WO1993001267A1 - Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system - Google Patents
Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system Download PDFInfo
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- WO1993001267A1 WO1993001267A1 PCT/US1992/005269 US9205269W WO9301267A1 WO 1993001267 A1 WO1993001267 A1 WO 1993001267A1 US 9205269 W US9205269 W US 9205269W WO 9301267 A1 WO9301267 A1 WO 9301267A1
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- clay
- alkyl
- detergent composition
- fatty acid
- sodium
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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
- C11D3/02—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
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
-
- 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
- C11D3/001—Softening 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to softening through the wash compositions containing a clay softening system.
- Clays in particular smectite clays are known fabric-softening agents, and their use in fabric-softening through the wash has been disclosed in the art. Representative of this art is GB-B-1 400 898. Yet, it is equally well recognized that * deposition of these clays is far from complete; in fact, under typical European laundry
- Patent 809,060 relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can include N-methyl glucamide, added as a low temperature suds enhancing agent.
- U.S. Patent 2,703,798 relates to aqueous detergent
- compositions containing the condensation reaction product of N-alkyl glucamine and an aliphatic ester of a fatty acid are said to be useable in aqueous detergent compositions without further
- PCT International Application WO 83/04412 relates to amphiphilic compounds containing polyhydroxyl aliphatic groups said to be useful for a variety of purposes
- N-alkylglucamide nonionic surfactant which is selected from N-methyl, N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.
- glucamide surfactants are disclosed, for example in DT 2,226,872, which relates to washing compositions
- surfactants comprising one or more surfactants and builder salts selected from polymeric phosphates, sequestering agents, and washing alkalis.
- G.B. Patent 745,036 relates to heterocyclic amides and carboxylic esters thereof that are said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners, etc.
- the present invention provides a detergent compositions comprising :
- R 1 is H, C 1 -C 4 hydrocarbyl , 2 hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R 2 is C 5 -C 31
- Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls connected directly to said chain, or alkoxylated derivatives thereof; (b) a clay-softening system.
- compositions hereof will comprise at least about 1%, typically from about 3% to about 50%, preferably from about 3% to about 30%, of the polyhydroxy fatty acid amide surfactant described below.
- the polyhydroxy fatty acid amide surfactant component of the present invention comprises compounds of the structural formula :
- R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5 -C 3 1 hydrocarbyl, preferably straight chain C 7 -C 19 alkyl or alkenyl, more preferably straight chain C 9 -C 17 alkyl or alkenyl, most preferably straight chain C 11 -C 17 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated
- Z preferably will be derived from a reducing sugar in reductive amination reaction; more preferably Z is a glycityl.
- Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose.
- high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. It should be understood that these corn syrups may yield a mix of sugar components for Z.
- Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 -OH, -CH(CH 2 OH)- (CHOH) n-1 -CH 2 OH, -CH 2 -(CHOH) 2 -(CHOR')-(CHOH)-CH 2 OH, and alkoxylated derivatives thereof, where n is an integer from
- R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
- R 1 can be, for example, N-methyl
- R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
- Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
- polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive
- the product is made by reacting N-alkyl- or N-hydroxyalkyl glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbon
- the amount of catalyst is preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about 10 mole %, on an N-alkyl or N-hydroxyalkylglucamine molar basis.
- the reaction is preferably carried out at from about 138°C to about 170 °C for typically from about 20 to about 90 minutes. When triglycerides are utilized as the fatty ester, the reaction is also
- phase transfer agent calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates
- alkylpolyglycosides straight-chain alkylpolyglycosides, linear glycamide surfactant, and mixtures thereof.
- this process is carried out as follows :
- N-linear glucosyl fatty acid amide product is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This seeds the reaction, thereby increasing reaction rate.
- polyhydroxy "fatty acid” amide materials used herein also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, non-petrochemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.
- the processes used to produce them will also typically produce quantities of nonvolatile by-product such as esteramides and cyclic polyhydroxy fatty acid amide.
- the level of these byproducts will vary depending upon the particular reactants and process conditions.
- the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition to be added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide.
- the preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide by-product.
- the clay softening system is the clay softening system
- the clay softening system comprises a fabric softening clay and, although this is not strictly necessary, it may additionally comprise a clay flocculating agent and/or a humectant.
