EP0596186A1 - Compositions détergentes avec additifs pour empêcher le transfert de colorant - Google Patents

Compositions détergentes avec additifs pour empêcher le transfert de colorant Download PDF

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Publication number
EP0596186A1
EP0596186A1 EP92870183A EP92870183A EP0596186A1 EP 0596186 A1 EP0596186 A1 EP 0596186A1 EP 92870183 A EP92870183 A EP 92870183A EP 92870183 A EP92870183 A EP 92870183A EP 0596186 A1 EP0596186 A1 EP 0596186A1
Authority
EP
European Patent Office
Prior art keywords
water
dye transfer
transfer inhibiting
composition according
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.)
Withdrawn
Application number
EP92870183A
Other languages
German (de)
English (en)
Inventor
Abdennaceur Fredj
James Pyott Johnston
Regine Labeque
Chistiaan Arthur Jacques Kamiel Thoen
Andre Christian Convents
Alfred Busch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP92870183A priority Critical patent/EP0596186A1/fr
Priority to CA 2148809 priority patent/CA2148809A1/fr
Priority to JP6512177A priority patent/JPH08503248A/ja
Priority to PCT/US1993/010548 priority patent/WO1994011479A1/fr
Priority to AU55908/94A priority patent/AU5590894A/en
Priority to CN 93112696 priority patent/CN1088255A/zh
Priority to MX9306970A priority patent/MX9306970A/es
Publication of EP0596186A1 publication Critical patent/EP0596186A1/fr
Withdrawn legal-status Critical Current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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3932Inorganic compounds or complexes
    • 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

