EP0587549B1 - Compositions pour éviter le transfert de colorant, comprenant des agents de blanchiment - Google Patents

Compositions pour éviter le transfert de colorant, comprenant des agents de blanchiment Download PDF

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Publication number
EP0587549B1
EP0587549B1 EP19930870105 EP93870105A EP0587549B1 EP 0587549 B1 EP0587549 B1 EP 0587549B1 EP 19930870105 EP19930870105 EP 19930870105 EP 93870105 A EP93870105 A EP 93870105A EP 0587549 B1 EP0587549 B1 EP 0587549B1
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EP
European Patent Office
Prior art keywords
group
dye transfer
composition according
transfer inhibiting
inhibiting composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP19930870105
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German (de)
English (en)
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EP0587549A1 (fr
Inventor
Abdennaceur Fredj
James Pyott Johnston
Christiaan Arthur Kamiel Thoen
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Priority claimed from EP19920870181 external-priority patent/EP0596184B1/fr
Priority claimed from EP93201198A external-priority patent/EP0579295B1/fr
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to ES93870109T priority Critical patent/ES2125970T3/es
Priority to DE1993624422 priority patent/DE69324422T2/de
Priority to EP19930870105 priority patent/EP0587549B1/fr
Priority to DE1993622449 priority patent/DE69322449T2/de
Priority to ES93870105T priority patent/ES2132210T3/es
Priority to CA002140287A priority patent/CA2140287C/fr
Priority to PCT/US1993/006224 priority patent/WO1994002581A1/fr
Priority to JP50448494A priority patent/JP3892033B2/ja
Priority to US08/373,197 priority patent/US5478489A/en
Priority to TR00616/93A priority patent/TR28340A/xx
Priority to CN93116491A priority patent/CN1040656C/zh
Priority to MX9304299A priority patent/MX9304299A/es
Priority to CN 93116770 priority patent/CN1047623C/zh
Priority to AU45457/93A priority patent/AU4545793A/en
Publication of EP0587549A1 publication Critical patent/EP0587549A1/fr
Publication of EP0587549B1 publication Critical patent/EP0587549B1/fr
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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
    • C11D3/3947—Liquid 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
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing. More in particular, this invention relates to dye transfer inhibiting compositions comprising polyamine N-oxide containing polymers and bleaching agents.
  • Bleaching agents have been commonly used in detergent compositions to assist in stain removal, as well as for whitening of fabrics. In general, bleaches remove soil and colored stains from fabrics by oxidation to make the soil or stain more soluble, and thus more easily to remove it. Bleaches have also been used to whiten light colored fabrics that have suffered from yellowing over time and use.
  • the relative ability of the bleaching agent to meet various performance criteria is among others depending on the presence of adjunct detergent ingredients. As a consequence, the detergent formulator is faced with a difficult task of providing detergent compositions which have an excellent overall performance.
  • adjunct detergent ingredients that is added to detergent compositions are dye transfer inhibiting polymers.
  • Said polymers are added to detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto other fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
  • Polymers have been used within detergent compositions to inhibit dye transfer.
  • EP-A-135 217 discloses water-soluble ethoxylated amine oxides selected from ethoxylated monoamine oxides, ethoxylated diamine oxides, ethoxylated polyamine oxides and/or ethoxylated amine oxide polymers, having clay soil removal/antiredeposition properties useful in detergent compositions.
  • polyamine N-oxide containing polymers are very compatible with bleaching agents.
  • dye transfer inhibiting performance of the polyamine N-oxide containing polymers has been increased in the presence of bleaching agents.
  • a process is also provided for laundering operations involving colored fabrics.
  • the present invention relates to inhibiting dye transfer compositions comprising
  • the present invention relates to the use of
  • compositions of the present invention comprise as an essential element polyamine N-oxide containing polymers which contain units having the following structure formula : wherein
  • the N-O group can be represented by the following general structures : wherein
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.
  • Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R groups. Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • the amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000.
  • the amount of amine oxide groups present in the polyamine N-oxide containing polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation.
  • the ratio of amine to amine N-oxide is from 2:3 to 1:1,000,000. More preferably from 1:4 to 1:1,000,000, most preferably from 1:7 to 1:1,000,000.
  • the polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • the polyamine N-oxide containing polymer can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight of the polyamine N-oxide containing polymer is within the range of 500 to 1,000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • the polyamine N-oxide containing polymers of the present invention are typically present from 0.001% to 10%, more preferably from 0.01% to 2%, most preferred from 0.05% to 1% by weight of the dye transfer inhibiting composition.