- the fabric softening clay may additionally comprise a clay flocculating agent and/or a humectant.
- 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 detergent 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./lOOg.
- Smectite clays can be described as three-layer expandable materials, consisting of alumino-silicates or magnesium silicates.
- magnesium oxide is present in the silicate crystal lattice.
- Al 2 (Si 2 O 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. Furthermore, 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. In such equilibrium
- 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
- the ion exchange capacity of clays varies widely in the range from about 2 meq/100 g. for kaolinites to about 150 meq/100 g., and greater, for certain clays of the montmorillonite variety.
- 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 a ionexchange capacity of approximately 50 meq/100 g.
- saponite which has an ionexchange 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 having an ion exchange capacity of 50 to 100 meq/100 g which corresponds to ca 0.2 to 0.6 layer charge.
- hectorites of natural origin in the form of particles having the general formula
- the value of (x+y) is the layer charge of the hectorite clay.
- Such 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
- 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, if 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.
- the polymers should be fairly long chain, i.e., have a weight average molecular weight of at least 100,000. For sufficient water-solubility the weight average
- the organic humectant optionally employed in the clay agglomerates herein may be any of the various water soluble materials utilized for such a purpose.
- the organic humectant is preferably selected from the group consisting of a) aliphatic hydrocarbon polyols having from 2 to 9 carbon atoms; b) ether alcohols derived from the polyols of a); c) ester alcohols derived from the polyols of a); d) mono- and oligosaccharides; and mixtures thereof.
- Highly preferred humectants include glycerol, ethylene glycol, propylene glycol and the dimers and trimers of glycerol, of ethylene glycol and of propylene glycol.
- the clay softening system can comprise from 0.5% to 30%, preferably from 2% to 15%, of the humectant by weight of the clay.
- compositions may contain one or more additional surfactants which can be anionic, cationic or nonionic.
- the surfactant system will include one or more anionic and/or nonionic surfactants in addition to the polyhydroxy fatty acid amide. It is especially preferred to include an anionic surfactant for effective overall cleaning under a wide variety of wash conditions.
- the benefits of this invention are especially realized when the compositions hereof include hardness sensitive surfactants such as alkyl sulfates, alkyl ester sulfonates (e.g., methyl ester sulfonates), alkyl
- alkoxylated sulfonates e.g., alkyl ethoxylated
- alkyl benzene sulfonates e.g., linear alkyl benzene sulfonate
- a conventional nonionic surfactant such as an alkyl ethoxylate or an alkyl polyglycoside, as described below, is desirable.
- the levels of such conventional nonionic surfactants in clay-containing detergent are desirable.
- compositions have to be limited, in view of a negative interaction with the clay.
- conventional nonionic surfactants should not be present at levels in excess of 4% by weight of the detergent composition.
- the amount of additional detersive surfactant present is from 1% to 50% by weight, of the detergent composition, preferably from 3% to 40%, more preferably from 5% to 30%.
- Suitable anionic surfactants include alkyl ester
- sulfonate surfactants of the structural formula :
- R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 hydrocarbyl,
- Suitable salts would include metal salts such as sodium, potassium, and lithium salts, and
- substituted or unsubstituted ammonium salts such as methyl-, dimethyl, -trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammonium and dimethyl
- piperdinium, and cations derived from alkanolamines e.g. monoethanolamine, diethanolamine, and triethanolamine.
- R 3 is C 10 -C 16 alkyl
- R 4 is methyl, ethyl or isopropyl.
- methyl ester sulfonates wherein R 3 is C 14 -C 16 alkyl.
- M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from
- an alkali metal cation e.g., sodium, potassium, lithium
- substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from
- alkanolamines such as ethanolamine , diethanolamine, triethanolamine, and mixtures thereof, and the like.
- alkyl chains of C 12 -C 16 are preferred for lower wash temperatures (e.g., below 50oC) and C 16 -C 18 alkyl chains are preferred for higher wash temperatures (e.g., above 50 oC).