Definitions

  • the present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing.
  • Suspended or solubilized dyes can to some degree be oxidized in solution by employing known bleaching agents.
  • U.S. Patent 4,077,768 describes a process for inhibiting dye transfer by the use of an oxidizing bleaching agent together with a catalytic compound such as iron porphins.
  • Copending EP Patent Application 91202655.6 filed October 9, 1991, relates to dye transfer inhibiting compositions comprising an enzymatic system capable of generating hydrogen peroxide and porphin catalysts.
  • a dye transfer inhibiting composition which exhibits optimum dye transfer inhibiting properties.
  • the invention provides an efficient process for laundering operations involving colored fabrics.
  • the present invention relates to inhibiting dye transfer compositions comprising :
  • a process is also provided for laundering operations involving colored fabrics.
  • the present invention provides a dye transfer inhibiting composition comprising :
  • the preferred usage range of the catalyst in the wash is 10- 8 molar to 10- 3 molar, more preferred 10- 6 - 10- 4 molar.
  • the essential metallo porphin structure may be visualized as indicated in Formula I in the accompanying drawings.
  • Formula I the atom positions of the porphin structure are numbered conventionally and the double bonds are put in conventionally. In other formula, the double bonds have been omitted in the drawings, but are actually present as in I.
  • Preferred metallo porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of Formula I (Meso positions), with a phenyl or pyridyl substituent selected from the group consisting of wherein n and m may be 0 or 1; A is selected from water-solubilizing group, e.g., sulfate, sulfonate, phosphate, and carboxylate groups; and B is selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 1 polyethoxy alkyl or C 1 -C 1o hydroxy alkyl.
  • Preferred molecules are those in which the substituents on the phenyl or pyridyl groups are selected from the group consisting of
  • a particularly preferred metallo phorphin is one in which the molecule is substituted at the 5, 10 15, and 20 carbon positions with the substituent
  • This preferred compound is known as metallo tetrasulfonated tetraphenylporphin.
  • X 2 of Formula I represents an anion, preferably OH- or CI-.
  • the compound of Formula I may be substituted at one or more of the remaining carbon positions with C 1 -C 10 alkyl, hydroxyalkyl or oxyalkyl groups.
  • Porphin derivatives also include chlorophyls, chlorines, i.e. isobacterio chlorines and bacteriochlorines.
  • Metallo porphyrin and water-soluble or water-dispersable derivatives thereof have a structure given in formula II.
  • X can be alkyl, alkyl carboxy, alkyl hydroxyl, vinyl, alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate, aryl.
  • X 2 of Formula II represents an anion, preferably OH- or CI-.
  • the symbol X can be alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl, alkylsulfate, alkylsulfonate, sulfate, sulfonate.
  • Metallo phthalocyanine and derivatives have the structure indicated in Formula III, wherein the atom positions of the phthalocyanine structure are numbered conventionally.
  • the anionic groups in the above structures contain cations selected from the group consisting of sodium and potassium cations or other non- interfering cations which leave the structures water-soluble.
  • Preferred phthalocyanine derivatives are metallo phthalocyanine trisulfonate and metallo phthalocyanine tetrasulfonate.
  • the choice of the substituent groups can be used to control the solubility of the catalyst in water or in detergent solutions. Yet again, especially where it is desired to avoid attacking dyes attached to solid surfaces, the substituents can control the affinity of the catalyst compound for the surface.
  • strongly negatively charged substituted compounds for instance the tetrasulfonated porphin, may be repelled by negatively charged stained surfaces and are therefore most likely not to cause attack on fixed dyes, whereas the cationic or zwitterionic compounds may be attracted to, or at least not repelled by such stained surfaces.
  • the bleach used in the different examples should be such that at least 70%, preferably all of the oxygen active species is available after 5 min at 40 ° C.
  • the available oxygen species can be determined very easily by titration by the man skilled in the art.
  • a 1% solution of detergent is prepared in 40 °C water. 5 min later, the solution is centrifuged to precipitate all non-dissolving substances. From the supernatant the available oxygen is measured as follows: a known weight of the supernatant solution to be measured is sampled and the reaction is stopped using glacial acetic acid. Excess potassium iodide (KI) is added to the solution:
  • the liberated iodine (according to eq 1) is then titrated with sodium thiosulfate (Na2 S2 03). Starch which gives a purple/blue complex with I- is used as an indicator.
  • a quick releasing bleach should have at least 70%, preferably all the available oxygen in solution after 5 minutes at 40 ° C.
  • the quick releasing 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),3,5,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 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),3,5,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591), or pentaacetylglucose (PAG), which are perhydrolyzed to form a per
  • peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
  • an efficient amount of bleach is by definition the necessary amount of bleach which combined with a bleach catalyst leads to a level of dye oxidation which is between 40% to 100%, preferably 40% to 60%, more preferred 60% to 80%, most preferred 80%-100% of the maximum (Z) per cent of dye oxidation that can be achieved under the most optimal conditions determined by those skilled in the art.
  • a washing machine or launderometer add a known bleeding fabric and a known uncolored pick-up tracer (e.g. cotton) to the wash load. After simulating a wash cycle, determine the amount of dye that has been pick-up by the tracer according to methods known to those skilled in the art. Now to separate washing machines, add the same amount of bleeding fabric and pick-up tracer, a fixed amount of catalyst and vary the bleach level. Determine the level of dye transfer onto the pick tracers and vary the amount of bleach as to minimize dye transfer. In this way the most optimal bleach concentration can be determined.
  • a known bleeding fabric and a known uncolored pick-up tracer e.g. cotton
  • 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.
  • 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 -Cl8 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.
  • 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 C 9 -C 15 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 C 12 -C14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants comprises alkyl polyglucoside compounds of general formula 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.
  • 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 polyhydroxy 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 s - 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 0 5 ).
  • Suitab!e 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.
  • lauryl succinate 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.
  • 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 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.
  • Another preferred builder system for liquid compositions is based on dodecenyl succinic 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.
  • builder materials that can form part of the builder system for use in granular compositions for the purposes of this invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
  • Suitable water-soluble organic salts are the homo- or co-polymeric 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 suds boosting or depressing agents, enzymes and stabilizers or activators therefore, soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.
  • enzyme technologies which also provide a type of color care benefit. Examples are cellulase for color maintenance/ rejuvenation.
  • These components should preferably be chosen such that they are compatible with the bleach component of the composition.
  • 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/I; 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 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 90 ° C, especially 20 to 60, but the catalysts are effective at up to 95 ° C.
  • the pH of the treatment solution is preferably from 7 to 11, especially from 7.0 to 9.0.
  • the process and compositions of the invention can also be used as additive during laundry operations.
  • the extent of dye oxidation was measured by two different methods: (i) in solution dye bleaching and (2) measurement of the reduction of dye transfer from textile to textile.
  • a detergent solution (100 mL) containing dyes (40 ppm final concentration) and the catalyst (1 x 10-5 M) was prepared and its pH value adjusted to 8.0 or 10.
  • the absorbance spectrum was recorded from 350-800 nm. This region should encompasses the wavelength maximum of the dyes (as noted for some example in the table below) and the maximum absorbance of the catalyst (Soret band and Q band for porphyrins and phthalocyanines, respectively).
  • the oxidant H 2 0 2 , perborate, percarbonate, activated bleach or oxone
  • the level of oxidant should be optimum as defined in described test method. After 30 min the absorbance spectrum was recorded and the decrease in absorbance of the dyes noted.
  • b represents the intensity of reflected yellow light (positive b value) or the intensity of reflected blue light (negative b value), and a is the measure of the intensity of the reflected red light (positive a value) or the reflected green light (negative a value).
  • a liquid dye transfer inhibiting composition according to the present invention is prepared, having the following compositions :
  • a compact granular dye transfer inhibiting composition according to the present invention is prepared, having the following formulation:
EP92870183A 1992-11-06 1992-11-06 Compositions détergentes avec additifs pour empêcher le transfert de colorant Withdrawn EP0596186A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP92870183A EP0596186A1 (fr) 1992-11-06 1992-11-06 Compositions détergentes avec additifs pour empêcher le transfert de colorant
CA 2148809 CA2148809A1 (fr) 1992-11-06 1993-11-03 Detergents renfermant un catalyseur metallique non ferreux et un agent de blanchiment pour empecher le transfert de colorant lors du lavage
JP6512177A JPH08503248A (ja) 1992-11-06 1993-11-03 洗浄中における染料移動を抑制するための非鉄金属触媒と漂白剤とを含有する洗剤
PCT/US1993/010548 WO1994011479A1 (fr) 1992-11-06 1993-11-03 Detergents renfermant un metallocatalyseur non ferreux et un agent de blanchiment pour empecher le transfert des couleurs au lavage
AU55908/94A AU5590894A (en) 1992-11-06 1993-11-03 Detergents containing non-iron metallocatalyst and bleach to inhibit dye transfer in washing
CN 93112696 CN1088255A (zh) 1992-11-06 1993-11-06 抑制洗涤中染料转移的洗涤剂组合物
MX9306970A MX9306970A (es) 1992-11-06 1993-11-08 Composiciones detergentes que inhiben la transferencia de colorantedurante el lavado.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP92870183A EP0596186A1 (fr) 1992-11-06 1992-11-06 Compositions détergentes avec additifs pour empêcher le transfert de colorant

