EP0579295A1 - Detergent compositions inhibiting dye transfer - Google Patents
Detergent compositions inhibiting dye transfer Download PDFInfo
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- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
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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
- C11D3/3792—Amine 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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Abstract
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.
Description
- The present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing.
- One of the most persistent and troublesome problems arising during modern fabric laundering operations is the tendency of some colored fabrics to release dye into the laundering solutions. The dye is then transferred onto other fabrics being washed therewith.
- One way of overcoming this problem would be to complex or adsorb the fugitive dyes washed out of dyed fabrics before they have the opportunity to become attached to other articles in the wash.
- Polymers have been used within detergent compositions to inhibit dye transfer.
- EP-A-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.
- It is now surprisingly found that certain polyamine N-oxide polymers are very efficient in eliminating transfer of solubilized or suspended dyes. This finding allows to formulate compositions which exhibit excellent dye transfer inhibiting properties.
- According to another embodiment of this invention 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. - The 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.
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. - Other suitable 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. Examples of 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. However 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. Preferably, 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.
Typically, 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.
- The synthesis of 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. A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
- Mixtures of 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. In each instance 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. Examples of preferred 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. 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.
- Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
RO (CnH2nO)tZx
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. - Also suitable as 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. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. - The compositions according to the present invention may further comprise 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. Though less preferred for obvious environmental reasons, 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.
Especially for the liquid execution herein, 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.
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.
Other 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.
- Other components used in 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.
- Another optional ingredient is 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. Alternatively 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.
- As mentioned above, 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. - Especially preferred silicone suds controlling agents are described in Copending European Patent application N°92201649.8. Said 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.
- Other 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. 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.
- Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Proteolytic enzymes 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.
- Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, 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.
- Examples of such cellulases are 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. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-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)). 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.
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, 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. - A wide range of enzyme materials and means for their incorporation into synthetic detergent granules is also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al (incorporated herein by reference). Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. patent 4,507,219, Hughes, issued March 26, 1985, both incorporated herein by reference. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981, also incorporated herein by reference.
- For granular detergents, 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. In liquid formulations, an enzyme stabilization system is preferably utilized. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, 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. 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, di-isopropanolamime, etc.), and boric acid or alkali metal borate. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. patent 4,261,868, issued April 14, 1981 to Horn, et al, U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, both incorporated herein by reference, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. 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.
- The following examples 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 Δc value which represents the change in the Hunter a, b values which are determined by reflecting spectrometrie. The Δc value is defined by the following equation:
where the subscripts i and f refer to the Hunter value before and after washing in the presence of the bleeding fabric, respectively. The least significant difference is 1 at 95% confidence level. - 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.
- pH =7.8
- A: A detergent composition according to Table I which does not contain any dye transfer inhibition system.
- B: A detergent composition according to Table I containing 10 ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of 1:4.
-
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 - The test of Example I was carried out using the following experimental conditions:
pH= 7.8 - A: A detergent composition according to Table I without any dye transfer inhibition system
- B: A detergent composition according to Table I containing 100 ppm of poly(2-vinylpyridine-N-oxide) which has an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of 1:4.
-
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. The launder-o-meter beaker contains 400 ml of a detergent solution, a 20cm piece of the colored fabric and two multifiber swatches which are used as a pick-up tracer for the bleeding dye.
pH= 10.5 - A: A detergent composition according to Table I without any dye transfer inhibition system
- B: A detergent composition according to Table I containing 70 ppm of poly 2-(Dimethylamino)-ethylmethacryllate-N-oxide which has an average molecular weight of about 100,000.
-
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. The launder-o-meter beaker contains 200 ml of a detergent solution, a 4cmx10cm piece of the colored fabric and two multifiber swatches which are used as a pick-up tracer for the bleeding dye.
pH= 10.5 - A: A detergent composition according to Table I without any dye transfer inhibition system
- B: A detergent composition according to Table I containing 7ppm (B1), 35ppm (B2) and 70 ppm (B3) of poly-1-vinylimidazole-N-oxide which has an average molecular weight of about 150,000 .
