EP0753567A1 - Beim Waschen weichmachende Zusammensetzungen - Google Patents
Beim Waschen weichmachende Zusammensetzungen Download PDFInfo
- Publication number
- EP0753567A1 EP0753567A1 EP95201943A EP95201943A EP0753567A1 EP 0753567 A1 EP0753567 A1 EP 0753567A1 EP 95201943 A EP95201943 A EP 95201943A EP 95201943 A EP95201943 A EP 95201943A EP 0753567 A1 EP0753567 A1 EP 0753567A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- clay
- clays
- softening
- hydroxyethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
Definitions
- the present invention relates to detergent compositions containing a clay softening system. More in particular, the present invention relates to softening through the wash detergent compositions comprising a clay softening system and selected brighteners.
- Detergent compositions providing fabric softening through the wash cycle have been described in art.
- clays are well known as fabric softening agents through the wash.
- the relative ability of the softening clays to meet various performance criteria is very much depending on the presence and concentration of adjunct detergent ingredients.
- adjunct detergent ingredients that is added to detergent compositions are dye transfer inhibiting polymers.
- Said polymers are added to detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto other fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
- Polymers have been used within detergent compositions to inhibit dye transfer.
- examples of such polymers are vinylpyrrolidone polymers such as described EP-A-265 257 and EP 508 034.
- vinylpyrrolidone polymers tend to interact with the clays formulated therewith. Accordingly, both the dye transfer inhibiting performance of the polymers and the softening performance of the clays are negatively affected.
- a process is also provided for laundering operations involving colored fabrics.
- the present invention relates to detergent compositions comprising a clay softening system and specific selected brighteners.
- compositions of the present invention comprise as an essential element a clay softening system :
- the clay softening system comprises a fabric softening clay and may additionally comprise a clay flocculating agent.
- the clay softening system hereof will comprise a fabric softening clay present in an amount of at least 0.5%, preferable from 4% to 30% by weight of the dye transfer inhibiting composition.
- the preferred clays are of the smectite type. Smectite type clays are widely used as fabric softening ingredients in detergent compositions. Most of these clays have a cation exchange capacity of at least 50 meq./100g.
- Smectite clays can be described as three-layer expandable materials, consisting of alumino-silicates or magnesium silicates.
- smectite-type clays There are two distinct classes of smectite-type clays; in the first, aluminium oxide is present in the silicate crystal lattice, in the second class of smectites, magnesium oxide is present in the silicate crystal lattice.
- the general formulas of these smectites are A1 2 (Si 2 0 5 ) 2 (OH) 2 and Mg 3 (Si 2 O 5 ) (OH) 2 , for the aluminium and magnesium oxide type clay, respectively.
- the range of the water of hydration can vary with the processing to which the clay has been subjected.
- atom substitution by iron and magnesium can occur within the crystal lattice of the smectites, while metal cations such as Na + , Ca 2+ , as well as H + can be co-present in the water of hydration to provide electrical neutrality.
- clays on the basis of one cation predominantly or exclusively absorbed.
- a sodium clay is one in which the absorbed cation is predominantly sodium.
- Such absorbed cations can become involved in equilibrium exchange reactions with cations present in aqueous solutions.
- one equivalent weight of solution cation replaces an equivalent of sodium, for example, and it is customary to measure clay cation exchange capacity in terms of milliequivalents per 100g. of clay (meq/100g.).
- the cation exchange capacity of clays can be measured in several ways, including electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene blue procedure, all as set forth in Grimshaw, The Chemistry and Physics of Clays, Interscience Publishers, Inc. pp. 264-265(1971).
- the cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which in turn, is determinated at least in part by the lattice structure, and the like.
- the ion exchange capacity of clays varies widely in the range from about 2 meq/100 g.
- Illite clays have an ionexchange capacity somewhere in the lower portion of the range, ca. 26 meq/100 g. for an average illite clay.
- illite and kaolinite clays are not useful in the instant compositions. Indeed such illite and kaolinite clays constitute a major component of clay soils.
- smectites such as nontronite having an ionexchange capacity of approximately 50 meq/100 g.
- saponite which has an ion exchange capacity greater than 70 meq/100g.
- the smectite clays commonly used for this purpose herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite.
- the clays herein are available under commercial names such as "fooler clay” (clay found in a relatively thin vein above the main bentonite or montmorillonite veins in the Black Hills) and various tradenames such as Thixogel #1 (also, “Thixo-Jell”) and Gelwhite GP from Georgia Kaolin Co.
