EP1236793A2 - Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel - Google Patents
Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel Download PDFInfo
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- 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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- Prior art keywords
- alkyl
- color
- acid
- dye
- detergent
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
Description
oder
oder
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.
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.
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.
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.
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.
Folgende Typen von anionischen Tensiden sind besonders bevorzugt: Alkylestersulfonate, Alkylsulfate, Alkylethersulfate, Alkylbenzolsulfonate, Alkansulfonate und Seifen, wie im folgenden beschrieben.
Die Herstellung von primärer Alkansulfonsäure, aus der die als Tensid wirksamen entsprechenden Sulfonate erhalten werden, ist z.B. in EP 854 136-A1 beschrieben.
Für milde Tensidsysteme ist Magnesium als Kation bevorzugt, für Standardwaschanwendungen dagegen Natrium. Gleiches gilt für Alkenylbenzolsulfonate.
Weitere Beispiele sind in "Surface Active Agents and Detergents" (Vol. I und II, Schwartz, Perry und Berch) beschrieben.
Wichtige organische Gerüststoffe sind auch Polycarboxylate auf Basis von Acrylsäure und Maleinsäure, wie z.B. die Sokalan CP-Marken der BASF.
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.
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).
Durch die Verwendung der farbübertragungsinhibierenden Farbfixiermittel kann der schädigende Einfluß der Bleichmittel auf die Textilfarbstoffe reduziert werden.
- 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
- 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-
Bevorzugt als Alkanolamine sind Verbindungen gemäß der Formel mit
- R1 =
- C1-C3 Hydroxyalkyl, bevorzugt Hydroxyethyl und
- R2, R3 =
- R1 oder C1-C3 Alkyl, bevorzugt Methyl.
- 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
- 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.
Ferner wurde ein Waschversuch mit einem Flüssigwaschmittel durchgeführt.
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. |
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 |
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 |
Claims (7)
- Waschmittel enthaltend farbübertragungsinhibierende Farbfixiermittel, wobei diese farbübertragungsinhibierenden Farbfixiermittel erhalten werden durch Umsetzung vona) Polyaminen mit Cyanamiden und Amidoschwefelsäure
oderb) Cyanamiden mit Aldehyden und Ammoniumsalzen
oderc) Aminen mit Epichlorhydrin. - Waschmittel gemäß Anspruch 1 enthaltend anionische Tenside, nichtionische Tenside und anorganische oder organische Builder.
- Waschmittel gemäß Anspruch 1 enthaltend Farbübertragungsinhibitoren.
- Waschmittel gemäß Anspruch 1 enthaltend kationische Tenside.
- Waschmittel gemäß Anspruch 1 enthaltend Soil Release Polymere.
- Waschmittel gemäß Anspruch 1 enthaltend Cellulasen.
- Waschmittel gemäß Anspruch 1 enthaltend Bleichmittel.
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DE10150724A DE10150724A1 (de) | 2001-03-03 | 2001-10-13 | Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel |
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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-
2002
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- 2002-02-23 EP EP02004064A patent/EP1236793B1/de not_active Expired - Lifetime
- 2002-02-23 PT PT02004064T patent/PT1236793E/pt unknown
- 2002-02-23 DE DE50211176T patent/DE50211176D1/de not_active Expired - Lifetime
- 2002-02-23 ES ES02004064T patent/ES2294053T3/es not_active Expired - Lifetime
- 2002-02-28 US US10/085,712 patent/US6858570B2/en not_active Expired - Lifetime
- 2002-03-01 JP JP2002056352A patent/JP4315634B2/ja not_active Expired - Fee Related
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005097959A1 (de) * | 2004-04-08 | 2005-10-20 | Clariant Produkte (Deutschland) Gmbh | Wasch- und reinigungsmittel enthaltend farbfixiermittel und soil release polymere |
WO2006027203A1 (de) * | 2004-09-10 | 2006-03-16 | Clariant Produkte (Deutschland) Gmbh | Flüssigwaschmittel enthaltend farbfixiermittel |
US7541326B2 (en) | 2004-09-10 | 2009-06-02 | Clariant Produkte (Deutschland) Gmbh | Liquid washing agent containing a color fixing agent |
WO2006042717A1 (de) * | 2004-10-20 | 2006-04-27 | Clariant Produkte (Deutschland) Gmbh | Flüssigwaschmittel anthaltend sekundäres alkansulfonat und farbfixiermittel |
WO2006042716A1 (de) * | 2004-10-20 | 2006-04-27 | Clariant Produkte (Deutschland) Gmbh | Flüssigwaschmittel enthaltend anionische tenside und farbfixiermittel |
US7544652B2 (en) | 2004-10-20 | 2009-06-09 | Clariant Produkts (Deutschland) Gmbh | Liquid detergent comprising anionic surfactants and colour fixing agent |
WO2006045482A1 (de) * | 2004-10-23 | 2006-05-04 | Clariant Produkte (Deutschland) Gmbh | Flüssigwaschmittel enthaltend farbfixiermittel |
WO2006045481A1 (de) * | 2004-10-23 | 2006-05-04 | Clariant Produkte (Deutschland) Gmbh | Flüssigwaschmittel enthalthend farbfixiermitteln |
US7541327B2 (en) | 2004-10-23 | 2009-06-02 | Clariant Produkte (Deutschland) Gmbh | Liquid detergents containing colour fixing agents |
US7585831B2 (en) | 2004-10-23 | 2009-09-08 | Clariant Produkte (Deutschland) Gmbh | Liquid detergent comprising a dye fixing agent |
WO2006100246A1 (de) * | 2005-03-22 | 2006-09-28 | Basf Aktiengesellschaft | Verwendung von kationischen polykondensationsprodukten als farbfixierender und/oder farbübertragungsinhibierender zusatz zu waschmitteln und wäschenachbehandlungsmitteln |
US7919451B2 (en) | 2005-03-22 | 2011-04-05 | Basf Aktiengesellschaft | Use of cationic polycondensation products as additives for fixing colours and/or inhibiting the running of colours, for washing products and washing aftertreatment products |
Also Published As
Publication number | Publication date |
---|---|
EP1236793A3 (de) | 2003-09-03 |
US20030171249A1 (en) | 2003-09-11 |
JP2002338995A (ja) | 2002-11-27 |
US6858570B2 (en) | 2005-02-22 |
JP4315634B2 (ja) | 2009-08-19 |
PT1236793E (pt) | 2008-02-12 |
EP1236793B1 (de) | 2007-11-14 |
DE10150724A1 (de) | 2003-04-17 |
DE50211176D1 (de) | 2007-12-27 |
ES2294053T3 (es) | 2008-04-01 |
ATE378392T1 (de) | 2007-11-15 |
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