EP0754748A1 - Farbstoffübertragung hemmende Waschmittelzusammensetzungen - Google Patents
Farbstoffübertragung hemmende Waschmittelzusammensetzungen Download PDFInfo
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- EP0754748A1 EP0754748A1 EP95202004A EP95202004A EP0754748A1 EP 0754748 A1 EP0754748 A1 EP 0754748A1 EP 95202004 A EP95202004 A EP 95202004A EP 95202004 A EP95202004 A EP 95202004A EP 0754748 A1 EP0754748 A1 EP 0754748A1
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- Prior art keywords
- alkyl
- dye transfer
- detergent
- composition according
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
Definitions
- the present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing. More in particular, the present invention relates to detergent compositions comprising water-soluble vinylpyridine copolymers.
- Polymers have been used within detergent compositions to inhibit dye transfer.
- One type of such polymers are N-vinylimidazole homo-and copolymers. Examples of said polymers are described in prior art documents such as DE 2 814 287-A which relates to detergent compositions comprising 0.1 to 10 wt% water-soluble or water-dispersible N-vinyl imidazole homo- or copolymer in combination with anionic and/or nonionic surfactants and other detergent ingredients.
- EP 372 291 relates to a process for washing discolouration-sensitive textiles. The wash liquor contains anionic/nonionic surfactants and watersoluble polymers e.g.
- EP 327 927 describes a granular detergent additive comprising water-soluble polymeric compounds based on N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidone and cationic compounds.
- DE 4027832-A discloses electrolyte-free liquid detergent compositions comprising zeolite A, nonionic surfactants and dye transfer inhibiting polymers. The dye transfer inhibiting polymers are homo-and copolymers selected from N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidone. Polyamine N-oxide are described in European Patent Application No. 93201198.4.
- water-soluble vinylpyridine copolymers are very efficient in eliminating transfer of solubilized or suspended dyes.
- a process is also provided for laundering operations involving colored fabrics.
- the present invention relates to dye transfer inhibiting compositions comprising a polymer selected from water-soluble vinylpyridine copolymers.
- the present invention comprises as an essential ingredient a polymer selected from the class of water-soluble vinylpyridine copolymers.
- the vinylpyridine copolymers have an average molecular weight range from 5000-1,000,000.
- Highly preferred polymers for use in the dye transfer inhibiting compositions according to the present invention comprise a polymer selected from vinylpyridine copolymers wherein said polymer has an average molecular weight range from 5,000 to 100,000 more preferably from 10,000 to 30,000, most preferably from 10,000 to 2O,000.
- the average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113. "Modern Methods of Polymer Characterization.
- an excellent overall detergency performance of detergent compositions comprising vinylpyridine copolymers can be obtained by selecting a specific average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 to 20,000.
- the vinylpyridine copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
- Any copolymerizing groups can be used as long as the polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable copolymerizing groups include formic acid, arylic acid, maleic acid, vinylpyrrolidone, vinyl acetate.
- Preferred copolymers are based on 4-vinylpyridine with vinylpyrrolidone, acrylic acid and maleic acid.
- the vinylpyridine copolymerizing monomer of the present invention has a molar ratio of copolymer to vinylpyridine from 1 to 0.01, preferably from 0.5 to 0.05, most preferably from 0.3 to 0.05.
- the vinylpyridine copolymers can be linear or branched.
- the vinylpyridine copolymers 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 conventiently 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 level of the vinylpyridine copolymer present in the detergent compositions is from 0.01 to 10%, more preferably from 0.05 to 5%, most preferably from 0.1 to 1% by weight of the detergent composition.
- the polymer is usually prepared by copolymerizing vinylpyridine with water soluble monomers in one or a mixture of water, methanol, isopropanol and acetone in the presence of polymerization initiator(s) such as water soluble azo initiators, sodium persulfate and/or hydrogen peroxide, and optionally a chain transfer agent.