- smectite-type minerals obtained under the foregoing commercial and tradenames can comprise mixtures of the various discrete mineral entitites. Such mixtures of the smectite minerals are suitable for use herein.
- Preferred for use herein are the montmorrillonite clays.
- the value of (x+y) is the layer charge of the hectorite clay.
- hectorite clays are preferably selected on the basis of their layer charge properties, i.e. at least 50% is in the range of from 0.23 to 0.31.
- hectorite clays of natural origin having a layer charge distribution such that at least 65% is in the range of from 0.23 to 0.31.
- the hectorite clays suitable in the present composition should preferably be sodium clays, for better softening activity.
- Sodium clays are either naturally occuring, or are naturally-occuring calcium-clays which have been treated so as to convert them to sodium-clays. If calcium-clays are used in the present compositions, a salt of sodium can be added to the compositions in order to convert the calcium clay to a sodium clay. Preferably, such a salt is sodium carbonate, typically added at levels of up to 5% of the total amount of clay.
- hectorite clays suitable for the present compositions include Bentone EW and Macaloid, from NL Chemicals, N.J., U.S.A., and hectorites from Industrial Mineral Ventures.
- the clay softening system herein can comprise clay-flocculating agents.
- the compositions herein may comprise, from 0.05% to 20% by weight of the clay, of flocculating agent, if its molecular weight is 150.000-800.000 and from 0.005% to 2%, by weight of the clay, it its molecular weight is from 800.000 to 5 million.
- Most of these materials are fairly long chain polymers and copolymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine. Gums, like guar gum, are suitable as well.
- polymers of ethylene oxide, acryl amide, or acrylic acid are preferred.
- the polymers should be fairly long chain, i.e., have a weight average molecular weight of at least 100,000.
- weight average molecular weight of the polymers should not exceed 10 million.
- the detergent compositions herein also essentially contain from about 0.005% to 5% by weight of a certain type of hydrophilic optical brightener.
- the compositions herein will comprise from about 0.01% to 1% by weight of this optical brightener.
- hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R 1 is anilino, R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-M-methylamino and M is a salt-forming cation such as sodium or potassium.
- R 1 is anilino
- R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
- the brightener is 4,4'-bis [(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid disodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
- R 1 is anilino
- R 2 is N-2-hydroxyethyl-N-2-methylamino
- M is a cation such as sodium
- the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid disodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
- the liquid 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.
- 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.
- 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.
- 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 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 D E Linear alkyl benzene sulphonate 11.40 - - - 5 Polyhydroxy fatty acid amide - 10 - 5 5 Alkyl alkoxylated sulfate - - 9 9 9 Tallow alkyl sulphate 1.80 1.80 1.80 4 4 C45 alkyl sulphate 3.00 3.00 3.00 - - Dispersant 0.07 0.07 0.07 0.07 0.07 Silicone fluid 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 Trisodium citrate 14.00 14.00 14.00 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Zeolite 32.50 32.50 32.50 32.50 Maleic acid acrylic acid copolymer 5.00 5.00 5.00 5.00 Carezyme 0.1 0.1 0.1 0.1 0.1 0.1 Alkalase/BAN 0.60 0.60 0.60 0.60
- Example I (A/B/C/D/E)
- Example I (A/B/C/D/E)