  • the present compositions are conveniently used as additives to conventional detergent compositions for use in laundry operations.
  • the present invention also encompasses dye transfer inhibiting compositions which will contain detergent ingredients and thus serve as detergent compositions.
  • the production of the polyamine-N-oxide containing polymers may be accomplished by polymerizing the amine monomer and oxidizing the resultant polymer with a suitable oxidizing agent, or the amine oxide monomer may itself be polymerized to obtain the polyamine N-oxide.
  • polyamine N-oxide containing polymers can be exemplified by the synthesis of polyvinyl-pyridine N-oxide.
  • Poly-4-vinylpyridine ex Polysciences (mw. 50,000, 5.0 g., 0.0475 mole) was predissolved in 50 ml acetic acid and treated with a peracetic acid solution (25 g of glacial acetic acid, 6.4 g of a 30% vol. solution of H 2 O 2 , and a few drops of H 2 SO 4 give 0.0523 mols of peracetic acid) via a pipette. The mixture was stirred over 30 minutes at ambient temperature (32°C).
  • the mixture was then heated to 80-85°C using an oil bath for 3 hours before allowing to stand overnight.
  • the polymer solution then obtained is mixed with 11 of acetone under agitation.
  • the resulting yellow brown viscous syrup formed on the bottom is washed again with 11 of acetone to yield a pale crystalline solid.
  • the solid was filtered off by gravity, washed with acetone and then dried over P 2 O 5 .
  • the amine : amine N-oxide ratio of this polymer is 1:4 (determined by NMR).
  • the detergent compositions hereof contain oxygen bleaching agent components.
  • These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators.
  • bleaching compounds When present bleaching compounds will typically be present at levels of from 1% to 10%, of the detergent composition. In general, bleaching compounds are optional components in non-liquid formulations, e.g. granular detergents. If present, the amount of bleach activators will typically be from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition.
  • the bleaching agent component for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.
  • this invention further provides a method for cleaning fabrics, fibers, textiles, at temperatures below 50°C, especially below 40°C, with a detergent composition containing polyamine N-oxide containing polymers, optional auxiliary detersive surfactants, optional detersive adjunct ingredients, and a bleaching agent.
  • a detergent composition containing polyamine N-oxide containing polymers, optional auxiliary detersive surfactants, optional detersive adjunct ingredients, and a bleaching agent.
  • the bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.
  • oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
  • bleaching agents that can be used encompasses the halogen bleaching agents.
  • hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.
  • the bleaches suitable for the present invention include peroxygen bleaches.
  • suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates.
  • Preferred bleaches are percarbonates and perborates.
  • the hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP-A-120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP-A-120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 0 537 381 filed October 9, 1991.
  • peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
  • Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718.
  • detergent compositions will contain 0.025% to 1.25%, by weight, of sulfonated zinc phthalocyanine.
  • a wide range of surfactants can be used in the detergent compositions.
  • anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C 12 -C 18 fatty source preferably from a C 16 -C 18 fatty source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulphate surfactants are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
  • alkyl sulphates herein are tallow alkyl sulphate, coconut alkyl sulphate, and C 14-15 alkyl sulphates.
  • the cation in each instance is again an alkali metal cation, preferably sodium.
  • Nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophiliclipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophiliclipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C 9 -C 15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 14 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C 12 -C 14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula wherein R 1 is H, or R 1 is C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C 11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • phosphate builders can also be used herein.
  • Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2 O 5 ).
  • Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylate cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cistetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.
  • a suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na 2 EDDS and Na 4 EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg 2 EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Preferred builder systems for use in granular compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a water-soluble carboxylate chelating agent such as citric acid.