-
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. A 26cm by 31cm terry towel was used as the pick-up tracer for the bleeding dye.
pH= 10.5 - A: detergent solution without any dye transfer inhibition system
- B: detergent solution which delivers 7ppm of polydialkylmethy1amine-N-oxide in the wash solution(average molecular weight range of about 150,000).
-
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.
-
- A: detergent without any dye transfer inhibition system
- B: detergent composition which delivers 7 ppm of poly(4-vinylpyridine-N-oxide) in the wash solution (average molecular weight is about 50,000).
- The effect of degree of oxidation of polyvinylpyridine-N-oxide (PVNO) on the DTI performance was evaluated in a launder-o-meter test which simulates a 30 min wash cycle. The dye transfer inhibition capacity of the different PVNO samples was tested using the same amount of a cotton bleeding fabric dyed with Direct Blue 90. The pick-up tracer for dye transfer is a multifiber swatch.
The extent of dye transfer is reported in terms of the Hunter ΔE value which is calculated versus a reference washed in the absence of the bleeding fabric. - 10 ppm of PVNO (Average MW ∼ 60,000) in a detergent solution according to Table I.
The oxidation degree was determined by Nuclear Magnetic resonance (NMR). - Reference ΔE in the absence of PVNO is 17.0
Oxidation degree (%) ΔE 35 16.4 40 15.9 58 11.3 73 10.6 83 8.3 92 6.7 - 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 (ISOFOLr) 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
Claims (15)
- A dye transfer inhibiting composition comprising polyamine N-oxide polymers which contain units having the following structure formula :
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.
- A dye transfer inhibiting composition according to claim 1 wherein P is a polymerisable unit wherein the N-O group is attached to and wherein R is selected from an aromatic or heterocyclic group.
- A dye transfer inhibiting composition according to claim 2 wherein the nitrogen of the N-O group forms part of the R-group.
- A dye transfer inhibiting composition according to claim 3 wherein the R-group is selected from pyridine, pyrrole, quinoline, acridine, imidazole and derivatives thereof.
- A dye transfer inhibiting composition according to claim 1,2 wherein the nitrogen of the N-O group is attached to the R-group.
- A dye transfer inhibiting composition according to claim 5 wherein R is a phenyl group.
- A dye transfer composition according to claim 1 wherein P is a polymerisable unit, whereto the N-O group forms part of the polymerisable unit and wherein R is selected from an aromatic or heterocyclic group.
- A dye transfer inhibiting composition according to claim 7 wherein the nitrogen of the N-0 group forms part of the R-group.
- A dye transfer inhibiting composition according to claim 8 wherein the R-group is selected from pyridine, pyrrole, quinoline, acridine, imidazole and derivatives thereof.
- A dye transfer inhibiting composition according to claim 1-9 wherein the polymeric backbone is derived from the group of the polyvinyl polymers.
- A dye transfer inhibiting composition according to claim 1-10 wherein the ratio of amine to amine N-oxide is from 2:3 to 1:1000000, preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000.
- A dye transfer inhibiting composition according to claims 1-11 wherein the polyamine N-oxide has an average molecular weight 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.
- A dye transfer inhibiting composition according to claims 1-12 wherein the polyamine N-oxide is present at levels from 0.001 to 10 % by weight of the composition.
- A dye transfer inhibiting composition according to claim 1-13 which is a detergent additive, in the form of a non-dusting granule or a liquid.
- A detergent composition which comprises a dye transfer inhibiting composition according to claims 1-14 further comprising surfactants, builders, enzymes and other conventional detergent ingredients.