- a stable liquid detergent composition according to the present invention is prepared, having the following compositions : % by weight of the total detergent composition A B C D Linear alkylbenzene sulfonate 10 15 23 - Polyhydroxy fatty acid amide - 5 - 4 Alkyl alkoxylated sulfate - - - 3 Alkyl sulphate 2 2 4 13 C12-C14 dimethyl ammonium chloride 2 2 2 2 2 Fatty acid 8 8 10 17 Oleic acid 2 2 2 - Citric acid 2 1 1 1 1 Diethylenetriamine pentamethylene 1.5 1.5 1.5 1.5 Phosphonic acid NaOH 5 7 8 7 Propanediol 4 4 4 7 Ethanol 7 7 10 3 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7 0.7 Thermamyl R 300 KNU/g 0.1 0.1 0.1 0.1 Carezyme R 5000 CEVU/g 0.02 0.02 0.02 0.02 0.02 Protease 40 mg/g 0.6 0.6
- Example II (A/B/C/D) were very good at displaying excellent softening and brightener performance with outstanding color-care performance on colored fabrics and mixed loads of colored and white fabrics.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95201943A EP0753567A1 (de) | 1995-07-14 | 1995-07-14 | Beim Waschen weichmachende Zusammensetzungen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95201943A EP0753567A1 (de) | 1995-07-14 | 1995-07-14 | Beim Waschen weichmachende Zusammensetzungen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0753567A1 true EP0753567A1 (de) | 1997-01-15 |
Family
ID=8220490
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95201943A Ceased EP0753567A1 (de) | 1995-07-14 | 1995-07-14 | Beim Waschen weichmachende Zusammensetzungen |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP0753567A1 (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0976866A1 (de) * | 1998-07-28 | 2000-02-02 | Basf Aktiengesellschaft | Textile Flächengebilde |
US6645569B2 (en) | 2001-01-30 | 2003-11-11 | The Procter & Gamble Company | Method of applying nanoparticles |
US6713442B2 (en) | 2001-10-10 | 2004-03-30 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Detergent compositions |
US6794349B2 (en) | 2001-10-10 | 2004-09-21 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Detergent compositions |
EP2169040A1 (de) | 2008-09-30 | 2010-03-31 | The Procter and Gamble Company | Flüssige Reinigungsmittelzusammensetzungen mit zwei- oder mehrfarbigem Effekt |
EP2169041A1 (de) | 2008-09-30 | 2010-03-31 | The Procter and Gamble Company | Flüssige Reinigungsmittelzusammensetzungen mit zwei- oder mehrfarbigem Effekt |
Citations (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1082179A (en) | 1965-07-19 | 1967-09-06 | Citrique Belge Nv | Unsaturated carboxylic salt materials and derivatives thereof |
US3519570A (en) | 1966-04-25 | 1970-07-07 | Procter & Gamble | Enzyme - containing detergent compositions and a process for conglutination of enzymes and detergent compositions |
US3600319A (en) | 1968-06-25 | 1971-08-17 | Procter & Gamble | Process for application of enzymes to spray-dried detergent granules |
US3664961A (en) | 1970-03-31 | 1972-05-23 | Procter & Gamble | Enzyme detergent composition containing coagglomerated perborate bleaching agent |
GB1296839A (de) | 1969-05-29 | 1972-11-22 | ||
DE2247832A1 (de) | 1971-09-30 | 1973-04-05 | Rikagaku Kenkyusho | Alkalische cellulase und verfahren zu ihrer erzeugung |
GB1372034A (en) | 1970-12-31 | 1974-10-30 | Unilever Ltd | Detergent compositions |
US3929678A (en) | 1974-08-01 | 1975-12-30 | Procter & Gamble | Detergent composition having enhanced particulate soil removal performance |
US3933672A (en) | 1972-08-01 | 1976-01-20 | The Procter & Gamble Company | Controlled sudsing detergent compositions |
DE2646126A1 (de) | 1976-10-13 | 1978-04-20 | Baer Elektrowerke Kg | Schaltungsanordnung zur steuerung von elektrischen stromverbrauchern |
US4116885A (en) | 1977-09-23 | 1978-09-26 | The Procter & Gamble Company | Anionic surfactant-containing detergent compositions having soil-release properties |
US4228044A (en) | 1978-06-26 | 1980-10-14 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal and antiredeposition performance |
US4261868A (en) | 1979-08-08 | 1981-04-14 | Lever Brothers Company | Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound |
GB2075028A (en) | 1980-04-30 | 1981-11-11 | Novo Industri As | Enzymatic additive |