  • builder materials that can form part of the builder system for use in granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amiono polyalkylene phosphonates and amino polycarboxylates.
  • suitable water-soluble organic salts are the homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
  • detergent ingredients that can be included are detersive enzymes which can be included in the detergent formulations for a wide variety of purposes including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Enzymes are normally incorporated at levels sufficient to provide up to 5 mg by weight, more typically 0.05 mg to 3 mg, of active enzyme per gram of the composition.
  • proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms.
  • proteases suitable for removing protein-based stains that are commercially available include those sold under the tradenames Alcalase , Savinase and Esperase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands) and FN-base by Genencor, Optimase and Opticlean by MKC.
  • Protease A is described in European Patent Application 130,756.
  • Protease B is described in European Patent Application No. 0 251 446.
  • Amylases include, for example, amylases obtained from a special strain of B.licheniforms, described in more detail in British Patent Specification No. 1,296,839 (Novo).
  • Amylolytic proteins include, for example, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) and Termamyl (Novo Industries).
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2,075,028 ; GB-A-2,095,275 and DE-OS-2,247,832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
  • Especially suitable cellulase are the cellulase having color care benefits.
  • Examples of such cellulases are cellulase described in European patent application No. 0 495 257, filed November 6, 1991 Carezyme (Novo).
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunoligical cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057.
  • This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • Especially suitable Lipase are lipase such as M1 Lipase (Ibis) and Lipolase (Novo).
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes of pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT Internation Application WO 89/099813 and in European Patent application EP No. 0 540 784, filed on November 6, 1991.
  • an enzyme stabilization system is preferably utilized.
  • Enzyme stabilization techniques for aqueous detergent compositions are well known in the art.
  • one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate.
  • Calcium ions can be used in combination with short chain carboxylic acid salts, preferably formates. See, for example, U.S. patent 4,318,818. It has also been proposed to use polyols like glycerol and sorbitol.
  • Alkoxy-alcohols dialkylglycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (e.g., such as diethanolamine, triethanolamine or di-isopropanolamine), and boric acid or alkali metal borate.
  • Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. patent 4,261,868, U.S. Patent 3,600,319, and European Patent Application Publication No. 0 199 405. Non-boric acid and borate stabilizers are preferred.
  • Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319 and 3,519,570.
  • Suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application No. 0 553 607 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • Especially preferred detergent ingredients are combinations with technologies which also provide a type of color care benefit. Examples of these technologies are polyvinylpyrrolidone polymers and other polymers which have dye transfer inhibiting properties.
  • Other examples are cellulase and/or peroxidases and/or metallo catalysts for color maintance rejuvenation. Such metallo catalysts are described in copending European Patent Application No. 0 596 184.
  • the polyamine-N-oxide containing polymers eliminate or reduce the deposition of the metallo-catalyst onto the fabrics resulting in improved whiteness benefit.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DT 2 646 126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer.
  • Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-alcanols are 2-butyl-octanol which are commercially available under the trade name Isofol 12 R.
  • Such suds suppressor system are described in Copending European Patent application No. 0 593 841 filed 10 November, 1992.
  • compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil R .
  • the suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • detergent compositions may be employed, such as soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and/or encapsulated or more encapsulated perfumes.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include the polyacrylates and maleic anhydrideacrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s-triazin-6-ylamino)stilbene-2:2'-disulphonate, disodium 4,-4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2'-disulphonate, disodium 4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, monosodium 4',4"-bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'-disulphonate,
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033.
  • a particular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH 3 (PEG) 43 ) 0.75 (POH) 0.25 [T-PO) 2.8 (T-PEG) 0.4 ]T(POH) 0.25 ((PEG) 43 CH 3 ) 0.75 where PEG is -(OC 2 H 4 )O-,PO is (OC 3 H 6 O) and T is (pCOC 6 H 4 CO).
  • modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
  • the target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups.