Priority Applications (52)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93870108A EP0581752B1 (en) | 1992-07-15 | 1993-06-09 | Built dye transfer inhibiting compositions |
ES93870105T ES2132210T3 (en) | 1992-07-15 | 1993-06-09 | COMPOSITIONS TO INHIBIT THE TRANSFER OF DYE WHICH INCLUDE WHITENING AGENTS. |
DE1993622447 DE69322447T2 (en) | 1992-07-15 | 1993-06-09 | Detergent compositions containing enzyme to prevent dye transfer |
DE1993624422 DE69324422T2 (en) | 1992-07-15 | 1993-06-09 | Dye transfer preventing compositions containing bleach |
ES93870107T ES2125968T3 (en) | 1992-07-15 | 1993-06-09 | ENZYMATIC DETERGENT COMPOSITIONS THAT INHIBIT THE TRANSFER OF DYE. |
ES93870109T ES2125970T3 (en) | 1992-07-15 | 1993-06-09 | COMPOSITIONS INHIBITING THE TRANSFER OF DYE INCLUDING POLYMER DISPERSING AGENTS. |
EP93870109A EP0581753B1 (en) | 1992-07-15 | 1993-06-09 | Dye transfer inhibiting compositions comprising polymeric dispersing agents |
EP19930870105 EP0587549B1 (en) | 1992-07-15 | 1993-06-09 | Dye transfer inhibiting compositions comprising bleaching agents |
EP19930870107 EP0581751B1 (en) | 1992-07-15 | 1993-06-09 | Enzymatic detergent compositions inhibiting dye transfer |
DE1993622449 DE69322449T2 (en) | 1992-07-15 | 1993-06-09 | Compositions containing polymeric dispersants to prevent dye transfer |
ES93870108T ES2125969T3 (en) | 1992-07-15 | 1993-06-09 | COMPOSITIONS TO INHIBIT THE TRANSFER OF DYE WITH CONTENT IN IMPROVERS. |
DE1993622448 DE69322448T2 (en) | 1992-07-15 | 1993-06-09 | Compositions containing builders to prevent dye transfer |
EP19930870106 EP0587550B1 (en) | 1992-07-15 | 1993-06-09 | Surfactant containing dye transfer inhibiting compositions |
ES93870106T ES2125967T3 (en) | 1992-07-15 | 1993-06-09 | COMPOSITIONS INHIBITING THE TRANSFER OF DYE WITH SURFACE CONTENT. |
DE1993622461 DE69322461T2 (en) | 1992-07-15 | 1993-06-09 | Compositions containing surfactants to prevent dye transfer |
JP50448394A JP3795066B2 (en) | 1993-04-26 | 1993-06-30 | Dye transfer inhibiting detergent composition |
CA002140282A CA2140282A1 (en) | 1992-07-15 | 1993-06-30 | Dye transfer inhibiting compositions comprising polymeric dispersing agents |
US08/373,196 US5458809A (en) | 1992-07-15 | 1993-06-30 | Surfactant-containing dye transfer inhibiting compositions |
US08/373,259 US5633225A (en) | 1992-07-15 | 1993-06-30 | Detergent compositions inhibiting dye transfer |
AU46582/93A AU4658293A (en) | 1992-07-15 | 1993-06-30 | Detergent compositions inhibiting dye transfer |
US08/373,198 US5458810A (en) | 1992-07-15 | 1993-06-30 | Enzymatic detergent compositions inhibiting dye transfer |
PCT/US1993/006222 WO1994002579A1 (en) | 1992-07-15 | 1993-06-30 | Detergent compositions inhibiting dye transfer |
CA002140289A CA2140289C (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 (en) | 1992-07-15 | 1993-07-06 | |
PH46482A PH30425A (en) | 1992-07-15 | 1993-07-08 | Dye transfer inhibiting compositions comprising polymeric dispersing agents |
PH46483A PH30146A (en) | 1992-11-06 | 1993-07-08 | Surfactant containing dyf transfer inhibiting compositions |
PH46481A PH30144A (en) | 1992-07-15 | 1993-07-08 | Built dye transfer inhibiting compositions |
PH46487A PH29955A (en) | 1992-07-15 | 1993-07-08 | Enzymatic detergent compositions inhibiting dye transfer |
MX9304295A MX190415B (en) | 1992-07-15 | 1993-07-15 | DYE TRANSFER INHIBITOR COMPOSITIONS INCLUDING POLYMERIC DISPERSING AGENTS. |
CN 93116766 CN1043785C (en) | 1992-07-15 | 1993-07-15 | Enzymatic detergent compositions inhibiting dye transfer |
CN 93116770 CN1047623C (en) | 1992-07-15 | 1993-07-15 | Dye transfer inhibiting compositions comprising bleaching agents |
