EP0579295A1 - Détergents avec additifs pour éviter le transfert de colorant - Google Patents

Détergents avec additifs pour éviter le transfert de colorant Download PDF

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Publication number
EP0579295A1
EP0579295A1 EP93201198A EP93201198A EP0579295A1 EP 0579295 A1 EP0579295 A1 EP 0579295A1 EP 93201198 A EP93201198 A EP 93201198A EP 93201198 A EP93201198 A EP 93201198A EP 0579295 A1 EP0579295 A1 EP 0579295A1
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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.)
Granted
Application number
EP93201198A
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German (de)
English (en)
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EP0579295B1 (fr
Inventor
Alan David Willey
Frederick Edward Hardy
Abdennaceur Fredj
Christiaan Arthur Jacques Kamiel Thoen
James Pyott Johnston
Findley Maccorquedale
Alfred Busch
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to ES93870106T priority Critical patent/ES2125967T3/es
Priority to EP19930870105 priority patent/EP0587549B1/fr
Priority to DE1993622461 priority patent/DE69322461T2/de
Priority to ES93870108T priority patent/ES2125969T3/es
Priority to EP93870109A priority patent/EP0581753B1/fr
Priority to ES93870107T priority patent/ES2125968T3/es
Priority to EP19930870106 priority patent/EP0587550B1/fr
Priority to DE1993622448 priority patent/DE69322448T2/de
Priority to EP93870108A priority patent/EP0581752B1/fr
Priority to DE1993622449 priority patent/DE69322449T2/de
Priority to ES93870109T priority patent/ES2125970T3/es
Priority to EP19930870107 priority patent/EP0581751B1/fr
Priority to DE1993624422 priority patent/DE69324422T2/de
Priority to ES93870105T priority patent/ES2132210T3/es
Priority to DE1993622447 priority patent/DE69322447T2/de
Priority to US08/373,259 priority patent/US5633225A/en
Priority to JP50448394A priority patent/JP3795066B2/ja
Priority to US08/373,198 priority patent/US5458810A/en
Priority to CA002140289A priority patent/CA2140289C/fr
Priority to US08/373,196 priority patent/US5458809A/en
Priority to CA002140282A priority patent/CA2140282A1/fr
Priority to PCT/US1993/006222 priority patent/WO1994002579A1/fr
Priority to AU46582/93A priority patent/AU4658293A/en
Priority to US08/373,197 priority patent/US5478489A/en
Priority to IN692DE1993 priority patent/IN188182B/en
Priority to PH46482A priority patent/PH30425A/en
Priority to PH46481A priority patent/PH30144A/en
Priority to PH46483A priority patent/PH30146A/en
Priority to PH46487A priority patent/PH29955A/en
Priority to CN93116491A priority patent/CN1040656C/zh
Priority to TR00617/93A priority patent/TR28338A/xx
Priority to MX9304295A priority patent/MX190415B/es
Priority to CN 93116770 priority patent/CN1047623C/zh
Priority to CN 93116768 priority patent/CN1042647C/zh
Priority to MX9304298A priority patent/MX191084B/es
Priority to MX9304297A priority patent/MX9304297A/es
Priority to TR00616/93A priority patent/TR28340A/xx
Priority to CN 93116766 priority patent/CN1043785C/zh
Priority to MX9304299A priority patent/MX9304299A/es
Priority to MX9304294A priority patent/MX190414B/es
Priority to CN 93116769 priority patent/CN1040454C/zh
Priority to TR00594/93A priority patent/TR27575A/xx
Priority to MX9304296A priority patent/MX9304296A/es
Priority to CN93116767.1A priority patent/CN1042646C/zh
Priority to EP93870149A priority patent/EP0622447A1/fr
Priority to US08/432,130 priority patent/US5560858A/en
Priority to TW082109433A priority patent/TW235308B/zh
Publication of EP0579295A1 publication Critical patent/EP0579295A1/fr
Priority to AU66363/94A priority patent/AU6636394A/en
Priority to PCT/US1994/004221 priority patent/WO1994025555A1/fr
Priority to PE1994240880A priority patent/PE9195A1/es
Priority to US08/373,257 priority patent/US5470507A/en
Priority to US08/373,199 priority patent/US5460752A/en
Application granted granted Critical
Publication of EP0579295B1 publication Critical patent/EP0579295B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3792Amine oxide containing polymers