  • some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
  • the selected polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol, about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000.
  • the polyesters and their method of preparation are described in detail in EPA 311 342.
  • the detergent compositions according to the invention can be in liquid, paste, gels or granular forms.
  • Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l; in such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
  • liquid compositions according to the present invention can also be in "concentrated form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water,compared to conventional liquid detergents.
  • the water content of the concentrated liquid detergent is less than 30%, more preferably less than 20%, most preferably less than 10% by weight of the detergent compositions.
  • Other examples of liquid compositions are anhydrous compositions containing substantially no water. Both aqueous and non-aqueous liquid compositions can be structured or non-structured.
  • the present invention also relates to a process for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
  • the process comprises contacting fabrics with a laundering solution as hereinbefore described.
  • the process of the invention is conveniently carried out in the course of the washing process.
  • the washing process is preferably carried out at 5 °C to 75 °C, especially 20 to 60, but the polymers are effective at up to 95 °C and higher temperatures.
  • the pH of the treatment solution is preferably from 7 to 11, especially from 7.5 to 10.5.
  • the process and compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the detergent compositions according to the present invention include compositions which are to be used for cleaning substrates, such as fabrics, fibers, hard surfaces, for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non automatic dishwashing compositions.
  • compositions of the present invention are meant to exemplify compositions of the present invention , but are not necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.
  • a granular detergent composition according to the present invention is prepared, having the following compositions : % by weight of the total detergent composition
  • Dispersant 0.07 Silicone fluid 0.80 Trisodium citrate 14.00 Citric acid 3.00 Zeolite 32.50
  • the extent of dye transfer from different colored fabrics was studied using a launder-o-meter test that simulates a 30 min wash cycle.
  • the launder-o-meter beaker contains 200 ml of a detergent solution, a 10cmx10cm piece of the colored fabric and a multifiber swatch which is used as a pick-up tracer for the bleeding dye.
  • the multifiber swatch consists of 6 pieces (1.5cmx5cm each) of different material (polyacetate, cotton, polyamide, polyester, wool and orlon) which are sewn together.
  • the extent of dye transfer is assessed by a Hunter Colour measurement.
  • the Hunter Colour system evaluates the colour of a fabric sample in terms of the ⁇ E value which represents the change in the Hunter L, a, b, values which are determined by reflecting spectrophotometer.
  • Example I demonstrates the increased dye transfer inhibiting performance of the polyamine N-oxide containing polymers in combination with bleaching agents.
  • the bleaching agent that is used is an activated bleaching agent (Perborate (PB)/TAED).
  • PB Perborate
  • TED activated bleaching agent
  • the performance of said combination was determined by measuring the whiteness of textile items washed with compositions containing the PB/TAED and/or poly(4-vinylpyridine-N-oxide) (PVNO).
  • Bleeding fabric composition Bleeding fabric color A B C D 100% cotton Direct Blue 90 23.1 21.6 6.9 4.5
  • a liquid detergent composition according to the present invention is prepared, having the following compositions : % by weight of the total detergent composition A B C Linear alkylbenzene sulfonate 10 - - Polyhydroxy fatty acid amide - 9 - Alkyl alkoxylated sulfate - - 9 Alkyl sulphate 4 4 4 Fatty alcohol (C 12 -C 15 ) ethoxylate 12 12 12 Fatty acid 10 10 10 10 Oleic acid 4 4 4 Citric acid 1 1 1 1 Diethylenetriaminepentamethylene 1.5 1.5 1.5 Phosphonic acid NaOH 3.4 3.4 3.4 Propanediol 1.5 1.5 1.5 Ethanol 10 10 10 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 Poly(4-vinylpyridine)-N-oxide 0-1 0-1 0-1 Thermamyl 0.13 0.13 0.13 Carezyme 0.014 0.014 0.014 FN-Base 1.8 1.8 1.8 Lipolase 0.
  • a compact granular detergent composition according to the present invention is prepared, having the following formulation: % by weight of the total detergent composition A B C Linear alkyl benzene sulphonate 11.40 - - Polyhydroxy fatty acid amide - 10 - Alkyl alkoxylated sulfate - - 9 Tallow alkyl sulphate 1.80 1.80 1.80 C 45 alkyl sulphate 3.00 3.00 3.00 C 45 alcohol 7 times ethoxylated 4.00 4.00 4.00 Tallow alcohol 11 times ethoxylated 1.80 1.80 1.80 Dispersant 0.07 0.07 0.07 Silicone fluid 0.80 0.80 0.80 Trisodium citrate 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 3.00 Zeolite 32.50 32.50 32.50 Maleic acid acrylic acid copolymer 5.00 5.00 5.00 Cellulase (active protein) 0.03 0.03 0.03 Alkalase/BAN 0.60 0.60 0.60 Lipase 0.36 0.36 0.36 Sodium silicate
  • compositions (Example II (A/B/C) and III (A/B/C)) were very good at displaying excellent cleaning and detergency performance with outstanding color-care performance on colored fabrics and mixed loads of colored and white fabrics.