- 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 20 alkyl or hydroxyal
- Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
- Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium and cations derived from
- alkanolamines e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
- surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate,
- polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
- salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
- soap C 9 -C 20 linear alkylbenzenesulphonates, C 8 -C 22 primary or secondary alkanesulphonates, and C 8 -C 24 olefinsulphonates,
- sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
- alkyl glycerol sulfonates 1,082,179, 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 N-acyl isethionates, acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of
- sulfosuccinate diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), N-acyl
- sarcosinates sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH 2 CH 2 O)kCH 2 COO-M + wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation and fatty acids esterified with
- 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 Shwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678.
- Suitable conventional nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678.
- Exemplary, non-limiting classes of useful nonionic surfactants are :
- Nonionic surfactants of this type include IgepalTMCO-630, marketed by the GAF Corporation; and TritonTMX-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkyl phenol alkoxylates, e.g., alkyl phenol ethoxylates.
- the condensation products of C 12-22 aliphatic alcohols with from 1 to 25 moles of ethylene oxide include TergitolTM15-S-9 (the condensation product of C 11- C 15 linear secondary alcohol with 9 moles ethylene oxide), TergitolTM24-L-6 NMW (the condensation product of C 12 -C 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union
- NeodolTM45-9 the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide
- NeodolTM23-6.5 (the condensation product of C 12 -C 13 linear alcohol with 6.5 moles of ethylene oxide)
- NeodolTM45-7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide)
- NeodolTM45-4 (the condensation product of C 14 -C 15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company
- KyroTMEOB (the condensation product of C 13 -C 15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company.
- These surfactants are commonly referred to as alkyl
- condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
- Examples of compounds of this type include certain of the commercially-available
- PluronicTM surfactants marketed by BASF.
- surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF. Amine oxides, having the formula
- R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms
- R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof
- x is from 0 to 3
- each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
- the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
- the preferred alkylpolyglycosides have the formula
- R 2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3 , preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
- the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantely the 2-position.
- Cationic detersive surfactants can also be included in detergent compositions of the present invention.
- Cationic surfactants include the ammonium surfactants such as
- alkyldimethylammonium halogenides and those surfactants having the formula :
- 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 -,
- each R 4 is selected from the group consisting of C 1 -
- R 5 is the same as R 4 or is an alkyl chain
- Ampholytic surfactants can be incorporated into the
- detergent compositions hereof These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of
- heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
- One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate.
- Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary
- Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
- compositions of the present invention can be either in particulate form, or in form of an aqueous dispersion of the clay particles, depending on the required
- composition of the invention can be added during the main wash stage or during a rinse cycle of the washing
- the particulate form encompasses both "regular” and high density “compact” executions.
- Detergent compositions of the present invention can comprise inorganic or organic detergent builders to assist in mineral hardness control.
- the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
- Liquid formulations typically comprise at least 1%, more typically from 5% to 50%, preferably 5% to 30%, by weight of detergent builder.
- Granular formulations typically comprise at least 1%, more typically from 10% to 80%, preferably from 15% to 50% by weight of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
- Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and
- carbonates including bicarbonates and sesquicarbonates
- sulphates including bicarbonates and sesquicarbonates
- sulphates including bicarbonates and sesquicarbonates
- aluminosilicates including bicarbonates and sesquicarbonates
- silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839.
- layered silicates such as the layered sodium silicates described in U.S. Patent 4,664,839.
- other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
- carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent
- Aluminosilicate builders are especially useful in the present invention.
- Preferred aluminosilicates are
- z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
- aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be
- crystalline aluminosilicate ion exchange material has the formula :
- x is from about 20 to about 30, especially about 27.
- This material is known as Zeolite A.
- the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
- phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-1, 1-diphosphonate particularly the sodium and potassium salts, the water- soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene,
- Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
- polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
- Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt.
- alkali metals such as sodium, potassium, and lithium salts, especially sodium salts, or ammonium and substituted ammonium (e.g., alkanolammonium) salts are preferred.
- polycarboxylate builders include a variety of categories of useful materials.
- One important category of polycarboxylate builders encompasses the ether polycarboxylates.
- a number of ether polycarboxylates encompasses the ether polycarboxylates.
- polycarboxylates have been disclosed for use as detergent builders.
- useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, U.S. Patent 3,635,830.
