Einfluß der Bleichmittel auf die Textilfarbstoffe reduziert werden.    It is known that many of the bleaching agents mentioned above, the purpose of which is to oxidatively destroy colored soiling, also cause damage to the textile dyes of colored textiles.
    By using the dye transfer inhibiting dye fixative, the damaging influence of the bleaching agents on the textile dyes can be reduced.

    Die beschriebenen Farbfixiermittel können auch in handelsüblichen Wäscheweichspülern für die Haushaltsanwendung eingesetzt werden. Diese enthalten im wesentlichen weichmachende Komponenten, Co-Weichmacher, Emulgatoren, Parfüme, Farbstoffe und Elektrolyte, und sind auf einen sauren pH-Wert von unterhalb 7, bevorzugt zwischen 3 und 5, eingestellt.The color fixatives described can also be found in commercially available Fabric softeners are used for household applications. This essentially contain plasticizing components, co-plasticizers, Emulsifiers, perfumes, dyes and electrolytes, and are at an acidic pH from below 7, preferably between 3 and 5.

    Als weichmachende Komponenten werden quartäre Ammoniumsalze vom Typ

    Figure 00150001
    eingesetzt, worin

    R1 =
    C8-C24 n- bzw. iso-Alkyl, bevorzugt C10-C18 n-Alkyl
    R2 =
    C1-C4-Alkyl, bevorzugt Methyl
    R3 =
    R1 oder R2
    R4 =
    R2 oder Hydroxyethyl oder Hydroxypropyl oder deren Oligomere
    X- =
    Bromid, Chlorid, Jodid, Methosulfat, Acetat, Propionat, Lactat
    sind.Quaternary ammonium salts of the type are used as plasticizing components
    Figure 00150001
    used where
    R 1 =
    C 8 -C 24 n- or iso-alkyl, preferably C 10 -C 18 n-alkyl
    R 2 =
    C 1 -C 4 alkyl, preferably methyl
    R 3 =
    R 1 or R 2
    R 4 =
    R 2 or hydroxyethyl or hydroxypropyl or their oligomers
    X - =
    Bromide, chloride, iodide, methosulfate, acetate, propionate, lactate
    are.

    Beispiele hierfür sind Distearyldimethylammoniumchlorid, Ditalgalkyldimethylammoniumchlorid, Ditalgalkylmethylhydroxypropylammoniumchlorid, Cetyltrimethylammoniumchlorid oder auch die entsprechenden Benzylderivate wie etwa Dodecyldimethylbenzylammoniumchlorid. Cyclische quartäre Ammoniumsalze, wie etwa Alkyl-Morpholinderivate können ebenfalls verwendet werden.Examples include distearyldimethylammonium chloride, ditallow alkyldimethylammonium chloride, Ditalgalkylmethylhydroxypropylammoniumchlorid, Cetyltrimethylammonium chloride or the corresponding benzyl derivatives such as such as dodecyldimethylbenzylammonium chloride. Cyclic quaternary ammonium salts, such as alkyl morpholine derivatives can also be used.

    Darüber hinaus können neben den quartären Ammoniumverbindungen Imidazolinium-Verbindungen (1) und Imidazolinderivate (2) eingesetzt werden.

    Figure 00160001
    Figure 00160002
    worin

    R =
    C8-C24 n- bzw. iso-Alkyl, bevorzugt C10-C18 n-Alkyl
    X =
    Bromid, Chlorid, Jodid, Methosulfat
    A =
    -NH-CO-, -CO-NH-, -O-CO-, -CO-O-
    ist.In addition to the quaternary ammonium compounds, imidazolinium compounds (1) and imidazoline derivatives (2) can be used.
    Figure 00160001
    Figure 00160002
    wherein
    R =
    C 8 -C 24 n- or iso-alkyl, preferably C 10 -C 18 n-alkyl
    X =
    Bromide, chloride, iodide, methosulfate
    A =
    -NH-CO-, -CO-NH-, -O-CO-, -CO-O-
    is.