Definitions

  • the present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing.
  • Polymers have been used within detergent compositions to inhibit dye transfer.
  • EP-A-O 102 923 describes the use of carboxyl containing polymers within an aqueous compositions.
  • DE-A-2 814 329 discloses the use of N-vinyl-oxazolidone polymers and FR-A-2 144 721 discloses the use of 15-35% of a copolymer of polyvinylpyrrolidone and acrylic acid nitrile or maleic anhydride within a washing powder.
  • EP-265 257 describes detergent compositions comprising an alkali-metal carboxy-metal carboxymethylcellulose, a vinylpyrrolidone polymer and a polycarboxylate polymer.
  • a process is also provided for laundering operations involving colored fabrics.
  • the present invention relates to inhibiting dye transfer compositions comprising polyamine N-oxide polymers which contain units having the following structure formula : wherein P is a polymerisable unit, whereto the N-O group can be attached to or wherein the N-O group forms part of the polymerisable unit or a combination of both.
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group form part of these groups.
  • compositions of the present invention comprise as an essential element polyamine N-oxide polymers which contain units having the following structure formula : wherein P is a polymerisable unit, whereto the R-N-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both.
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures : wherein R1, R2, R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • 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 pyrridine, 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-0 functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, 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-0 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 oxide 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 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000.
  • 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 oxides 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 is within the range of 500 to 1000,000; 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-oxides 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-oxides 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 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 predisolved 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 H2O2, and a few drops of H2SO4 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 1l of acetone under agitation.
  • the resulting yellow brown viscous syrup formed on the bottom is washed again with 1l of aceton to yield a pale crystalline solid.
  • the solid was filtered off by gravity, washed with acetone and then dried over P2O5.
  • the amine : amine N-oxide ratio of this polymer is 1:4.
  • 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 C12-C18 fatty source preferably from a C16-C18 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 C14 ⁇ 15 alkyl sulphates.
  • the cation in each instance is again an alkali metal cation, preferably sodium.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic-lipophilic 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 C9-C15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C12-C14 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 R1 is H, or R1 is C1 ⁇ 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5 ⁇ 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.
  • R1 is methyl
  • R2 is a straight C11 ⁇ 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.
  • Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst).
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2O5).
  • Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well 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 watersoluble carboxylate chelating agent such as citric acid.
  • a water-insoluble aluminosilicate builder such as zeolite A
  • a watersoluble carboxylate chelating agent such as citric acid.
  • Other builder materials that can form part of the builder system for use in granular compositions the purposes of the invention 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 compositions may be employed, such as bleaches, bleach stabilizers or activators therefor, soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.
  • 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.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 millimicrons to 20 millimicrons and a specific surface area above 50 m2/g intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200 000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
  • 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 DTOS 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 N 92870174.7 filed 10 November, 1992.
  • compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil®.
  • 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.
  • the incorporation of the suds modifiers is preferably made as separate particulates, and this permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MW copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al U.S. Patent No. 3 933 672.
  • 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. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 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 and Protease B are enzymes referred to herein as Protease A and Protease B.
  • Protease A and methods for its preparation are described in European Patent Application 130,756, published January 9, 1985, incorporated herein by reference.
  • Protease B is a proteolytic enzyme which differs from Protease A in that it has a leucine substituted for tyrosine in position 217 in its amino acid sequence.
  • Protease B is described in European Patent Application Serial No. 87303761.8, filed April 28, 1987, incorporated herein by reference.
  • Methods for preparation of Protease B are also disclosed in European Patent Application 130,756, Bott et al, published January 9, 1985, incorporated herein by reference.