- a specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula :
- Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
- ether hydroxypolycarboxylates represented by the structure :
- each R is the same or different and selected from hydrogen, C 1 -4 alkyl or C 1 -4 subsituted alkyl (preferably R is hydrogen).
- Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxybenzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
- Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
- polyacetic builder salts include the sodium, potassium, lithium, ammonium and substituted ammonium salts of
- polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benzene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
- Citrate builders e.g., citric acid and soluble salts thereof, is a polycarboxylate builder of particular importance for heavy duty liquid detergent formulations, but can also be used in granular compositions.
- Suitable salts include the metal salts such as sodium, lithium, and potassium salts, as well as ammonium and substituted ammonium salts.
- carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6- hexanedioates and the related compounds disclosed in U.S.
- Useful succinic acid builders include the C 5 -C 20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is
- Alkyl succinic acids typically are of the general formula R-CH(COOH)CH 2 (COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
- the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
- succinate builders include :
- Laurylsuccinates are the preferred
- useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, water-soluble polyacrylates (these polyacrylates having molecular weight to above 2,000 can also be effectively utilized as dispersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
- polyacetal carboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the
- Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
- nonocarboxylic acids, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps". Chain lengths of C 10 -C 20 are typically utlized.
- the hydrocarbyls can be saturated or unsaturated.
- Enzymes can be included in the detergent formulations for a 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. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
- Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASETM and SAVINASETM by Novo Industries A/S (Denmark) and MAXATASETM by International Bio-Synthetics, Inc. (The Netherlands).
- Amylolytic proteins include, for example, RAPIDASETM, International Bio-Synthetics, Inc. and TERMAMYLTM, Novo Industries.
- the cellulases usable in the present invention include both bacterial or fungal cellulase.
- Suitable lipase enzymes for detergent usage include those sold under the tradename Lipolase R by Novo
- the detergent compositions hereof may contain bleaching agents or bleaching compositions containing bleaching agent and one or more bleaching activators.
- One category of bleaching agents that can be used encompasses both a peroxyacid per se and systems which are able to yield peroxyacids in situ.
- Peroxyacids are meant here to include the alkaline and alkaline-earth metal salts thereof.
- Peroxyacids and diperoxyacids are commonly used; examples are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.
- Systems capable of delivering peracids in situ consist in a peroxygen bleaching agent and an activator thereof.
- the peroxygen bleaching agents are those capable of yielding hydrogen peroxide in an aqueous solution; those compounds are well-known in the art, and include hydrogen peroxide, alkali-metal peroxides, organic peroxide bleaching agents such as urea peroxide, inorganic persalt bleaching agents such as the alkali metal perborates, percarbonates, perphosphates, persilicates, and the like.
- sodium perborate commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate.
- the liberated hydrogen peroxide reacts with the bleach activator to form the peroxyacid bleach.
- Classes of bleach activators include esters, imides, imidazoles, oximes, and carbonates. In both classes, preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium
- 4,539,130 are alpha-substituted alkyl or alkenyl esters, such as sodium-4 (2-chlorooctanoyloxy) benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy) benzene sulfonate.
- Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent
- Application No. 0 166 571 i.e., compounds of the general type RXAOOH and RXAL, wherein R is a hydroxcarbyl group, X is a hetero-atom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.
- compositions herein can contain other ingredients which aid in their cleaning performance; this includes polymeric soil release agents, chelating agents, clay soil removal/anti-redeposition agents.
- Polymeric dispersing agents such as acrylic/maleic- based copolymers may also be used as a preferred
- Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
- the average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000.
- copolymers will generally range from 30:1 to 1:1, more preferably from 10:1 to 2:1.
- Water-soluble salts of such acrylic acid-maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915.
- PEG polyethylene glycol
- 100,000 preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
- Optical brighteners and suds suppressors can be
- Liquid detergent compositions can further contain water and other solvents as carriers.
- Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
- Monohydric alcohols are preferred for solubilizing surfactants, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,2-prpoanediol) can also be used.
- polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,2-prpoanediol) can also be used.
- the detergent compositions hereof will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5.
- Liquid product formulations preferably have a pH between 7.5 and 9.5, more preferably between 7.5 and 9.0.
- Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
- one suitable apparatus for use herein comprises a three-liter four-necked flask fitted with a motor-driven paddle stirrer and a thermometer of length sufficient to contact the reaction medium.
- the other two necks of the flask are fitted with a nitrogen sweep and a wide-bore side-arm (caution : a wide-bore side-arm is important in case of very rapid methanol evolution) to which is connected an efficient collecting condenser and vacuum outlet.
- the latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap.
- a 500 watt heating mantle with a variable transformer temperature controller (“Variac”) used to heat the reaction is so placed on a lab-jack that it may be readily raised or lowered to further control temperature of the reaction.
- Variac variable transformer temperature controller
- N-methylglucamine 195 g. , 1. 0 mole , Aldrich, M4700-0
- methyl laurate Procter & Gamble CE 1270, 220.9 g., 1.0 mole
- the solid/liquid mixture is heated with stirring under a nitrogen sweep to form a melt (approximately 25 minutes).
- catalyst anhydrous powdered sodium carbonate, 10.5 g., 0.1 mole, J.T. Baker
- the nitrogen sweep is shut off and the aspirator and nitrogen bleed are adjusted to give 5 inches (5/31 atm.) Hg. vacuum (16343 Pa). From this point on, the reaction temperature is held at 150 oC by adjusting the Variac and/or by raising or lowering the mantle.
- compositions of the present invention are not
- Test procedure 3.5 kg of clean fabric laundry loads were washed in an automatic drum washing machine Miele 423 at 60 °C. The hardness of the water was 2,5 mM
- Alkyl trimethylammonium chloride 1.5 1.5 Fatty alcohol (C 12 -C 15 ) ethoxylate 5 -
- Example I Admix and spray-on (suds suppression, miscellaneous,...) balance to 100
- the softness performance of Example I was compared to Reference I (with 5% ethoxylated nonionic surfactant).
- compositions are prepared with clay-flocculating agent.
- the softness performance of the product with 5% alkylamide (example II) is compared versus the same product with 5% ethoxylated nonionic surfactant
- test II The test conditions are identical to those described in example I.
- nonionic surfactant is nonionic surfactant.
- Admix and spray-on perfumes, enzymes, savinase, buffer,
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP5502234A JPH06508876A (en) | 1991-07-08 | 1992-06-24 | Detergent composition containing polyhydroxy fatty acid amide surfactant and clay softening system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP91201773.8 | 1991-07-08 | ||
EP19910201773 EP0522206B1 (en) | 1991-07-08 | 1991-07-08 | Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system |
Publications (1)
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WO1993001267A1 true WO1993001267A1 (en) | 1993-01-21 |
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PCT/US1992/005269 WO1993001267A1 (en) | 1991-07-08 | 1992-06-24 | Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system |
Country Status (15)
Country | Link |
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EP (1) | EP0522206B1 (en) |
JP (1) | JPH06508876A (en) |
CN (1) | CN1037452C (en) |
CA (1) | CA2113067C (en) |
DE (1) | DE69113259T2 (en) |
ES (1) | ES2077154T3 (en) |
HU (1) | HUT66853A (en) |
IE (1) | IE922133A1 (en) |
IN (1) | IN186294B (en) |
MA (1) | MA22585A1 (en) |
MX (1) | MX9203995A (en) |
PT (1) | PT100644A (en) |
TR (1) | TR26835A (en) |
TW (1) | TW216802B (en) |
WO (1) | WO1993001267A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0593406A1 (en) * | 1992-10-13 | 1994-04-20 | The Procter & Gamble Company | Non-aqueous liquid detergent compositions |
WO1995033038A1 (en) * | 1994-06-01 | 1995-12-07 | The Procter & Gamble Company | Sarcosinate with clay softeners in laundry compositions |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9303721D0 (en) * | 1993-02-24 | 1993-04-14 | Unilever Plc | Detergent composition |