MX9304298A MX191084B (en) | 1992-07-15 | 1993-07-15 | DYE TRANSFER INHIBITOR COMPOSITIONS CONTAINING SURGICAL CONTAINER. |
CN93116767.1A CN1042646C (en) | 1992-07-15 | 1993-07-15 | Built dye transfer inhibiting compositions |
TR00594/93A TR27575A (en) | 1992-07-15 | 1993-07-15 | Paint transfer inhibiting composition containing polymeric dispersing agents. |
TR00616/93A TR28340A (en) | 1992-07-15 | 1993-07-15 | Paint transfer preventive compositions containing bleaching agents. |
MX9304296A MX9304296A (en) | 1992-07-15 | 1993-07-15 | DYE TRANSFER INHIBITOR COMPOSITIONS WITH DETERGENCE IMPROVER. |
TR00617/93A TR28338A (en) | 1992-07-15 | 1993-07-15 | Compositions containing surfactant, which inhibit dye transfer. |
MX9304294A MX190414B (en) | 1992-07-15 | 1993-07-15 | DETERGENT COMPOSITIONS THAT INHIBIT THE TRANSFER OF DYES. |
CN 93116768 CN1042647C (en) | 1992-07-15 | 1993-07-15 | Dye transfer inhibiting compositions comprising polymeric dispersing agents |
CN93116491A CN1040656C (en) | 1992-07-15 | 1993-07-15 | Surfactant-containing dye transfer inhibiting compositions |
MX9304299A MX9304299A (en) | 1992-07-15 | 1993-07-15 | DYE TRANSFER INHIBITOR COMPOSITIONS INCLUDING WHITENING AGENTS. |
MX9304297A MX9304297A (en) | 1992-07-15 | 1993-07-15 | ENZYMATIC DETERGENT COMPOSITIONS, INHIBITING THE TRANSFER OF DYE. |
CN 93116769 CN1040454C (en) | 1992-07-15 | 1993-07-15 | Detergent compositions inhibiting dye transfer |
EP93870149A EP0622447A1 (en) | 1993-04-26 | 1993-07-22 | Enzymatic detergent compositions inhibiting dye transfer |
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 (en) | 1992-07-15 | 1993-11-10 | |
PCT/US1994/004221 WO1994025555A1 (en) | 1993-04-26 | 1994-04-11 | Enzymatic detergent compositions inhibiting dye transfer |
AU66363/94A AU6636394A (en) | 1993-04-26 | 1994-04-11 | Enzymatic detergent compositions inhibiting dye transfer |
PE1994240880A PE9195A1 (en) | 1993-04-26 | 1994-04-25 | ENZYMATIC DETERGENT COMPOSITIONS DYE TRANSFER INHIBITORS |
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)
Publication Number | Publication Date |
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EP0579295A1 true EP0579295A1 (en) | 1994-01-19 |
EP0579295B1 EP0579295B1 (en) | 1998-10-28 |
Family
ID=8210784
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93201198A Expired - Lifetime EP0579295B1 (en) | 1992-07-15 | 1993-04-26 | Detergent compositions inhibiting dye transfer |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0579295B1 (en) |
AT (1) | ATE172749T1 (en) |
DE (1) | DE69321778T2 (en) |
DK (1) | DK0579295T3 (en) |
ES (1) | ES2125299T3 (en) |
PE (1) | PE6495A1 (en) |
SA (1) | SA93140122B1 (en) |
TW (1) | TW235308B (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0664333A1 (en) * | 1994-01-19 | 1995-07-26 | The Procter & Gamble Company | Detergent compositions containing polyamine N-oxide polymers |
EP0664332A1 (en) * | 1994-01-19 | 1995-07-26 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
WO1995028462A1 (en) * | 1994-04-14 | 1995-10-26 | The Procter & Gamble Company | Detergent compositions comprising dye transfer inhibitors, and process for making them |
WO1995033026A1 (en) * | 1994-06-01 | 1995-12-07 | The Procter & Gamble Company | Dye transfer inhibiting compositions containing oleoyl sarcosinate |
EP0754748A1 (en) * | 1995-07-20 | 1997-01-22 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
US5597795A (en) * | 1992-10-27 | 1997-01-28 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