  • 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), previously incorporated herein by reference.
  • 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, issued March 6, 1984, incorporated herein by reference, 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).
  • Other suitable cellulases are cellulases originated from Humicola Insulens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
  • Such cellulase are described in Copending European patent application No. 93200811.3, filed March 19, 1993. Especially suitable cellulase are the cellulase having color care benefits. Examples of such cellulases are cellulase described in European patent application No. 91202879.2, 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, incorporated herein by reference.
  • 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 and a method for its purification have been described in Japanese Patent Application 53-20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co.
  • Lipase P Lipase P
  • Amano-P Lipase P
  • Such lipases of the present invention should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)).
  • Ouchterlony Acta. Med. Scan., 133, pages 76-79 (1950)
  • These lipases, and a method for their immunological cross-reaction with Amano-P are also described in U.S. Patent 4,707,291, Thom et al, issued November 17, 1987, incorporated herein by reference.
  • Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • 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, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S, and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
  • the enzymes are preferably coated or prilled with additives inert toward the enzymes to minimize dust formation and improve storage stability. Techniques for accomplishing this are well-known in the art.
  • 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, Letton, et al, issued March 9, 1982, incorporated herein by reference.
  • 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.
  • Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent aplication N 92870018.6 filed on January 31, 1992. Examples of such 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 cellulase and/or peroxidases and/or metallo catalysts for color maintance rejuvenation.
  • the detergent compositions according to the invention can be in liquid, paste 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.
  • the liquid compositions according to the present invention can also be in "compact 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 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.
  • 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 additive during laundry operations.
  • 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 liquid detergent composition according to the present invention is prepared, having the following compositions :
  • 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 ⁇ c value which represents the change in the Hunter a, b values which are determined by reflecting spectrometrie.
  • 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.
  • Bleeding fabric composition Bleeding fabric color A B 55% Linen/45% Polyester Green 4.2 1.7 Jeans Blue 15.7 3.3 60% Polyester/40% Flax Blue 4.3 1.9 100% cotton Brown 7.6 0.8 100% Flax Brown 3.6 1.1
  • Bleeding fabric composition Bleeding fabric color A B 33% Viscose/67% Polyester Green 10.0 4.9 35% Viscose/65% Polyester Blue 4.9 0.8 100% cotton Black 3.5 2.2 Jeans Blue 15.7 14 60% Polyester/40% Flax Blue 4.3 2.3 100% cotton Brown 7.6 5.9 60% Wool/40% Polyamide Mauve 2.2 1.1
  • the extent of dye transfer from brown cotton fabric was studied using a launder-o-meter test which simulates a 30 min wash cycle.
  • Bleeding fabric composition Bleeding fabric color A B 100% Cotton Brown 4.0 2,5
  • the extent of dye transfer from brown cotton fabric was studied using a launder-o-meter test which simulates a 30 min wash cycle.
  • Bleeding fabric composition Bleeding fabric color A B1 B2 B3 100% cotton Brown 16.9 5.5 3.6 2.1 100% cotton Blue 11.1 8.5 6.2 3.9
  • the dye transfer inhibition performance of poly(Dimethylamino)-ethylmethacryllate-N-oxide was tested in a domestic washing machine using a 40° C cycle.
  • the washing machine loads consisted of ballast laundry and 1000 cm2 of a known bleeding fabric.
  • Bleeding fabric composition Bleeding fabric color A B 100% cotton Brown 15.9 11.9 100% cotton Blue 8.08 2.8
  • the dye transfer inhibition performance of poly(4-vinylpyridine)-N-oxide was tested in a domestic washing machine using a 40° C cycle.
  • the washing machine loads consisted of ballast laundry and 1000 cm2 of a known bleeding fabric.
  • a 26cm by 31cm terry towel was used as the pick-up tracer for the bleeding dye.
  • PVNO polyvinylpyridine-N-oxide
  • a liquid detergent composition according to the present invention is prepared, having the following compositions : Linear alkylbenzene sulfonate 10 Alkyl sulphate 4 Fatty alcohol (C12-C15) ethoxylate 12 Fatty acid 10 Oleic acid 4 Citric acid 1 Diethylenetriaminepentamethylene Phosphonic acid 1.5 NaOH 3.4 Propanediol 1.5 Ethanol 10 Ethoxylated tetraethylene pentamine 0.7 Poly(4-vinylpyridine)-N-oxide 0.3 Thermamyl 0.13 Carezyme 0.014 FN-Base 1.8 Lipolase 0.14 Endoglucanase A 0.53 Suds supressor (ISOFOL r ) 2.5 Minors up to 100
  • a compact granular detergent composition according to the present invention is prepared, having the following formulation: Linear alkyl benzene sulphonate 11.40 Tallow alkyl sulphate 1.80 C45 alkyl sulphate 3.00 C45 alcohol 7 times ethoxylated 4.00 Tallow alcohol 11 times ethoxylated 1.80 Dispersant 0.07 Silicone fluid 0.80 Trisodium citrate 14.00 Citric acid 3.00 Zeolite 32.50 Maleic acid actylic acid copolymer 5.00 DETMPA 1.00 Cellulase (active protein) 0.03 Alkalase/BAN 0.60 Lipase 0.36 Sodium silicate 2.00 Sodium sulphate 3.50 Glucose 10.00 Poly(4-vinylpyridine)-N-oxide 0.3 Minors up to 100