    Eine besonders bevorzugte Verbindungsklasse sind die sogenannten Esterquats. Es handelt sich hierbei um Umsetzungsprodukte von Alkanolaminen und Fettsäuren, die anschließend mit üblichen Alkylierungs- oder Hydroxyalkylierungsagenzien quaterniert werden.
    Bevorzugt als Alkanolamine sind Verbindungen gemäß der Formel

    Figure 00160003
    mit

    R1 =
    C1-C3 Hydroxyalkyl, bevorzugt Hydroxyethyl und
    R2, R3 =
    R1 oder C1-C3 Alkyl, bevorzugt Methyl.
    A particularly preferred class of compounds are the so-called ester quats. These are reaction products of alkanolamines and fatty acids, which are then quaternized with customary alkylation or hydroxyalkylation agents.
    Preferred alkanolamines are compounds according to the formula
    Figure 00160003
    With
    R 1 =
    C 1 -C 3 hydroxyalkyl, preferably hydroxyethyl and
    R 2 , R 3 =
    R 1 or C 1 -C 3 alkyl, preferably methyl.

    Besonders bevorzugt sind Triethanolamin und Methyldiethanolamin.Triethanolamine and methyldiethanolamine are particularly preferred.

    Weitere besonders bevorzugte Ausgangsprodukte für Esterquats sind Aminoglycerinderivate, wie z.B. Dimethylaminopropandiol. Other particularly preferred starting products for esterquats are Aminoglycerol derivatives, e.g. Dimethylaminopropanediol.

    Alkylierungs- bzw. Hydroxyalkylierungsagenzien sind Alkylhalogenide, bevorzugt Methylchlorid, Dimethylsulfat, Ethylenoxid und Propylenoxid.Alkylation or hydroxyalkylation agents are preferred, preferably alkyl halides Methyl chloride, dimethyl sulfate, ethylene oxide and propylene oxide.

    Beispiele für Esterquats sind Verbindungen der Formeln:

    Figure 00170001
    Figure 00170002
    Figure 00170003
    wobei R-C-O abgeleitet ist von C8-C24-Fettsäuren, die gesättigt oder ungesättigt sein können. Beispiele hierfür sind Capronsäure, Caprylsäure, hydrierte oder nicht oder nur teilweise hydrierte Talgfettsäuren, Stearinsäure, Ölsäure, Linolensäure, Behensäure, Palminstearinsäure, Myristinsäure und Elaidinsäure. n liegt im Bereich von 0 bis 10, vorzugsweise 0 bis 3, besonders bevorzugt 0 bis 1.Examples of ester quats are compounds of the formulas:
    Figure 00170001
    Figure 00170002
    Figure 00170003
    where RCO is derived from C 8 -C 24 fatty acids, which can be saturated or unsaturated. Examples include caproic acid, caprylic acid, hydrogenated or not or only partially hydrogenated tallow fatty acids, stearic acid, oleic acid, linolenic acid, behenic acid, palminstearic acid, myristic acid and elaidic acid. n is in the range from 0 to 10, preferably 0 to 3, particularly preferably 0 to 1.

    Weitere bevorzugte Wäscheweichspülerrohstoffe mit denen die Farbfixiermittel kombiniert werden können sind Amido-Amine auf der Basis von beispielsweise Dialkyltriaminen und langkettigen Fettsäuren, sowie deren Oxethylate bzw. quaternierten Varianten. Diese Verbindungen besitzen folgende Struktur:

    Figure 00180001
    worin

    R1 und R2
    unabhängig voneinander C8-C24 n- bzw. iso-Alkyl, bevorzugt C10-C18 n-Alkyl,
    A
    -CO-NH- oder -NH-CO-,
    n
    1 - 3, bevorzugt 2,
    m
    1 - 5, bevorzugt 2 - 4
    bedeuten.Further preferred fabric softener raw materials with which the color fixing agents can be combined are amido amines based on, for example, dialkyltriamines and long-chain fatty acids, and their oxyethylates or quaternized variants. These connections have the following structure:
    Figure 00180001
    wherein
    R 1 and R 2
    independently of one another C 8 -C 24 n- or iso-alkyl, preferably C 10 -C 18 n-alkyl,
    A
    -CO-NH- or -NH-CO-,
    n
    1 - 3, preferably 2,
    m
    1-5, preferably 2-4
    mean.