- polymerization initiator(s) such as water soluble azo initiators, sodium persulfate and/or hydrogen peroxide, and optionally a chain transfer agent.
- Typical reaction temperatures are 70-90°C and pH is 3-7.
- the detergent composition may comprise one or more of a surfactant selected from a wide range of surfactants.
- alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 18 alkyl component, more preferably a C 12 -C 15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
- R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 18 alkyl component, more preferably a C 12 -C 15 alkyl or hydroxyalkyl
- M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted
- alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
- Branched alkylsulfates are especially preferred.
- Preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 18 alkyl or hydroxyalkyl, more preferably C 12 -C 15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation (e.g.
- R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C
- alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
- alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
- substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
- Exemplary surfactants are C 12 -C 15 alkyl polyethoxylate (1.0) sulfate (C 12 -C 15 E(1.0)M), C 12 -C 15 alkyl polyethoxylate (2.25) sulfate (C 12 -C 15 E(2.25)M), C 12 -C 15 alkyl polyethoxylate (3.0) sulfate (C 12 -C 15 E(3.0)M), and C 12 -C 15 alkyl polyethoxylate (4.0) sulfate (C 12 -C 15 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
- alkyl ester sulfonate surfactants including linear esters of C 8 -C 20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
- Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
- the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula : wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
- Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, triethanolamine.
- R 3 is C 10 -C 16 alkyl
- R 4 is methyl, ethyl or isopropyl.
- methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl.
- anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
- These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary of secondary alkanesulfonates, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
- alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 6 -C 12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
- Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
- the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
- 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 14, more preferably from 12 to 14.
- 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 3-12 moles of ethylene oxide per mole of alcohol, particularly the C 12 -C 15 primary alcohols containing 5-8 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.
- Highly preferred 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 of the present invention may comprise amine oxide in accordance with the general formula I: R 1 (EO) x (PO) y (BO) z N(O)(CH 2 R') 2 .qH 2 O (I)
- the structure (I) provides one long-chain moiety R 1 (EO) x (PO) y (BO) z and two short chain moieties, CH 2 R'.
- R' is preferably selected from hydrogen, methyl and -CH 2 OH.
- R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
- R 1 is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
- R 1 may be somewhat longer, having a chainlength in the range C 12 -C 24 .
- amine oxides are illustrated by C12-14 alkyldimethyl amine oxide,hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594, incorporated herein by reference.
- the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R 1 is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
- amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
- Preferred embodiments include dodecyldimethylamine, tetradecyldimethylamineoxidedihydrate, hexadecyldimethylamin eoxidedihydrate and octadecyldimethylamine oxide dihydrate.
- R' H
- R' CH 2 OH
- hexadecylbis(2- hydroxyethyl)amine oxide such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide, dodecyldimethyl(2- hydroxyethyl)amine oxide dihydrate.
- Suitable 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.
- the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to 2:1.
- Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
- cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula : [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N+X- wherein R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, - CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups,
- Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R 1 R 2 R 3 R 4 N + X - (i) wherein R 1 is C 8 -C 16 alkyl, each of R 2 , R 3 and R 4 is independently C 1 -C 4 alkyl, C 1 -C 4 hydroxy alkyl, benzyl, and -(C 2 H 4 0) x H where x has a value from 1 to 5, and X is an anion. Not more than one of R 2 , R 3 or R 4 should be benzyl.
- the preferred alkyl chain length for R 1 is C 12 -C 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
- Preferred groups for R 2 R 3 and R 4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
- the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants.
- 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 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 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 and citric acid.
- 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 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 is described in European Patent Application 130,756.
- Protease B is described in European Patent Application Serial No. 87303761.8.
- Amylases include, for example, - amylases obtained from a special strain of B.licheniformis, 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).
- 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).