US4318818A (en) | 1979-11-09 | 1982-03-09 | The Procter & Gamble Company | Stabilized aqueous enzyme composition |
GB2095275A (en) | 1981-03-05 | 1982-09-29 | Kao Corp | Enzyme detergent composition |
EP0130756A1 (de) | 1983-06-24 | 1985-01-09 | Genencor International, Inc. | Prokaryotische Carbonyl-Hydrolasen, Verfahren, DNA, Vektoren und transformierte Wirte zu ihrer Herstellung und diese Hydrolasen enthaltende Detergenszusammensetzungen |
GB2168717A (en) * | 1984-12-24 | 1986-06-25 | Colgate Palmolive Co | Controlling viscosity of fabric softening heavy duty liquid detergent containing bentonite |
EP0094118B1 (de) | 1982-05-10 | 1986-09-03 | THE PROCTER & GAMBLE COMPANY | Phosphatarme Wäschewaschmittelzusammensetzungen |
EP0199405A2 (de) | 1985-04-15 | 1986-10-29 | The Procter & Gamble Company | Flüssige Reinigungsmittel mit einer oberflächenaktiven Verbindung, einem proteolytischen Enzym und Borsäure |
EP0070077B1 (de) | 1981-07-13 | 1987-01-21 | THE PROCTER & GAMBLE COMPANY | Feinwaschpulverzusammensetzung |
EP0075996B1 (de) | 1981-09-28 | 1987-01-21 | THE PROCTER & GAMBLE COMPANY | Ein Alkylpolysaccharid, eine nichtionische Tensidmischung und einen anionischen optischen Aufheller enthaltende Detergenszusammensetzungen |
US4663071A (en) | 1986-01-30 | 1987-05-05 | The Procter & Gamble Company | Ether carboxylate detergent builders and process for their preparation |
US4711730A (en) | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
EP0265257A2 (de) | 1986-10-24 | 1988-04-27 | Unilever Plc | Reinigungsmittel |
EP0272033A2 (de) | 1986-12-15 | 1988-06-22 | The Procter & Gamble Company | Terephthalatestercopolymere und ihre Verwendung in Zusammensetzungen für Wäschereinigung |
EP0297673A2 (de) * | 1987-06-30 | 1989-01-04 | The Procter & Gamble Company | Hektorittonhaltige Waschmittel-/Weichspülerzusammensetzungen |
EP0311342A2 (de) | 1987-10-05 | 1989-04-12 | The Procter & Gamble Company | Sulfoaroylendgruppenhaltige Oligomerester, verwendbar als Vergrauungsinhibitoren in Reinigungsmitteln und in Produkten zum Weichmachen von Wäsche |
WO1989008695A1 (en) * | 1988-03-14 | 1989-09-21 | Novo-Nordisk A/S | Stabilized particulate composition |
WO1989009813A1 (en) | 1988-04-15 | 1989-10-19 | Novo Nordisk A/S | A detergent additive for bleaching fabric |
GB2223028A (en) * | 1988-06-28 | 1990-03-28 | Unilever Plc | Detergent composition including fabric softening clay |
US5071594A (en) | 1989-10-02 | 1991-12-10 | Ethyl Corporation | Free flowing granular laundry detergent comprising tert-amine oxide dihydrate |
US5075501A (en) | 1989-10-02 | 1991-12-24 | Ethyl Corporation | Mixed tert-amine oxide dihydrates |
EP0495345A1 (de) | 1991-01-16 | 1992-07-22 | THE PROCTER & GAMBLE COMPANY | Schaumkontrollmittel in granulierter Form |
EP0508034A1 (de) | 1991-04-12 | 1992-10-14 | The Procter & Gamble Company | Polyvinylpyrrolidon enthaltendes Kompaktwaschmittel |
WO1995013354A1 (en) * | 1993-11-10 | 1995-05-18 | The Procter & Gamble Company | Detergent compositions which provide dye transfer inhibition benefits |
-
1995
- 1995-07-14 EP EP95201943A patent/EP0753567A1/de not_active Ceased
Patent Citations (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1082179A (en) | 1965-07-19 | 1967-09-06 | Citrique Belge Nv | Unsaturated carboxylic salt materials and derivatives thereof |
US3519570A (en) | 1966-04-25 | 1970-07-07 | Procter & Gamble | Enzyme - containing detergent compositions and a process for conglutination of enzymes and detergent compositions |
US3600319A (en) | 1968-06-25 | 1971-08-17 | Procter & Gamble | Process for application of enzymes to spray-dried detergent granules |
GB1296839A (de) | 1969-05-29 | 1972-11-22 | ||
US3664961A (en) | 1970-03-31 | 1972-05-23 | Procter & Gamble | Enzyme detergent composition containing coagglomerated perborate bleaching agent |
GB1372034A (en) | 1970-12-31 | 1974-10-30 | Unilever Ltd | Detergent compositions |
DE2247832A1 (de) | 1971-09-30 | 1973-04-05 | Rikagaku Kenkyusho | Alkalische cellulase und verfahren zu ihrer erzeugung |