    Durch Quaternierung der tertiären Aminogruppe kann zusätzlich ein Rest R3, welcher C1-C4-Alkyl, bevorzugt Methyl, sein kann und ein Gegenion X, welches Chlorid, Bromid, Jodid oder Methylsulfat sein kann, eingeführt werden. Amidoaminooxethylate bzw. deren quaternierten Folgeprodukte werden unter den Handelsnamen ®Varisoft 510, ®Varisoft 512, ®Rewopal V 3340 und ®Rewoquat W 222 LM angeboten.By quaternization of the tertiary amino group, a radical R 3 , which can be C 1 -C 4 -alkyl, preferably methyl, and a counterion X, which can be chloride, bromide, iodide or methyl sulfate, can additionally be introduced. Amidoaminooxethylates and their quaternized secondary products are offered under the trade names ®Varisoft 510, ®Varisoft 512, ®Rewopal V 3340 and ®Rewoquat W 222 LM.

    Die bevorzugten Anwendungskonzentrationen der Farbfixiermittel in den Weichspülerformulierungen entsprechen denen, die für Waschmittelformulierungen genannt sind.The preferred application concentrations of the color fixative in the Fabric softener formulations correspond to those for detergent formulations are mentioned.

    BeispieleExamples

    Beispiele für die in den erfindungsgemäßen Waschmitteln eingesetzten farbübertragungsinhibierenden Farbfixiermittel sind:

    Beispiel 1:
    Umsetzungsprodukt aus Diethylentriamin mit Dicyandiamid und Amidoschwefelsäure.
    Beispiel 2:
    Umsetzungsprodukt aus Dicyandiamid mit Formaldehyd und Ammoniumchlorid.
    Beispiel 3:
    Umsetzungsprodukt aus Dimethylaminopropylamin mit Epichlorhydrin.
    Examples of the color transfer inhibiting color fixing agents used in the detergents according to the invention are:
    Example 1:
    Reaction product from diethylenetriamine with dicyandiamide and amidosulfuric acid.
    Example 2:
    Reaction product from dicyandiamide with formaldehyde and ammonium chloride.
    Example 3:
    Reaction product from dimethylaminopropylamine with epichlorohydrin.

    Die farbübertragungsinhibierenden Farbfixiermittel wurden in Kombination mit Standardwaschmitteln an verschiedenen Farbgeweben auf ihren farberhaltenden Effekt hin untersucht. Gleichzeitig erfolgte die Prüfung auf eine farbübertragungsinhibierende Wirkung.The color transfer inhibiting color fixatives were used in combination with Standard detergents on different color fabrics on their color-preserving Effect examined. At the same time, the test was carried out for an ink transfer inhibitor Effect.

    Dazu wurden zu einer Waschlauge, enthaltend 6 g/l eines phosphatfreien bzw. eines phosphathaltigen Testwaschpulvers, ohne Bleichmittelzusatz (Zusammensetzung siehe Tabellen 1 und 3) und mit einem Bleichmittelzusatz (Zusammensetzung siehe Tabellen 2 und 4), jeweils 300 ppm der Farbfixiermittel gegeben und farbiges Baumwollgewebe zusammen mit weißem Baumwollgewebe gewaschen.
    Ferner wurde ein Waschversuch mit einem Flüssigwaschmittel durchgeführt.    For this purpose, 300 ppm of the color fixative were added to each of a wash liquor containing 6 g / l of a phosphate-free or a phosphate-containing test washing powder without bleach additive (composition see tables 1 and 3) and with a bleach additive (composition see tables 2 and 4) and colored Cotton fabric washed together with white cotton fabric.
    A washing test with a liquid detergent was also carried out.

    Anschließend wurden die Gewebe mit klarem Wasser gespült, getrocknet und die dL,da,db-Werte bestimmt, aus denen sich die Farbdifferenzen delta E ergeben. Zum Vergleich wurden die Gewebe mit den Testwaschmitteln ohne Zusatz der Farbfixiermittel gewaschen. Die Waschbedingungen sind in Tabelle 3 angegeben. Insgesamt wurden fünf Waschzyklen durchgeführt.The tissues were then rinsed with clear water, dried and the dL, da, determines db values from which the color differences delta E result. For comparison, the fabrics with the test detergents were added without the Color fixative washed. The washing conditions are given in Table 3. A total of five wash cycles were carried out.