- cellulases are preferred enzymes in that cellulases achieve a multicycle softening benefit, which is restricted to cotton containing fibers, by cleaving and assisting the removal of cellulosic fibrils. These normally form on the fibers during the normal washing process, and increase after consecutive washes and upon ageing of the fabric. The interaction of these fibrils with each other impart a degree of rigidity to the fabric surface that is felt by the consumer as harshness, which is alleviated by the use of cellulase enzymes.
- the cellulases can be added in combination with softening silicones.
- Softening silicones deliver their single cycle softening benefit by depositing directly on the fabric.
- 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. 91202882.6, 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, diisopropanolamime, etc.), 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, Application No. 86200586.5.
- Non-boric acid and borate stabilizers are preferred.
- Borate may be conveniently incorporated into Heavy Duty Liquid detergent in the form of a solution. Boric acid has a solubility in water of about 13% at 60°C. Sodium metaborate is commercially available as a solution with activity of 10.1% (expressed in terms of B2O3) at 20°C.
- the solution be concentrated. More concentrated solutions may be obtained by neutralising boric acid with organic amines, such as monoethanolamine (MEA).
- organic amines such as monoethanolamine (MEA).
- a highly preferred concentrated borate solution can be prepared by heat treatment of aqueous borate solution.
- a solution heated to a temperature above 60°C, and preferably above 90°C, and maintained at that temperature for at least 5 minutes, preferably between 30 and 60 minutes will be stable at 20°C for at least a month.
- a solution with activity of at least 33% (expressed in terms of B2O3) can be made and stored without separation or precipitation.
- the preferred molar ratio of Na2O: B2O3 is 0.15:1 to 0.38:1, more preferably 0.22:1 to 0.35:1.
- Boric acid, metaborate or borax may all be used as raw materials.
- Other polyols such as glycerol may also be incorporated into the concentrated solution.
- Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319 and 3,519,570.
- enzyme oxidation scavengers which are described in Copending European Patent aplication N 92870018.6 filed on January 31, 1992.
- enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
- 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 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 R .
- suds controlling agents comprise a silicone antifoam compound, a carrier material and an organic coating material further containing glycerol at a weight ratio with the silicone antifoam compound of 1:2 to 3:1.
- 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 non-encapsulated and 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 anhydride-acrylic 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.
- 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(PO H) 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 sulfobenzoid 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.
- Preferred polymers for incorporation into the dye transfer inhibiting composition of the present invention include polyamine N-oxide polymers, copolymers of N-vinylpyrolidone and N-vinylimidazole, polyvinylpyrolidone, polyvinyloxazolidone and polyvinylimidazole. Said polymers are described in EP 622 447.
- the detergent compositions according to the invention can be in liquid, paste, gels, bars 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.
- 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.
- 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.
- a liquid detergent composition according to the present invention is prepared, having the following compositions : Table I % by weight of the total detergent composition Fatty acid 10 Oleic acid 4 Citric acid 1 NaOH 3.4 Propanediol 1.5 Ethanol 10
- 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 DE value which represents the change in the Hunter L, a, b , values which are determined by reflecting spectrometrie.
- Example I demonstrates the enhanced dye transfer inhibiting performance of the vinylpyridine copolymers.
- 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 - - Alkyl alkoxylated sulfate - 9 - Polyhydroxy fatty acid - - 9 Trimethyl ammonium chloride C12-C14 - - 4 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 Phosphonic acid 1.5 1.5 1.5 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)-co-(acrylate) 0-1 0-1 0-1 Thermamyl 0.13 0.13 0.13 Carezyme 0.014 0.014
- 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 - - Alkyl alkoxylated sulfate - 10 - Polyhydroxy fatty acid - - 9 Trimethyl ammonium chloride C12-C14 - - 4 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 actylic acid copolymer 5.00 5.00 5.00 Cellulase (active protein) 0.03 0.03 0.03 Alkalase/BAN 0.60 0.