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
EP93201198A 1992-07-15 1993-04-26 Détergents avec additifs pour éviter le transfert de colorant Expired - Lifetime EP0579295B1 (fr)

Priority Applications (52)

Application Number Priority Date Filing Date Title
ES93870106T ES2125967T3 (es) 1992-07-15 1993-06-09 Composiciones que inhiben la transferencia de colorante con contenido en tensioactivo.
EP19930870105 EP0587549B1 (fr) 1992-07-15 1993-06-09 Compositions pour éviter le transfert de colorant, comprenant des agents de blanchiment
DE1993622461 DE69322461T2 (de) 1992-07-15 1993-06-09 Tenside enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung
ES93870108T ES2125969T3 (es) 1992-07-15 1993-06-09 Composiciones para inhibir la transferencia de colorante con contenido en mejoradores.
EP93870109A EP0581753B1 (fr) 1992-07-15 1993-06-09 Compositions pour éviter le transfert de colorant contenant des agents dispersants polymères
ES93870107T ES2125968T3 (es) 1992-07-15 1993-06-09 Composiciones detergentes enzimaticas que inhiben la transferencia de colorante.
EP19930870106 EP0587550B1 (fr) 1992-07-15 1993-06-09 Compositions pour éviter le transfert de colorant contenant des agents tensio-actifs
DE1993622448 DE69322448T2 (de) 1992-07-15 1993-06-09 Builder enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung
EP93870108A EP0581752B1 (fr) 1992-07-15 1993-06-09 Compositions pour éviter le transfert de colorant contenant des adjuvants
DE1993622449 DE69322449T2 (de) 1992-07-15 1993-06-09 Polymere Dispergiermittel enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung
ES93870109T ES2125970T3 (es) 1992-07-15 1993-06-09 Composiciones que inhiben la transferencia de colorante que comprenden agentes dispersantes polimeros.
EP19930870107 EP0581751B1 (fr) 1992-07-15 1993-06-09 Compositions détergentes pour éviter le transfert de colorant contenant des enzymes
DE1993624422 DE69324422T2 (de) 1992-07-15 1993-06-09 Zusammensetzungen zur Verhinderung der Farbstoffübertragung die Bleichmittel enthalten
ES93870105T ES2132210T3 (es) 1992-07-15 1993-06-09 Composiciones para inhibir la transferencia de colorante que comprenden agentes blanqueadores.
DE1993622447 DE69322447T2 (de) 1992-07-15 1993-06-09 Enzym enthaltende Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung
US08/373,259 US5633225A (en) 1992-07-15 1993-06-30 Detergent compositions inhibiting dye transfer
JP50448394A JP3795066B2 (ja) 1993-04-26 1993-06-30 転染抑制洗剤組成物
US08/373,198 US5458810A (en) 1992-07-15 1993-06-30 Enzymatic detergent compositions inhibiting dye transfer
CA002140289A CA2140289C (fr) 1992-07-15 1993-06-30 Compositions detergentes qui inhibent le transfert des couleurs
US08/373,196 US5458809A (en) 1992-07-15 1993-06-30 Surfactant-containing dye transfer inhibiting compositions
CA002140282A CA2140282A1 (fr) 1992-07-15 1993-06-30 Compositions qui inhibent le transfert des couleurs et qui contiennent des agents dispersants polymeriques
PCT/US1993/006222 WO1994002579A1 (fr) 1992-07-15 1993-06-30 Compositions detergentes qui inhibent le transfert de colorants
AU46582/93A AU4658293A (en) 1992-07-15 1993-06-30 Detergent compositions inhibiting dye transfer
US08/373,197 US5478489A (en) 1992-07-15 1993-06-30 Dye transfer inhibiting compositions comprising bleaching agents and a polyamine N-oxide polymer
IN692DE1993 IN188182B (fr) 1992-07-15 1993-07-06
PH46482A PH30425A (en) 1992-07-15 1993-07-08 Dye transfer inhibiting compositions comprising polymeric dispersing agents
PH46481A PH30144A (en) 1992-07-15 1993-07-08 Built dye transfer inhibiting compositions
PH46483A PH30146A (en) 1992-11-06 1993-07-08 Surfactant containing dyf transfer inhibiting compositions
PH46487A PH29955A (en) 1992-07-15 1993-07-08 Enzymatic detergent compositions inhibiting dye transfer
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
TR00617/93A TR28338A (tr) 1992-07-15 1993-07-15 Sürfaktan ihtiva eden, boya transferini engelleyici bilesimler.
MX9304295A MX190415B (es) 1992-07-15 1993-07-15 Composiciones inhibidoras de transferencia de colorante que comprenden agentes dispersantes polimericos.
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
CN 93116768 CN1042647C (zh) 1992-07-15 1993-07-15 包含聚合物分散剂的染料转移抑制组合物
MX9304298A MX191084B (es) 1992-07-15 1993-07-15 Composiciones inhibidoras de trasnferencia de colorante que contienenagente tensioactivo.
MX9304297A MX9304297A (es) 1992-07-15 1993-07-15 Composiciones detergentes enzimaticas, que inhiben la transferencia de colorante.
TR00616/93A TR28340A (tr) 1992-07-15 1993-07-15 Agartma maddelerini iceren boya transferi önleyici bilesimler.
CN 93116766 CN1043785C (zh) 1992-07-15 1993-07-15 抑制染料转移的加酶洗涤组合物
MX9304299A MX9304299A (es) 1992-07-15 1993-07-15 Composiciones inhibidoras de trasnferencia de colorante que comprenden agentes blanqueadores.
MX9304294A MX190414B (es) 1992-07-15 1993-07-15 Composiciones detergentes que inhiben la transferencia de colorantes.
CN 93116769 CN1040454C (zh) 1992-07-15 1993-07-15 可抑制染料转移的洗涤剂组合物
TR00594/93A TR27575A (tr) 1992-07-15 1993-07-15 Polimerik dagitma maddeleri iceren boya transferi engelleyici bilesim.
MX9304296A MX9304296A (es) 1992-07-15 1993-07-15 Composiciones inhibidoras de trasnferencia de colorante con mejorador de detergencia.
CN93116767.1A CN1042646C (zh) 1992-07-15 1993-07-15 加助剂的染料转移抑制组合物
EP93870149A EP0622447A1 (fr) 1993-04-26 1993-07-22 Compositions détergentes pour éviter le transfer de colorant contenant des enzymes
US08/432,130 US5560858A (en) 1992-07-15 1993-11-03 Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine N-oxide polymer
TW082109433A TW235308B (fr) 1992-07-15 1993-11-10
AU66363/94A AU6636394A (en) 1993-04-26 1994-04-11 Enzymatic detergent compositions inhibiting dye transfer
PCT/US1994/004221 WO1994025555A1 (fr) 1993-04-26 1994-04-11 Compositions detergentes enzymatiques empechant le transfert des teintures
PE1994240880A PE9195A1 (es) 1993-04-26 1994-04-25 Composiciones detergentes enzimaticas inhibidoras de transferencia de tinte
US08/373,257 US5470507A (en) 1992-07-15 1995-01-17 Dye transfer inhibiting compositions comprising polymeric dispersing agents
US08/373,199 US5460752A (en) 1992-07-15 1995-01-17 Built dye transfer inhibiting compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92202168 1992-07-15
EP92202168 1992-07-15