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Claims (21)

  1. Composition inhibant le transfert de teintures comprenant:
    a) un polymère choisi parmi les polymères contenant un poly(N-oxyde d'amine) qui contiennent des motifs de structure suivante:
    Figure 00350001
    dans laquelle
    P est un motif polymérisable, auquel le groupe N-O peut être fixé ou dont fait partie le groupe N-O,
    A est
    Figure 00350002
    x vaut 0 ou 1;
    R est un groupe aliphatique, aromatique, hétérocyclique ou alicyclique auquel l'atome d'azote du groupe N-O peut être fixé ou dont fait partie l'atome d'azote du groupe N-O, à la condition que R ne soit pas un groupe éthoxylé,
    b) un agent de blanchiment.
  2. Composition inhibant le transfert de teintures selon la revendication 1, dans laquelle P est un motif polymérisable auquel le groupe N-O est fixé et dans laquelle R est choisi parmi un groupe aromatique et un groupe hétérocyclique.
  3. Composition inhibant le transfert de teintures selon la revendication 2, dans laquelle l'atome d'azote du groupe N-O fait partie du groupe R.
  4. Composition inhibant le transfert de teintures selon la revendication 3, dans laquelle le groupe R est choisi parmi la pyridine, le pyrrole, l'imidazole et leurs dérivés.
  5. Composition inhibant le transfert de teintures selon la revendication 1 ou 2, dans laquelle l'atome d'azote du groupe N-O est fixé au groupe R.
  6. Composition inhibant le transfert de teintures selon la revendication 5, dans laquelle le groupe R est un groupe phényle.
  7. Composition inhibant le transfert de teintures selon la revendication 1, dans laquelle P est un motif polymérisable dont fait partie le groupe N-O et dans laquelle R est choisi parmi un groupe aromatique et un groupe hétérocyclique.
  8. Composition inhibant le transfert de teintures selon la revendication 7, dans laquelle l'atome d'azote du groupe N-O fait partie du groupe R.
  9. Composition inhibant le transfert de teintures selon la revendication 8, dans laquelle le groupe R est choisi parmi la pyridine, le pyrrole, l'imidazole et leurs dérivés.
  10. Composition inhibant le transfert de teintures selon les revendications 1 à 9, dans laquelle le squelette polymère est dérivé du groupe des polymères polyvinyliques.
  11. Composition inhibant le transfert de teintures selon les revendications 1 à 10, dans laquelle le rapport des groupes amine aux groupes N-oxyde d'amine est de 2:3 à 1:1 000 000, de préférence de 1:4 à 1:1 000 000, tout particulièrement de 1:7 à 1:1 000 000.
  12. Composition inhibant le transfert de teintures selon les revendications 1 à 11, dans laquelle le polymère contenant un poly(N-oxyde d'amine) possède une masse moléculaire moyenne dans la gamme de 500 à 1 000 000, de préférence de 1000 à 50 000, mieux encore de 2 000 à 30 000, tout particulièrement de 3 000 à 20 000.
  13. Composition inhibant le transfert de teintures selon les revendications 1 à 12, dans laquelle ledit polymère contenant un poly(N-oxyde d'amine) est le poly(N-oxyde de 4-vinylpyridine).
  14. Composition inhibant le transfert de teintures selon les revendications 1 à 13, dans laquelle le polymère contenant un poly(N-oxyde d'amine) est présent dans une proportion de 0,001 à 10% en poids de la composition.
  15. Composition inhibant le transfert de teintures selon les revendications 1 à 14, dans laquelle ledit agent de blanchiment est un agent de blanchiment activé ou non activé.
  16. Composition inhibant le transfert de teintures selon les revendications 1 à 15, dans laquelle ledit agent de blanchiment est un agent de blanchiment peroxygéné choisi parmi le peroxyde d'hydrogène, les perborates, les persulfates, les percarbonates, les peroxydisulfates, les perphosphates et les peroxyhydrates, ou leurs mélanges.
  17. Composition inhibant le transfert de teintures selon les revendications 15 et 16, qui comprend en outre un activateur de blanchiment choisi parmi la TAED, l'ISONOBS, le PAG, l'ATC, ou leurs mélanges.
  18. Composition inhibant le transfert de teintures selon les revendications 1 à 17, comprenant en outre un catalyseur métallique.
  19. Composition inhibant le transfert de teintures selon les revendications 1 à 18, qui est un additif pour détergents, sous la forme d'un granulé non poussiéreux ou d'un liquide.
  20. Composition détergente qui comprend une composition inhibant le transfert de teintures selon les revendications 1 à 19 et qui comprend en outre des tensioactifs et d'autres ingrédients détergents classiques.
  21. Utilisation
    a) d'un polymère choisi parmi les polymères contenant un poly(N-oxyde d'amine) comportant des motifs de formule développée suivante:
    Figure 00370001
    dans laquelle
    P est un motif polymérisable, auquel le groupe N-O peut être fixé ou dont fait partie le groupe N-O, ou une combinaison des deux,
    A est
    Figure 00370002
    x vaut 0 ou 1;
    R est un groupe aliphatique, aliphatique éthoxylé, aromatique, hétérocyclique ou alicyclique ou toute combinaison de ces groupes auquel l'atome d'azote du groupe N-O peut être fixé ou dont fait partie l'atome d'azote du groupe N-O, et
    b) d'un agent de blanchiment,
    pour inhiber le transfert de teintures entre des tissus pendant un lavage.
EP19930870105 1992-07-15 1993-06-09 Compositions pour éviter le transfert de colorant, comprenant des agents de blanchiment Expired - Lifetime EP0587549B1 (fr)