- compositions (Example II(A/B/C) and III(A/B/C)) were very good at displaying excellent clay and detergent performance with outstanding color-care performance on colored fabrics and mixed loads of colored and white fabrics.
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69522679T DE69522679T2 (de) | 1995-07-20 | 1995-07-20 | Farbstoffübertragung hemmende Waschmittelzusammensetzungen |
EP95202004A EP0754748B1 (de) | 1995-07-20 | 1995-07-20 | Farbstoffübertragung hemmende Waschmittelzusammensetzungen |
PT95202004T PT754748E (pt) | 1995-07-20 | 1995-07-20 | Composicoes detergentes que inibem a transferencia de corantes |
AT95202004T ATE205524T1 (de) | 1995-07-20 | 1995-07-20 | Farbstoffübertragung hemmende waschmittelzusammensetzungen |
ES95202004T ES2162893T3 (es) | 1995-07-20 | 1995-07-20 | Composiciones detergentes que inhiben la transferencia de colorantes. |
DK95202004T DK0754748T3 (da) | 1995-07-20 | 1995-07-20 | Detergentsammensætninger, der hæmmer farvestofoverførsel |
JP50674797A JP2002515921A (ja) | 1995-07-20 | 1996-07-12 | ビニルピリジン共重合体をベースとする染料移動抑制洗剤組成物 |
MX9800573A MX9800573A (es) | 1995-07-20 | 1996-07-12 | Composiciones detergentes que inhiben la transferencia de colorante con base en copolimeros de vinilpiridina. |
CA002227412A CA2227412A1 (en) | 1995-07-20 | 1996-07-12 | Detergent compositions inhibiting dye transfer based on vinylpyridine copolymers |
BR9609751A BR9609751A (pt) | 1995-07-20 | 1996-07-12 | Composições detergentes inibidoras de transferéncia de corante á base de copolímeros de vinil piridina |
PCT/US1996/011594 WO1997004062A1 (en) | 1995-07-20 | 1996-07-12 | Detergent compositions inhibiting dye transfer based on vinylpyridine copolymers |
ARP960103634A AR002874A1 (es) | 1995-07-20 | 1996-07-18 | Composicion detergente inhibidora de la transferencia de colorante que contiene copolimeros de vinilpiridina. |
GR20010401320T GR3036613T3 (en) | 1995-07-20 | 2001-09-13 | Detergent compositions inhibiting dye transfer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95202004A EP0754748B1 (de) | 1995-07-20 | 1995-07-20 | Farbstoffübertragung hemmende Waschmittelzusammensetzungen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0754748A1 true EP0754748A1 (de) | 1997-01-22 |
EP0754748B1 EP0754748B1 (de) | 2001-09-12 |
Family
ID=8220516
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95202004A Expired - Lifetime EP0754748B1 (de) | 1995-07-20 | 1995-07-20 | Farbstoffübertragung hemmende Waschmittelzusammensetzungen |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0754748B1 (de) |
JP (1) | JP2002515921A (de) |
AR (1) | AR002874A1 (de) |
AT (1) | ATE205524T1 (de) |
BR (1) | BR9609751A (de) |
CA (1) | CA2227412A1 (de) |
DE (1) | DE69522679T2 (de) |
DK (1) | DK0754748T3 (de) |
ES (1) | ES2162893T3 (de) |
GR (1) | GR3036613T3 (de) |
MX (1) | MX9800573A (de) |
PT (1) | PT754748E (de) |
WO (1) | WO1997004062A1 (de) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1023430A1 (de) * | 1997-09-19 | 2000-08-02 | Isp Investments Inc. | Wasserlösliche farbstoff komplexierende polymere als farbstoffübertragungsinhibitoren in wäschewasch- und weichspülerzusammensetzungen |
WO2000056849A1 (en) * | 1999-03-25 | 2000-09-28 | The Procter & Gamble Company | Laundry detergent compositions with certain cationically charged dye maintenance polymers |