US3933672A (en) | 1972-08-01 | 1976-01-20 | The Procter & Gamble Company | Controlled sudsing detergent compositions |
US3929678A (en) | 1974-08-01 | 1975-12-30 | Procter & Gamble | Detergent composition having enhanced particulate soil removal performance |
DE2646126A1 (de) | 1976-10-13 | 1978-04-20 | Baer Elektrowerke Kg | Schaltungsanordnung zur steuerung von elektrischen stromverbrauchern |
US4116885A (en) | 1977-09-23 | 1978-09-26 | The Procter & Gamble Company | Anionic surfactant-containing detergent compositions having soil-release properties |
US4228044A (en) | 1978-06-26 | 1980-10-14 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal and antiredeposition performance |
US4261868A (en) | 1979-08-08 | 1981-04-14 | Lever Brothers Company | Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound |
US4318818A (en) | 1979-11-09 | 1982-03-09 | The Procter & Gamble Company | Stabilized aqueous enzyme composition |
GB2075028A (en) | 1980-04-30 | 1981-11-11 | Novo Industri As | Enzymatic additive |
US4435307A (en) | 1980-04-30 | 1984-03-06 | Novo Industri A/S | Detergent cellulase |
GB2095275A (en) | 1981-03-05 | 1982-09-29 | Kao Corp | Enzyme detergent composition |
EP0070077B1 (de) | 1981-07-13 | 1987-01-21 | THE PROCTER & GAMBLE COMPANY | Feinwaschpulverzusammensetzung |
EP0075996B1 (de) | 1981-09-28 | 1987-01-21 | THE PROCTER & GAMBLE COMPANY | Ein Alkylpolysaccharid, eine nichtionische Tensidmischung und einen anionischen optischen Aufheller enthaltende Detergenszusammensetzungen |
EP0094118B1 (de) | 1982-05-10 | 1986-09-03 | THE PROCTER & GAMBLE COMPANY | Phosphatarme Wäschewaschmittelzusammensetzungen |
EP0130756A1 (de) | 1983-06-24 | 1985-01-09 | Genencor International, Inc. | Prokaryotische Carbonyl-Hydrolasen, Verfahren, DNA, Vektoren und transformierte Wirte zu ihrer Herstellung und diese Hydrolasen enthaltende Detergenszusammensetzungen |
GB2168717A (en) * | 1984-12-24 | 1986-06-25 | Colgate Palmolive Co | Controlling viscosity of fabric softening heavy duty liquid detergent containing bentonite |
EP0199405A2 (de) | 1985-04-15 | 1986-10-29 | The Procter & Gamble Company | Flüssige Reinigungsmittel mit einer oberflächenaktiven Verbindung, einem proteolytischen Enzym und Borsäure |
US4663071B1 (de) | 1986-01-30 | 1992-04-07 | Procter & Gamble | |
US4663071A (en) | 1986-01-30 | 1987-05-05 | The Procter & Gamble Company | Ether carboxylate detergent builders and process for their preparation |
US4711730A (en) | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
EP0265257A2 (de) | 1986-10-24 | 1988-04-27 | Unilever Plc | Reinigungsmittel |
EP0272033A2 (de) | 1986-12-15 | 1988-06-22 | The Procter & Gamble Company | Terephthalatestercopolymere und ihre Verwendung in Zusammensetzungen für Wäschereinigung |
EP0297673A2 (de) * | 1987-06-30 | 1989-01-04 | The Procter & Gamble Company | Hektorittonhaltige Waschmittel-/Weichspülerzusammensetzungen |
EP0311342A2 (de) | 1987-10-05 | 1989-04-12 | The Procter & Gamble Company | Sulfoaroylendgruppenhaltige Oligomerester, verwendbar als Vergrauungsinhibitoren in Reinigungsmitteln und in Produkten zum Weichmachen von Wäsche |
WO1989008695A1 (en) * | 1988-03-14 | 1989-09-21 | Novo-Nordisk A/S | Stabilized particulate composition |
WO1989009813A1 (en) | 1988-04-15 | 1989-10-19 | Novo Nordisk A/S | A detergent additive for bleaching fabric |
GB2223028A (en) * | 1988-06-28 | 1990-03-28 | Unilever Plc | Detergent composition including fabric softening clay |
US5071594A (en) | 1989-10-02 | 1991-12-10 | Ethyl Corporation | Free flowing granular laundry detergent comprising tert-amine oxide dihydrate |
US5075501A (en) | 1989-10-02 | 1991-12-24 | Ethyl Corporation | Mixed tert-amine oxide dihydrates |
EP0495345A1 (de) | 1991-01-16 | 1992-07-22 | THE PROCTER & GAMBLE COMPANY | Schaumkontrollmittel in granulierter Form |
EP0508034A1 (de) | 1991-04-12 | 1992-10-14 | The Procter & Gamble Company | Polyvinylpyrrolidon enthaltendes Kompaktwaschmittel |
WO1995013354A1 (en) * | 1993-11-10 | 1995-05-18 | The Procter & Gamble Company | Detergent compositions which provide dye transfer inhibition benefits |