Publications (1)

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EP0596186A1 true EP0596186A1 (fr) 1994-05-11

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EP92870183A Withdrawn EP0596186A1 (fr) 1992-11-06 1992-11-06 Compositions détergentes avec additifs pour empêcher le transfert de colorant

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EP (1) EP0596186A1 (fr)
JP (1) JPH08503248A (fr)
CN (1) CN1088255A (fr)
AU (1) AU5590894A (fr)
CA (1) CA2148809A1 (fr)
MX (1) MX9306970A (fr)
WO (1) WO1994011479A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998008926A1 (fr) * 1996-08-26 1998-03-05 The Procter & Gamble Company Regulation de l'activite de la cellulase par un terminateur

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5401034B2 (ja) 2007-12-19 2014-01-29 ライオン株式会社 漂白助剤、および該漂白助剤を含有する漂白助剤粒子
CN113338061A (zh) * 2021-05-27 2021-09-03 广州骏亚纺织科技有限公司 双氧水催化剂的组合物及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2316371A1 (fr) * 1975-06-20 1977-01-28 Procter & Gamble Inhibition du transfert de matiere colorante pendant le lavage ou le blanchiment
EP0003861A1 (fr) * 1978-02-28 1979-09-05 THE PROCTER & GAMBLE COMPANY Composition de blanchiment détergente et procédé pour enlever des taches sur des tissus de coton
EP0054992A1 (fr) * 1980-12-22 1982-06-30 Unilever N.V. Composition contenant un activateur de photo ayant un blanchiment amélioré
EP0062523A2 (fr) * 1981-04-08 1982-10-13 THE PROCTER & GAMBLE COMPANY Compositions additives pour détergents, leur préparation et leur emploi dans des compositions détergentes
EP0153278A2 (fr) * 1984-02-17 1985-08-28 Ciba-Geigy Ag Composés phtalocyaniniques aquasolubles et leur utilisation comme photoactivateurs
EP0384503B1 (fr) * 1989-02-22 1995-06-28 Unilever N.V. Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1408144A (en) * 1972-06-02 1975-10-01 Procter & Gamble Ltd Bleaching process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2316371A1 (fr) * 1975-06-20 1977-01-28 Procter & Gamble Inhibition du transfert de matiere colorante pendant le lavage ou le blanchiment
EP0003861A1 (fr) * 1978-02-28 1979-09-05 THE PROCTER & GAMBLE COMPANY Composition de blanchiment détergente et procédé pour enlever des taches sur des tissus de coton
EP0054992A1 (fr) * 1980-12-22 1982-06-30 Unilever N.V. Composition contenant un activateur de photo ayant un blanchiment amélioré
EP0062523A2 (fr) * 1981-04-08 1982-10-13 THE PROCTER & GAMBLE COMPANY Compositions additives pour détergents, leur préparation et leur emploi dans des compositions détergentes
EP0153278A2 (fr) * 1984-02-17 1985-08-28 Ciba-Geigy Ag Composés phtalocyaniniques aquasolubles et leur utilisation comme photoactivateurs
EP0384503B1 (fr) * 1989-02-22 1995-06-28 Unilever N.V. Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998008926A1 (fr) * 1996-08-26 1998-03-05 The Procter & Gamble Company Regulation de l'activite de la cellulase par un terminateur

Also Published As

Publication number Publication date
MX9306970A (es) 1995-01-31
WO1994011479A1 (fr) 1994-05-26
CN1088255A (zh) 1994-06-22
JPH08503248A (ja) 1996-04-09
CA2148809A1 (fr) 1994-05-26
AU5590894A (en) 1994-06-08

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