EP0628624A1 (en) | 1993-06-09 | 1994-12-14 | The Procter & Gamble Company | Protease containing dye transfer inhibiting compositions |
AU7244594A (en) * | 1993-06-25 | 1995-01-17 | Procter & Gamble Company, The | Granular laundry detergent compositions containing lipase and sodium nonanoyloxybenzene sulfonate |
EP0635563A1 (en) * | 1993-07-22 | 1995-01-25 | The Procter & Gamble Company | Dye-transfer-inhibiting compositions containing fabric-softening agent |
US5604197A (en) * | 1993-07-22 | 1997-02-18 | The Procter & Gamble Company | Softening through the wash compositions |
DE69319237T2 (en) * | 1993-07-23 | 1999-02-25 | The Procter & Gamble Co., Cincinnati, Ohio | Dye transfer inhibiting detergent compositions |
EP0635565B1 (en) * | 1993-07-23 | 1997-11-12 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
DE4430085C2 (en) * | 1994-08-25 | 1997-02-27 | Henkel Kgaa | Hair shampoos |
EP0719856B1 (en) * | 1994-12-29 | 2002-10-16 | The Procter & Gamble Company | Softening-through-the-wash laundry detergent compositions |
EP0919608A1 (en) * | 1997-11-25 | 1999-06-02 | The Procter & Gamble Company | Use of a polyhydroxyfatty acid amide compound as a softening compound |
GB2352245A (en) * | 1999-07-22 | 2001-01-24 | Procter & Gamble | Detergent compositions |
DE19948671A1 (en) * | 1999-10-08 | 2001-04-19 | Cognis Deutschland Gmbh | laundry detergent |
JP6085454B2 (en) * | 2012-11-29 | 2017-02-22 | 株式会社ミルボン | Washing soap |
EP3085761A1 (en) * | 2015-04-20 | 2016-10-26 | Hayata Kimya Sanayi Anonim Sirketi | Laundry detergent for use in washing of white and coloured fabrics together |
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- 1991-07-08 DE DE1991613259 patent/DE69113259T2/en not_active Expired - Fee Related
- 1991-07-08 ES ES91201773T patent/ES2077154T3/en not_active Expired - Lifetime
- 1991-07-08 EP EP19910201773 patent/EP0522206B1/en not_active Expired - Lifetime
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1992
- 1992-06-24 WO PCT/US1992/005269 patent/WO1993001267A1/en active Application Filing
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- 1992-06-24 JP JP5502234A patent/JPH06508876A/en active Pending
- 1992-06-24 CA CA 2113067 patent/CA2113067C/en not_active Expired - Fee Related
- 1992-06-30 PT PT10064492A patent/PT100644A/en not_active Application Discontinuation
- 1992-06-30 TR TR00615/92A patent/TR26835A/en unknown
- 1992-07-01 IE IE922133A patent/IE922133A1/en not_active Application Discontinuation
- 1992-07-01 IN IN579DE1992 patent/IN186294B/en unknown
- 1992-07-07 MA MA22868A patent/MA22585A1/en unknown
- 1992-07-07 MX MX9203995A patent/MX9203995A/en not_active IP Right Cessation
- 1992-07-08 CN CN92109294A patent/CN1037452C/en not_active Expired - Fee Related
- 1992-07-25 TW TW81105902A patent/TW216802B/zh active
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WO1995033038A1 (en) * | 1994-06-01 | 1995-12-07 | The Procter & Gamble Company | Sarcosinate with clay softeners in laundry compositions |
Also Published As
Publication number | Publication date |
---|---|
ES2077154T3 (en) | 1995-11-16 |
MA22585A1 (en) | 1993-04-01 |
IN186294B (en) | 2001-07-28 |
DE69113259D1 (en) | 1995-10-26 |
PT100644A (en) | 1993-09-30 |
CA2113067A1 (en) | 1993-01-21 |
CN1070223A (en) | 1993-03-24 |
IE922133A1 (en) | 1993-01-13 |
HUT66853A (en) | 1995-01-30 |
CN1037452C (en) | 1998-02-18 |
TW216802B (en) | 1993-12-01 |
CA2113067C (en) | 1997-12-16 |
EP0522206A1 (en) | 1993-01-13 |
TR26835A (en) | 1994-08-12 |
DE69113259T2 (en) | 1996-05-15 |
MX9203995A (en) | 1993-04-30 |
HU9400051D0 (en) | 1994-05-30 |
JPH06508876A (en) | 1994-10-06 |
EP0522206B1 (en) | 1995-09-20 |
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