US6191098B1 (en) | 1999-04-28 | 2001-02-20 | National Starch And Chemical Investment Holding Corporation | Polyvinylpyridinium derivatives as anti-dye transfer agents |
EP1083218A1 (de) * | 1999-09-10 | 2001-03-14 | National Starch and Chemical Investment Holding Corporation | Quaternäre Polyvinylpyridinium-Derivate und ihre Verwendung als entfärbungshemmender Wirkstoff |
WO2002046347A1 (en) * | 2000-12-05 | 2002-06-13 | Isp Investments Inc. | Laundry detergent compositions containing water soluble dye complexing polymers |
US6642200B1 (en) * | 1999-03-25 | 2003-11-04 | The Procter & Gamble Company | Fabric maintenance compositions comprising certain cationically charged fabric maintenance polymers |
US6733538B1 (en) | 1999-03-25 | 2004-05-11 | The Procter & Gamble Company | Laundry detergent compositions with certain cationically charged dye maintenance polymers |
USRE39450E1 (en) * | 1999-04-28 | 2006-12-26 | National Starch And Chemical Investment Holding Co | Polyvinylpyrridinium derivatives as anti-dye transfer agents |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0579295A1 (de) * | 1992-07-15 | 1994-01-19 | The Procter & Gamble Company | Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung |
WO1994011482A1 (en) * | 1992-11-16 | 1994-05-26 | The Procter & Gamble Company | Fabric softening compositions with dye transfer inhibitors for improved fabric appearance |
EP0622447A1 (de) * | 1993-04-26 | 1994-11-02 | The Procter & Gamble Company | Enzym enthaltende Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung |
EP0663438A1 (de) * | 1994-01-13 | 1995-07-19 | The Procter & Gamble Company | Verwendung von Polymeren in aufhellerhaltigen flüssigen Detergenszusammensetzungen zur Vermeidung von Gewebeflecken |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4237016A (en) * | 1977-11-21 | 1980-12-02 | The Procter & Gamble Company | Textile conditioning compositions with low content of cationic materials |
US4179382A (en) * | 1977-11-21 | 1979-12-18 | The Procter & Gamble Company | Textile conditioning compositions containing polymeric cationic materials |
DE3206883A1 (de) * | 1982-02-26 | 1983-09-15 | Basf Ag, 6700 Ludwigshafen | Verwendung von copolymerisaten, die basische gruppen enthalten, als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut |
DE4235798A1 (de) * | 1992-10-23 | 1994-04-28 | Basf Ag | Verwendung von Vinylpyrrolidon- und Vinylimidazol-Copolymerisaten als Waschmitteladditiv, neue Polymerisate des Vinylpyrrolidons und des Vinylimidazols und Verfahren zu ihrer Herstellung |
-
1995
- 1995-07-20 DE DE69522679T patent/DE69522679T2/de not_active Expired - Lifetime
- 1995-07-20 ES ES95202004T patent/ES2162893T3/es not_active Expired - Lifetime
- 1995-07-20 DK DK95202004T patent/DK0754748T3/da active
- 1995-07-20 PT PT95202004T patent/PT754748E/pt unknown
- 1995-07-20 AT AT95202004T patent/ATE205524T1/de active
- 1995-07-20 EP EP95202004A patent/EP0754748B1/de not_active Expired - Lifetime
-
1996
- 1996-07-12 JP JP50674797A patent/JP2002515921A/ja active Pending
- 1996-07-12 WO PCT/US1996/011594 patent/WO1997004062A1/en active Application Filing
- 1996-07-12 BR BR9609751A patent/BR9609751A/pt not_active Application Discontinuation
- 1996-07-12 MX MX9800573A patent/MX9800573A/es unknown
- 1996-07-12 CA CA002227412A patent/CA2227412A1/en not_active Abandoned
- 1996-07-18 AR ARP960103634A patent/AR002874A1/es unknown