    Die an dem weißen Gewebe nach der ersten Wäsche erhaltenen Werte dienen zur Quantifizierung des farbübertragungsinhibierenden Effekts.
    Die an dem farbigen Gewebe gemessenen Werte quantifizieren den erzielten Farberhalt. Zum Vergleich der farberhaltenden Wirkung der Farbfixiermittel wurde der an fünf verschiedenen Farbgeweben erhaltene durchschnittliche dE-Wert berechnet. Phosphatfreies Standardtestwaschpulver IEC-A. Lineares Alkylbenzolsulfonat (Cmittel = 11,5) 11,0 % C12-18-Alkohol * EO7 5,90 % Seife (65 % C12-18, 35 % C20-22) 4,10 % Zeolith A 36,80 % Natriumcarbonat 13,40 % Na-Salz eines Acryl- und Maleinsäure Copolymerisats (Sokalan CP5®) 5,90 % Natriumsilikat (SiO2 : NaO2 = 3,32 : 1) 3,80 % Carboxymethylcellulose 1,50 % Phosphonat ((Dequest 2066®) 3,50 % Stilbenaufheller 0,30 % Schauminhibitor (Dow Corning DC2-4248S®) 5,00 % Natriumsulfat 8,40 % Protease (Savinase 8,0®) 0,40 % Phosphatfreies Standardtestwaschpulver IEC-A mit Bleichmittel Lineares Alkylbenzolsulfonat (Cmittel = 11,5) 8,80 % C12-18-Alkohol * EO7 4,72% Seife (65 % C12-18, 35 % C20-22) 3,28 % Zeolith A 29,44 % Natriumcarbonat 10,72 % Na-Salz eines Acryl- und Maleinsäure Copolymerisats (Sokalan CP5®) 4,72 % Natriumsilikat (SiO2 : NaO2 = 3,32 : 1) 3,04 % Carboxymethylcellulose 1,20 % Phosphonat ((Dequest 2066®) 2,80 % Stilbenaufheller 0,24 % Schauminhibitor (Dow Corning DC2-4248S®) 4,00 % Natriumsulfat 6,72 % Protease (Savinase 8,0®) 0,32 % TAED (Peractive P®) 5,00 % Natriumpercarbonat 15,00 % Phosphathaltiges Standardtestwaschpulver IEC-B Lineares Alkylbenzolsulfonat (Cmittel = 11,5) 8,00 % C12-18-Alkohol * EO14 2,90 % Seife (13-25 % C12-16, 74-87 % C18-22) 3,50 % Natriumtripolyphosphat 43,70 % Natriumsilikat (SiO2 : NaO2 = 3,3 : 1) 7,50 % Magnesiumsilikat 1,90 % Carboxymethylcellulose 1,25 % EDTA 0,25 % Stilbenaufheller 0,25 % Natriumsulfat 21,00 % Wasser 9,75 % Phosphathaltiges Standardtestwaschpulver IEC-B mit Bleichmittel Lineares Alkylbenzolsulfonat (Cmittel = 11,5) 6,40 % C12-18-Alkohol * EO14 2,30 % Seife (13-25 % C12-16, 74-87 % C18-22) 2,80 % Natriumtripolyphosphat 35,00 % Natriumsilikat (SiO2 : NaO2 = 3,3 : 1) 6,00 % Magnesiumsilikat 1,50 % Carboxymethylcellulose 1,00 % EDTA 0,20 % Stilbenaufheller 0,20 % Natriumsulfat 16,80 % Wasser 7,80 % TAED (Peractive P®) 5,00 % Natriumpercarbonat 15,00 % Flüssigwaschmittel C14/C15-Oxoalkoholpolyglykolether mit 8 EO (Genapol OA-080®) 12,0% Fettsäuremischung (Prifac 7976®) 14,0% Kaliumhydroxid (85 %ig) 2,6% Triethanolamin 2,0% 1,2 Propylenglykol 5,0% Wasser 35,4% Tri-Natriumcitrat-2-hydrat 5,0% Sekundäres Alkansufonat (Hostapur SAS 60®) 17,0% Phosphonat (Dequest 2066®) 4,0% Ethanol 3,0% Waschbedingungen Waschmaschine: Linitest Waschmittelkonzentration: 6 g/l Additivkonzentration: 300 ppm Wasserhärte: 15° dH Flottenverhältnis: 1 : 40 Waschtemperatur: 60°C Waschzeit: 30 Min.     The values obtained on the white fabric after the first wash serve to quantify the color transfer inhibiting effect.
    The values measured on the colored fabric quantify the color retention achieved. To compare the color-preserving effect of the color fixative, the average dE value obtained on five different color fabrics was calculated. Standard phosphate-free washing powder IEC-A. Linear alkyl benzene sulfonate (C medium = 11.5) 11.0% C 12-18 alcohol * EO 7 5.90% Soap (65% C 12-18 , 35% C 20-22 ) 4.10% Zeolite A 36.80% sodium 13.40% Na salt of an acrylic and maleic acid copolymer (Sokalan CP5®) 5.90% Sodium silicate (SiO 2 : NaO 2 = 3.32: 1) 3.80% carboxymethylcellulose 1.50% Phosphonate ((Dequest 2066®) 3.50% stilbene 0.30% Foam inhibitor (Dow Corning DC2-4248S®) 5.00% sodium sulphate 8.40% Protease (Savinase 8.0®) 0.40% Standard phosphate-free washing powder IEC-A with bleach Linear alkyl benzene sulfonate (C medium = 11.5) 8.80% C 12-18 alcohol * EO 7 4.72% Soap (65% C 12-18 , 35% C 20-22 ) 3.28% Zeolite A 29.44% sodium 10.72% Na salt of an acrylic and maleic acid copolymer (Sokalan CP5®) 4.72% Sodium silicate (SiO 2 : NaO 2 = 3.32: 1) 3.04% carboxymethylcellulose 1.20% Phosphonate ((Dequest 2066®) 2.80% stilbene 0.24% Foam inhibitor (Dow Corning DC2-4248S®) 4.00% sodium sulphate 6.72% Protease (Savinase 8.0®) 0.32% TAED (Peractive P®) 5.00% Sodium percarbonate 15.00% Standard test washing powder containing phosphate IEC-B Linear alkyl benzene sulfonate (C medium = 11.5) 8.00% C 12-18 alcohol * EO 14 2.90% Soap (13-25% C 12-16 , 74-87% C 18-22 ) 3.50% sodium tripolyphosphate 43.70% Sodium silicate (SiO 2 : NaO 2 = 3.3: 1) 7.50% magnesium silicate 1.90% carboxymethylcellulose 1.25% EDTA 0.25% stilbene 0.25% sodium sulphate 21.00% water 9.75% Standard test washing powder containing phosphate IEC-B with bleach Linear alkyl benzene sulfonate (C medium = 11.5) 6.40% C 12-18 alcohol * EO 14 2.30% Soap (13-25% C 12-16 , 74-87% C 18-22 ) 2.80% sodium tripolyphosphate 35.00% Sodium silicate (SiO 2 : NaO 2 = 3.3: 1) 6.00% magnesium silicate 1.50% carboxymethylcellulose 1.00% EDTA 0.20% stilbene 0.20% sodium sulphate 16.80% water 7.80% TAED (Peractive P®) 5.00% Sodium percarbonate 15.00% liquid detergent C 14 / C 15 oxo alcohol polyglycol ether with 8 EO (Genapol OA-080®) 12.0% Fatty acid mixture (Prifac 7976®) 14.0% Potassium hydroxide (85%) 2.6% triethanolamine 2.0% 1,2 propylene glycol 5.0% water 35.4% Tri-sodium citrate-2 hydrate 5.0% Secondary alkane sulfonate (Hostapur SAS 60®) 17.0% Phosphonate (Dequest 2066®) 4.0% ethanol 3.0% washing conditions Washing machine: Linitest Detergent concentration: 6 g / l Additive concentration: 300 ppm Water hardness: 15 ° dH Liquor ratio: 1:40 Washing temperature: 60 ° C Washing time: 30 min.