Publications (2)

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EP0579295A1 true EP0579295A1 (fr) 1994-01-19
EP0579295B1 EP0579295B1 (fr) 1998-10-28

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AT (1) ATE172749T1 (fr)
DE (1) DE69321778T2 (fr)
DK (1) DK0579295T3 (fr)
ES (1) ES2125299T3 (fr)
PE (1) PE6495A1 (fr)
SA (1) SA93140122B1 (fr)
TW (1) TW235308B (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0664332A1 (fr) * 1994-01-19 1995-07-26 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
EP0664333A1 (fr) * 1994-01-19 1995-07-26 The Procter & Gamble Company Compositions détergentes contenant des polymères polyamine N-oxydes
WO1995028462A1 (fr) * 1994-04-14 1995-10-26 The Procter & Gamble Company Compositions detergentes contenant des inhibiteurs du transfert de couleurs et procede pour les fabriquer
WO1995033026A1 (fr) * 1994-06-01 1995-12-07 The Procter & Gamble Company Compositions contenant oleoyle sarcosinate empechant le transfert de colorants
EP0754748A1 (fr) * 1995-07-20 1997-01-22 The Procter & Gamble Company Compositions détergentes empêchant le transfert de colorant
US5597795A (en) * 1992-10-27 1997-01-28 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
EP0800570A1 (fr) * 1994-12-29 1997-10-15 The Procter & Gamble Company Composition detergente de lessive contenant un agent polymere inhibiteur de la decoloration sensiblement insoluble dans l'eau
US5730760A (en) * 1995-07-11 1998-03-24 Rohm And Haas Company Fabric washing composition and method for inhibiting deposition of dye
WO1998016437A1 (fr) * 1996-10-15 1998-04-23 The Procter & Gamble Company Emballage et combinaison de produit lessiviel moussant
US5843192A (en) * 1995-07-11 1998-12-01 Rohm And Haas Company Washing composition and use of polymer to clean and provide soil resistance to an article
US5939513A (en) * 1994-01-19 1999-08-17 The Procter & Gamble Company Methods of removing pigment stain using detergent compositions containing polyamine N-oxide polymers
US6140295A (en) * 1989-09-29 2000-10-31 Unilever Patent Holdings B.V. Perfumed laundry detergents containing lipase

Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0135217A1 (fr) * 1983-07-22 1985-03-27 THE PROCTER & GAMBLE COMPANY Oxydes d'amines éthoxylés ayant des propriétés pour enlever des taches et d'antiredéposition, utilisables dans les compositions détergentes
EP0265257A2 (fr) * 1986-10-24 1988-04-27 Unilever Plc Composition détergente
EP0327927A2 (fr) * 1988-02-06 1989-08-16 Henkel Kommanditgesellschaft auf Aktien Additif pour détergents

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0135217A1 (fr) * 1983-07-22 1985-03-27 THE PROCTER & GAMBLE COMPANY Oxydes d'amines éthoxylés ayant des propriétés pour enlever des taches et d'antiredéposition, utilisables dans les compositions détergentes
EP0265257A2 (fr) * 1986-10-24 1988-04-27 Unilever Plc Composition détergente
EP0327927A2 (fr) * 1988-02-06 1989-08-16 Henkel Kommanditgesellschaft auf Aktien Additif pour détergents

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6140295A (en) * 1989-09-29 2000-10-31 Unilever Patent Holdings B.V. Perfumed laundry detergents containing lipase
US5597795A (en) * 1992-10-27 1997-01-28 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
US5939513A (en) * 1994-01-19 1999-08-17 The Procter & Gamble Company Methods of removing pigment stain using detergent compositions containing polyamine N-oxide polymers
EP0664333A1 (fr) * 1994-01-19 1995-07-26 The Procter & Gamble Company Compositions détergentes contenant des polymères polyamine N-oxydes
EP0664332A1 (fr) * 1994-01-19 1995-07-26 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
WO1995028462A1 (fr) * 1994-04-14 1995-10-26 The Procter & Gamble Company Compositions detergentes contenant des inhibiteurs du transfert de couleurs et procede pour les fabriquer
CN1077135C (zh) * 1994-04-14 2002-01-02 普罗格特-甘布尔公司 包含染料转移抑制剂的洗涤剂组合物及其生产方法
WO1995033026A1 (fr) * 1994-06-01 1995-12-07 The Procter & Gamble Company Compositions contenant oleoyle sarcosinate empechant le transfert de colorants
EP0800570A1 (fr) * 1994-12-29 1997-10-15 The Procter & Gamble Company Composition detergente de lessive contenant un agent polymere inhibiteur de la decoloration sensiblement insoluble dans l'eau
EP0800570A4 (fr) * 1994-12-29 1998-01-28 Procter & Gamble Composition detergente de lessive contenant un agent polymere inhibiteur de la decoloration sensiblement insoluble dans l'eau
US5843192A (en) * 1995-07-11 1998-12-01 Rohm And Haas Company Washing composition and use of polymer to clean and provide soil resistance to an article
US5730760A (en) * 1995-07-11 1998-03-24 Rohm And Haas Company Fabric washing composition and method for inhibiting deposition of dye
EP0754748A1 (fr) * 1995-07-20 1997-01-22 The Procter & Gamble Company Compositions détergentes empêchant le transfert de colorant
WO1998016437A1 (fr) * 1996-10-15 1998-04-23 The Procter & Gamble Company Emballage et combinaison de produit lessiviel moussant

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DE69321778T2 (de) 1999-06-10
ES2125299T3 (es) 1999-03-01
DE69321778D1 (de) 1998-12-03
EP0579295B1 (fr) 1998-10-28
ATE172749T1 (de) 1998-11-15
TW235308B (fr) 1994-12-01
SA93140122B1 (ar) 2005-07-31
PE6495A1 (es) 1995-03-24
DK0579295T3 (da) 1999-07-05

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