EP0800570A1 (en) * | 1994-12-29 | 1997-10-15 | The Procter & Gamble Company | Laundry detergent composition comprising substantially water-insoluble polymeric dye transfer inhibiting agent |
US5730760A (en) * | 1995-07-11 | 1998-03-24 | Rohm And Haas Company | Fabric washing composition and method for inhibiting deposition of dye |
WO1998016437A1 (en) * | 1996-10-15 | 1998-04-23 | The Procter & Gamble Company | A package and a sudsing product combination |
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 |
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EP0135217A1 (en) * | 1983-07-22 | 1985-03-27 | THE PROCTER & GAMBLE COMPANY | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
EP0265257A2 (en) * | 1986-10-24 | 1988-04-27 | Unilever Plc | Detergent composition |
EP0327927A2 (en) * | 1988-02-06 | 1989-08-16 | Henkel Kommanditgesellschaft auf Aktien | Detergent additive |
-
1993
- 1993-04-26 ES ES93201198T patent/ES2125299T3/en not_active Expired - Lifetime
- 1993-04-26 AT AT93201198T patent/ATE172749T1/en not_active IP Right Cessation
- 1993-04-26 DK DK93201198T patent/DK0579295T3/en active
- 1993-04-26 EP EP93201198A patent/EP0579295B1/en not_active Expired - Lifetime
- 1993-04-26 DE DE69321778T patent/DE69321778T2/en not_active Expired - Lifetime
- 1993-07-15 PE PE1993224525A patent/PE6495A1/en not_active Application Discontinuation
- 1993-08-29 SA SA93140122A patent/SA93140122B1/en unknown
- 1993-11-10 TW TW082109433A patent/TW235308B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0135217A1 (en) * | 1983-07-22 | 1985-03-27 | THE PROCTER & GAMBLE COMPANY | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
EP0265257A2 (en) * | 1986-10-24 | 1988-04-27 | Unilever Plc | Detergent composition |
EP0327927A2 (en) * | 1988-02-06 | 1989-08-16 | Henkel Kommanditgesellschaft auf Aktien | Detergent additive |
Cited By (14)
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 |
EP0664332A1 (en) * | 1994-01-19 | 1995-07-26 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
EP0664333A1 (en) * | 1994-01-19 | 1995-07-26 | The Procter & Gamble Company | Detergent compositions containing polyamine N-oxide polymers |
WO1995028462A1 (en) * | 1994-04-14 | 1995-10-26 | The Procter & Gamble Company | Detergent compositions comprising dye transfer inhibitors, and process for making them |
CN1077135C (en) * | 1994-04-14 | 2002-01-02 | 普罗格特-甘布尔公司 | Detergent compositions comprising dye transfer inhibitors, and process for making them |
WO1995033026A1 (en) * | 1994-06-01 | 1995-12-07 | The Procter & Gamble Company | Dye transfer inhibiting compositions containing oleoyl sarcosinate |
EP0800570A1 (en) * | 1994-12-29 | 1997-10-15 | The Procter & Gamble Company | Laundry detergent composition comprising substantially water-insoluble polymeric dye transfer inhibiting agent |
EP0800570A4 (en) * | 1994-12-29 | 1998-01-28 | Procter & Gamble | Laundry detergent composition comprising substantially water-insoluble polymeric dye transfer inhibiting agent |
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 (en) * | 1995-07-20 | 1997-01-22 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
WO1998016437A1 (en) * | 1996-10-15 | 1998-04-23 | The Procter & Gamble Company | A package and a sudsing product combination |
Also Published As
Publication number | Publication date |
---|---|
TW235308B (en) | 1994-12-01 |
DE69321778T2 (en) | 1999-06-10 |
SA93140122B1 (en) | 2005-07-31 |
DE69321778D1 (en) | 1998-12-03 |
EP0579295B1 (en) | 1998-10-28 |
PE6495A1 (en) | 1995-03-24 |
ATE172749T1 (en) | 1998-11-15 |
ES2125299T3 (en) | 1999-03-01 |
DK0579295T3 (en) | 1999-07-05 |
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