Priority Applications (14)

Application Number Priority Date Filing Date Title
ES93870109T ES2125970T3 (es) 1992-07-15 1993-06-09 Composiciones que inhiben la transferencia de colorante que comprenden agentes dispersantes polimeros.
DE1993624422 DE69324422T2 (de) 1992-07-15 1993-06-09 Zusammensetzungen zur Verhinderung der Farbstoffübertragung die Bleichmittel enthalten
EP19930870105 EP0587549B1 (fr) 1992-07-15 1993-06-09 Compositions pour éviter le transfert de colorant, comprenant des agents de blanchiment
DE1993622449 DE69322449T2 (de) 1992-07-15 1993-06-09 Polymere Dispergiermittel enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung
ES93870105T ES2132210T3 (es) 1992-07-15 1993-06-09 Composiciones para inhibir la transferencia de colorante que comprenden agentes blanqueadores.
US08/373,197 US5478489A (en) 1992-07-15 1993-06-30 Dye transfer inhibiting compositions comprising bleaching agents and a polyamine N-oxide polymer
JP50448494A JP3892033B2 (ja) 1993-06-09 1993-06-30 漂白剤を含む染料移動抑制組成物
PCT/US1993/006224 WO1994002581A1 (fr) 1992-07-15 1993-06-30 Compositions inhibant le transfert de teintures, contenant des agents de blanchiment
CA002140287A CA2140287C (fr) 1992-07-15 1993-06-30 Compositions inhibitrices de transfert hydrotypique de colorants, contenant des agents de blanchiment
CN 93116770 CN1047623C (zh) 1992-07-15 1993-07-15 含有漂白剂的能抑制染料转移的组合物
TR00616/93A TR28340A (tr) 1992-07-15 1993-07-15 Agartma maddelerini iceren boya transferi önleyici bilesimler.
CN93116491A CN1040656C (zh) 1992-07-15 1993-07-15 含有表面活性剂的染料转移抑制组合物
MX9304299A MX9304299A (es) 1992-07-15 1993-07-15 Composiciones inhibidoras de trasnferencia de colorante que comprenden agentes blanqueadores.
AU45457/93A AU4545793A (en) 1992-07-15 1993-07-16 Dye transfer inhibiting compositions comprising bleaching agents

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
EP92202168 1992-07-15
EP92202168 1992-07-15
EP19920870181 EP0596184B1 (fr) 1992-11-06 1992-11-06 Compositions détergentes avec additifs pour empêcher le transfert de colorant
EP92870181 1992-11-06
EP93201198 1993-04-26
EP93201198A EP0579295B1 (fr) 1992-07-15 1993-04-26 Détergents avec additifs pour éviter le transfert de colorant
EP19930870105 EP0587549B1 (fr) 1992-07-15 1993-06-09 Compositions pour éviter le transfert de colorant, comprenant des agents de blanchiment

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EP0587549B1 true EP0587549B1 (fr) 1999-04-14

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GB1541576A (en) * 1975-06-20 1979-03-07 Procter & Gamble Ltd Inhibiting dye ltransfer in washing
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
DE3803630A1 (de) * 1988-02-06 1989-08-17 Henkel Kgaa Waschmittelzusatz
ES2083560T3 (es) * 1991-04-12 1996-04-16 Procter & Gamble Composicion detergente compacta que contiene polivinilpirrolidona.

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CN1047623C (zh) 1999-12-22
ES2125970T3 (es) 1999-03-16
TR28340A (tr) 1996-05-02
DE69324422T2 (de) 1999-11-18
MX9304299A (es) 1994-05-31
DE69324422D1 (de) 1999-05-20
EP0587549A1 (fr) 1994-03-16

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