    In den Tabellen 7 bis 11 sind die durchschnittlichen delta E-Werte angegeben, die an rotem, blauem, grünem, violetten und schwarzen Farbgeweben erhalten wurden. Je niedriger diese Werte sind, desto besser ist der mit den Farbfixiermitteln in den erfindungsgemäßen Waschmitteln erzielte Farberhalt. Farberhaltende Wirkung in Kombination mit dem phosphatfreien Testwaschpulver IEC-A. Waschpulver/Additiv Ødelta E-Werte Farbdifferenzen zum ungewaschenen Gewebe nach fünf Wäschen IEC-A ohne Additiv 7,6 + Bsp. 1 5,3 + Bsp. 2 3,9 + Bsp. 3 4,7 Farberhaltende Wirkung in Kombination mit dem phosphatfreien Testwaschpulver IEC-A mit Bleichmittelzusatz Waschpulver/Additiv Ødelta E-Werte Farbdifferenzen zum ungewaschenen Gewebe nach fünf Wäschen IEC-A ohne Additiv 7,4 + Bsp. 1 6,4 + Bsp. 2 4,6 + Bsp.3 5,5 Farberhaltende Wirkung in Kombination mit dem phosphathaltigen Waschpulver IEC-B Waschpulver/Additiv Ødelta E-Werte Farbdifferenzen zum ungewaschenen Gewebe nach fünf Wäschen IEC-B ohne Additiv 6,1 + Bsp. 1 4,9 + Bsp. 2 3,9 + Bsp. 3 2,9 Farberhaltende Wirkung in Kombination mit dem phosphathaltigen Waschpulver IEC-B mit Bleichmittelzusatz Waschpulver/Additiv Ødelta E-Werte Farbdifferenzen zum ungewaschenen Gewebe nach fünf Wäschen IEC-B ohne Additiv 6,6 + Bsp. 1 5,6 + Bsp. 2 4,5 + Bsp. 3 3,6 Farberhaltende Wirkung in Kombination mit einem Flüssigwaschmittel Waschmittel/Additiv Ødelta E-Werte Farbdifferenzen zum ungewaschenen Gewebe nach fünf Wäschen Flüssigwaschmittel ohne Additiv 3,9 + Bsp. 1 2,9 + Bsp. 2 2,0 + Bsp. 3 0,6 Tables 7 to 11 show the average delta E values obtained on red, blue, green, violet and black colored fabrics. The lower these values are, the better the color retention achieved with the color fixing agents in the detergents according to the invention. Color-preserving effect in combination with the phosphate-free test washing powder IEC-A. Detergent / additive Ødelta E values Color differences to the unwashed fabric after five washes IEC-A without additive 7.6 + Ex. 1 5.3 + Ex. 2 3.9 + Ex. 3 4.7 Color-preserving effect in combination with the phosphate-free test washing powder IEC-A with bleach additive Detergent / additive Ødelta E values Color differences to the unwashed fabric after five washes IEC-A without additive 7.4 + Ex. 1 6.4 + Ex. 2 4.6 + Example 3 5.5 Color-preserving effect in combination with the phosphate-containing washing powder IEC-B Detergent / additive Ødelta E values Color differences to the unwashed fabric after five washes IEC-B without additive 6.1 + Ex. 1 4.9 + Ex. 2 3.9 + Ex. 3 2.9 Color preserving effect in combination with the phosphate-containing washing powder IEC-B with bleach additive Detergent / additive Ødelta E values Color differences to the unwashed fabric after five washes IEC-B without additive 6.6 + Ex. 1 5.6 + Ex. 2 4.5 + Ex. 3 3.6 Color preserving effect in combination with a liquid detergent Detergent / additive Ødelta E values Color differences to the unwashed fabric after five washes Liquid detergent without additive 3.9 + Ex. 1 2.9 + Ex. 2 2.0 + Ex. 3 0.6