-
2001
- 2001-09-13 GR GR20010401320T patent/GR3036613T3/el unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0579295A1 (de) * | 1992-07-15 | 1994-01-19 | The Procter & Gamble Company | Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung |
WO1994011482A1 (en) * | 1992-11-16 | 1994-05-26 | The Procter & Gamble Company | Fabric softening compositions with dye transfer inhibitors for improved fabric appearance |
EP0622447A1 (de) * | 1993-04-26 | 1994-11-02 | The Procter & Gamble Company | Enzym enthaltende Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung |
EP0663438A1 (de) * | 1994-01-13 | 1995-07-19 | The Procter & Gamble Company | Verwendung von Polymeren in aufhellerhaltigen flüssigen Detergenszusammensetzungen zur Vermeidung von Gewebeflecken |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1023430A1 (de) * | 1997-09-19 | 2000-08-02 | Isp Investments Inc. | Wasserlösliche farbstoff komplexierende polymere als farbstoffübertragungsinhibitoren in wäschewasch- und weichspülerzusammensetzungen |
EP1023430A4 (de) * | 1997-09-19 | 2000-11-15 | Isp Investments Inc | Wasserlösliche farbstoff komplexierende polymere als farbstoffübertragungsinhibitoren in wäschewasch- und weichspülerzusammensetzungen |
WO2000056849A1 (en) * | 1999-03-25 | 2000-09-28 | The Procter & Gamble Company | Laundry detergent compositions with certain cationically charged dye maintenance polymers |
US6642200B1 (en) * | 1999-03-25 | 2003-11-04 | The Procter & Gamble Company | Fabric maintenance compositions comprising certain cationically charged fabric maintenance polymers |
US6733538B1 (en) | 1999-03-25 | 2004-05-11 | The Procter & Gamble Company | Laundry detergent compositions with certain cationically charged dye maintenance polymers |
US6191098B1 (en) | 1999-04-28 | 2001-02-20 | National Starch And Chemical Investment Holding Corporation | Polyvinylpyridinium derivatives as anti-dye transfer agents |
USRE39450E1 (en) * | 1999-04-28 | 2006-12-26 | National Starch And Chemical Investment Holding Co | Polyvinylpyrridinium derivatives as anti-dye transfer agents |
EP1083218A1 (de) * | 1999-09-10 | 2001-03-14 | National Starch and Chemical Investment Holding Corporation | Quaternäre Polyvinylpyridinium-Derivate und ihre Verwendung als entfärbungshemmender Wirkstoff |
US6306815B1 (en) | 1999-09-10 | 2001-10-23 | National Starch And Chemical Investment Holding Corporation | Quaternary polyvinylpyrridinium derivatives as anti-dye transfer agents |
WO2002046347A1 (en) * | 2000-12-05 | 2002-06-13 | Isp Investments Inc. | Laundry detergent compositions containing water soluble dye complexing polymers |
US6482790B2 (en) * | 2000-12-05 | 2002-11-19 | Isp Investments Inc. | Laundry detergent compositions containing water soluble dye complexing polymers |
Also Published As
Publication number | Publication date |
---|---|
JP2002515921A (ja) | 2002-05-28 |
ES2162893T3 (es) | 2002-01-16 |
EP0754748B1 (de) | 2001-09-12 |
ATE205524T1 (de) | 2001-09-15 |
BR9609751A (pt) | 1999-07-06 |
GR3036613T3 (en) | 2001-12-31 |
DK0754748T3 (da) | 2001-11-26 |
DE69522679T2 (de) | 2002-06-20 |
AR002874A1 (es) | 1998-04-29 |
DE69522679D1 (de) | 2001-10-18 |
WO1997004062A1 (en) | 1997-02-06 |
PT754748E (pt) | 2002-02-28 |
MX9800573A (es) | 1998-04-30 |
CA2227412A1 (en) | 1997-02-06 |
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