Non-Patent Citations (3)
Title |
---|
GRIMSHAW: "Chemistry and Physics of Clays", 1971, INTERSCIENCE PUBLISHERS, INC., pages: 264 - 265 |
JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY, vol. 52, 1975, pages 323 - 329 |
SCHWARTZ, PERRY, BERCH: "Surface Active Agents and Detergents", vol. I AND II |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0976866A1 (de) * | 1998-07-28 | 2000-02-02 | Basf Aktiengesellschaft | Textile Flächengebilde |
US6645569B2 (en) | 2001-01-30 | 2003-11-11 | The Procter & Gamble Company | Method of applying nanoparticles |
US6863933B2 (en) | 2001-01-30 | 2005-03-08 | The Procter And Gamble Company | Method of hydrophilizing materials |
US6872444B2 (en) | 2001-01-30 | 2005-03-29 | The Procter & Gamble Company | Enhancement of color on surfaces |
US7112621B2 (en) | 2001-01-30 | 2006-09-26 | The Proctor & Gamble Company | Coating compositions for modifying surfaces |
US6713442B2 (en) | 2001-10-10 | 2004-03-30 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Detergent compositions |
US6794349B2 (en) | 2001-10-10 | 2004-09-21 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Detergent compositions |
EP2169040A1 (de) | 2008-09-30 | 2010-03-31 | The Procter and Gamble Company | Flüssige Reinigungsmittelzusammensetzungen mit zwei- oder mehrfarbigem Effekt |
EP2169041A1 (de) | 2008-09-30 | 2010-03-31 | The Procter and Gamble Company | Flüssige Reinigungsmittelzusammensetzungen mit zwei- oder mehrfarbigem Effekt |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0581753B1 (de) | Polymere Dispergiermittel enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung | |
EP0635565B1 (de) | Die Farbstoffübertragung hemmende Waschmittelzusammensetzungen | |
US5710119A (en) | Detergent compositions inhibiting dye transfer comprising copolymers of N-vinylimidazole and N-vinylpyrrolidone | |
EP0635566B1 (de) | Die Farbstoffübertragung hemmende Waschmittelzusammensetzungen | |
US5710118A (en) | Detergent compostions inhibiting dye transfer comprising copolymers of n-vinylimidazole and n-vinylpyrrolidone | |
EP0579295B1 (de) | Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung | |
WO1995017496A1 (en) | Protease containing dye transfer inhibiting compositions | |
JPH10506664A (ja) | ベタインを含有する染料移動抑制組成物 | |
EP0754748B1 (de) | Farbstoffübertragung hemmende Waschmittelzusammensetzungen | |
EP0719856B1 (de) | Beim Waschen weichmachende Waschmittelzusammensetzungen | |
EP0675194A1 (de) | Reinigungszusätze in strukturierten Flüssigkeiten | |
EP0753567A1 (de) | Beim Waschen weichmachende Zusammensetzungen | |
US5604197A (en) | Softening through the wash compositions | |
EP0653480B1 (de) | Beim Waschen weichmachende Zusammensetzungen | |
CA2179010A1 (en) | Use of polymers in liquid detergent compositions containing brighteners for preventing fabric spotting | |
US5883064A (en) | Protease containing dye transfer inhibiting composition | |
MXPA98000573A (en) | Detergent compositions that inhibit the transfer of colorant based on vinilpirid copolymers | |
EP0800570B1 (de) | Waschmittelzusammensetzung mit wasserunlöslichem, entfärbungshemmendem polymerwirkstoff | |
EP0753569A1 (de) | Stabile flüssige, beim Waschen weichmachende Zusammensetzungen | |
EP0635563A1 (de) | Zusammensetzungen zur Verhinderung der Farbstoffübertragung mit Wascheweichspülmittel | |
WO1994002578A1 (en) | Dye transfer inhibiting compositions comprising polymeric dispersing agents | |
EP0664334A1 (de) | Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung | |
JPH10501278A (ja) | オレオイルサルコシネートを含有する染料移動抑制組成物 | |
EP0863967A1 (de) | Flüssige waschmittelzusammensetzungen enthaltend alkylpolyetherglyceryl-sulfate oder sulfonate | |
EP0664335A1 (de) | Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE |
|
17P | Request for examination filed |
Effective date: 19970701 |
|
17Q | First examination report despatched |
Effective date: 20000110 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 20020119 |