    In den folgenden Beispielen ist die farbübertragungsinhibierende Wirkung der erfindungsgemäßen Waschmittel enthaltend die farbübertragungsinhibierend wirkenden Farbfixiermittel an den zusammen mit den Farbgeweben gewaschenen Weißgeweben dargestellt.
    Je niedriger die gemessenen dE-Werte des weißen Gewebes, desto geringer dessen Anfärbung durch den ausgebluteten Farbstoff. Farbübertragungsinhibierende Wirkung in Kombination mit dem phosphatfreien Testwaschpulver IEC-A an violettem Testgewebe. Waschpulver/Additiv delta E-Werte des weißen Testgewebes gewaschen zusammen mit violettem Farbgewebe nach einer Wäsche IEC-A ohne Additiv 36,9 + Bsp. 1 12,7 + Bsp. 2 15,2 + Bsp. 3 14,6 Farbübertragungsinhibierende Wirkung in Kombination mit dem phosphatfreien Testwaschpulver IEC-A an blauem Testgewebe. Waschpulver/Additiv delta E-Werte des weißen Testgewebes gewaschen zusammen mit blauem Farbgewebe nach einer Wäsche IEC-A ohne Additiv 32,6 + Bsp. 1 8,7 + Bsp. 2 18,9 + Bsp. 3 14,7 Farbübertragungsinhibierende Wirkung von Beispiel 1 in Kombination mit dem phosphatfreien Testwaschpulver IEC-A an weiteren Farbtestgeweben. Waschpulver/Additiv delta E-Werte des weißen Testgewebes gewaschen zusammen mit weiteren Farbgeweben nach einer Wäsche. schwarz grün rot IEC-A ohne Additiv 35,1 22,0 37,5 + Bsp. 1 15,1 10,9 28,3     The following examples show the color transfer-inhibiting effect of the detergents according to the invention containing the color transfer-inhibiting color fixatives on the white fabrics washed together with the color fabrics.
    The lower the measured dE values of the white tissue, the less its staining due to the bled-out dye. Color transfer inhibiting effect in combination with the phosphate-free test washing powder IEC-A on violet test fabric. Detergent / additive delta E values of the white test fabric washed together with violet color fabric after a wash IEC-A without additive 36.9 + Ex. 1 12.7 + Ex. 2 15.2 + Ex. 3 14.6 Color transfer inhibiting effect in combination with the phosphate-free test washing powder IEC-A on blue test fabric. Detergent / additive delta E values of the white test fabric washed together with blue color fabric after a wash IEC-A without additive 32.6 + Ex. 1 8.7 + Ex. 2 18.9 + Ex. 3 14.7 Color transfer inhibiting effect of Example 1 in combination with the phosphate-free test washing powder IEC-A on other color test fabrics. Detergent / additive delta E values of the white test fabric washed together with other color fabrics after a wash. black green red IEC-A without additive 35.1 22.0 37.5 + Ex. 1 15.1 10.9 28.3

    Claims (7)

    Waschmittel enthaltend farbübertragungsinhibierende Farbfixiermittel, wobei diese farbübertragungsinhibierenden Farbfixiermittel erhalten werden durch Umsetzung von a) Polyaminen mit Cyanamiden und Amidoschwefelsäure
    oder     b) Cyanamiden mit Aldehyden und Ammoniumsalzen
    oder     c) Aminen mit Epichlorhydrin.     Detergents containing color transfer-inhibiting color fixatives, these color transfer-inhibiting color fixatives being obtained by reacting a) Polyamines with cyanamides and amidosulfuric acid
    or     b) cyanamides with aldehydes and ammonium salts
    or     c) amines with epichlorohydrin.     Waschmittel gemäß Anspruch 1 enthaltend anionische Tenside, nichtionische Tenside und anorganische oder organische Builder.Detergent according to claim 1 containing anionic surfactants, nonionic Surfactants and inorganic or organic builders. Waschmittel gemäß Anspruch 1 enthaltend Farbübertragungsinhibitoren.Detergent according to claim 1 containing color transfer inhibitors. Waschmittel gemäß Anspruch 1 enthaltend kationische Tenside.Detergent according to claim 1 containing cationic surfactants. Waschmittel gemäß Anspruch 1 enthaltend Soil Release Polymere.Detergent according to claim 1 containing soil release polymers. Waschmittel gemäß Anspruch 1 enthaltend Cellulasen.Detergent according to claim 1 containing cellulases. Waschmittel gemäß Anspruch 1 enthaltend Bleichmittel.Detergent according to claim 1 containing bleach.
    EP02004064A 2001-03-03 2002-02-23 Washing agent and laundry treatment agent comprising one or more dye transfer inhibiting dye fixatives Expired - Lifetime EP1236793B1 (en)

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    DE10110338 2001-03-03
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    DE10150724A DE10150724A1 (en) 2001-03-03 2001-10-13 Washing agents such as detergents contain dye transfer inhibitors which are polyamine/cyanamide/amidosulfuric acid, cyanamide/aldehyde/ammonium salt or amine/epichlorhydrin reaction products
    US10/085,712 US6858570B2 (en) 2001-03-03 2002-02-28 Laundry detergents and laundry treatment compositions comprising one or more dye-transfer-inhibiting dye fixatives

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    ATE378392T1 (en) 2007-11-15
    DE50211176D1 (en) 2007-12-27
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    EP1236793B1 (en) 2007-11-14
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    US20030171249A1 (en) 2003-09-11

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