EP0522206B1 - Polyhydroxyfettsäureamidtenside und ein weichmachendes System auf Basis von Ton enthaltenden Waschmittelzusammensetzungen - Google Patents
Polyhydroxyfettsäureamidtenside und ein weichmachendes System auf Basis von Ton enthaltenden Waschmittelzusammensetzungen Download PDFInfo
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- EP0522206B1 EP0522206B1 EP19910201773 EP91201773A EP0522206B1 EP 0522206 B1 EP0522206 B1 EP 0522206B1 EP 19910201773 EP19910201773 EP 19910201773 EP 91201773 A EP91201773 A EP 91201773A EP 0522206 B1 EP0522206 B1 EP 0522206B1
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- clay
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- detergent composition
- fatty acid
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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
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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
- C11D1/52—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
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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
- C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
- 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
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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
- C11D1/143—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 conditions, less than half of the available clay is deposited onto the fabrics, the remainder being rinsed away with the laundry liquor during the subsequent rinsing steps.
- U.S. Patent 2,965,576 and G.B. 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.
- the product of this reaction is said to be useable in aqueous detergent compositions without further purification.
- PCT International Application WO 83/04412 relates to amphiphilic compounds containing polyhydroxyl aliphatic groups said to be useful for a variety of purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments.
- U.S. Patent 2,982,737 relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an 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 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 :
- compositions hereof will comprise at least 1%, typically from 3% to 50%, preferably from 3% to 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 : wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 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 derivative (preferably ethoxylated or propoxylated) thereof.
- 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 -CH2-(CHOH) n -CH2-OH, -CH(CH2OH)-(CHOH) n-1 -CH2OH, -CH2-(CHOH)2-(CHOR')-(CHOH)-CH2OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2OH.
- R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
- R2-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 amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
- Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, U.S. Patent 2,965,576, U.S. Patent 2,703,798 and U.S. Patent 1,985,424.
- 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 0.5 mole % to 50 mole %, more preferably from 2.0 mole % to 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis.
- the reaction is preferably carried out at from 138°C to 170°C for typically from 20 to 90 minutes.
- the reaction is also preferably carried out using from 1 to 10 weight % of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, 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 by-products 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 10%, preferably less than 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 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./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 Al2(Si2O5)2(OH)2 and Mg3(Si2O5)(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+, Ca2+, 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 2 meq/100 g. for kaolinites to 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.
- 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 Chemicals, N.J., U.S.A., and hectorites from Industrial Mineral Ventures.
- 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.
- 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 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.
- the present 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.
- 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 sulfonates), and 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 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 : wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
- 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.
- R3 is C10-C16 alkyl
- R4 is methyl, ethyl or isopropyl.
- methyl ester sulfonates wherein R3 is C14-C16 alkyl.
- Alkyl sulfate surfactants of the formula ROSO3M wherein R is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and 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 alkanolamines such as ethanolamine , diethanolamine, triethanolamine, and mixtures thereof, and the like.
- alkyl chains of C12-C16 are preferred for lower wash temperatures (e.g., below 50°C) and C16-C18
- Alkyl alkoxylated sulfate surfactants of the formula RO(A) m SO3M wherin R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6, more preferably between 0.5 and 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.
- R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably
- 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.
- Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl 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 C9-C20 linear alkylbenzenesulphonates, C8-C22 primary or secondary alkanesulphonates, and C8-C24 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 C6-C14 diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds
- 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 C12 ⁇ 22 aliphatic alcohols with from 1 to 25 moles of ethylene oxide examples include TergitolTM15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles ethylene oxide), TergitolTM24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), NeodolTM45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and KyroTMEOB (the condensation product of C
- 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.
- condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine include certain of the commercially available TetronicTM compounds, marketed by BASF.
- Amine oxides having the formula wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof; x is from 0 to 3; and each R5 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 R5 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 R2O(C n H 2n O) t (glycosyl) x wherein R2 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.
- 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 : [(R2(OR3) y ][R4(OR3) y ]2R5N+X ⁇ wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, ring structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH2OH wherein R6 is any he
- 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 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 for examples of ampholytic surfactants.
- 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 ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 for examples of zwitterionic surfactants.
- 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 conditions of utilization. In either form, the composition of the invention can be added during the main wash stage or during a rinse cycle of the washing process.
- 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 alkanolammonium salts of phosphonates, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
- silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O 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 Application No. 2,321,001.
- Aluminosilicate builders are especially useful in the present invention.
- Preferred aluminosilicates are zeolite builders which have the formula Na z [(AlO2) z (SiO2) y ].xH2O wherein 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 naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669.
- the crystalline aluminosilicate ion exchange material has the formula : Na12[(AlO2)12(SiO2)12].xH2O wherein x is from 20 to 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.
- Examples of 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, isopyropylidene benzylmethylidene and halo methylidene phosphonates.
- Phosphonate builder salts of the aforementioned types are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,030, U.S. Patent No. 3,422,021, and U.S. Patent Nos. 3,400,148 and 3,422,137.
- 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 have been disclosed for use as detergent builders.
- Examples of 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 : CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming cation.
- a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts.
- TDS tartrate disuccinic acid
- Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
- ether hydroxypolycarboxylates represented by the structure : HO-[C(R)(COOM)-C(R)(COOM)-O] n -H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from 2 to 15 (preferably n is from 2 to 10, more preferably n averages from 2 to 4) and each R is the same or different and selected from hydrogen, C1 ⁇ 4 alkyl or C1 ⁇ 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 ethylenediamine tetraacetic acid and nitrilotriacetic acid.
- 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.
- succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof.
- a particularly preferred compound of this type is dodecenylsuccinic acid.
- Alkyl succinic acids typically are of the general formula R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
- R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 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 : laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application EP-A- 200,263.
- 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 polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
- 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 C10-C20 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® by Novo Industries.
- 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 "per se” 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.
- DPDA diperoxydodecanoic 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-nonanoxyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4-decanoyloxybenzenesulfonate; biophenol A diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.
- peroxygen bleach activators which are disclosed in U.S. Patents 4,483,778 and 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.
- RXAOOH and RXAL 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 component of the dispersing/anti-redeposition agent.
- 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.
- the ratio of acrylate to maleate segments in such 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 EP-A-66915.
- PEG polyethylene glycol
- PEG can exhibit dispersing agent performance as well as act as a clay soil removal/anti-redeposition agent.
- Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
- compositions hereof can be included in the compositions hereof.
- 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.
- 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) and methyl laurate (Procter & Gamble CE 1270, 220.9 g., 1.0 mole) are placed in a flask.
- 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°C by adjusting the Variac and/or by raising or lowering the mantle.
- 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) Calcium and the composition concentration was 0.7% in the wash liquor.
- swatches of terry towel were line dried prior to assessment of softness. Comparative softness assessment was done by expert judges using a scale of 0 to 4 panel-score-units (PSU). In this scale 0 is given for no difference and 4 is given for maximum difference. Softness was assessed after one and after four wash cycles.
- PSU panel-score-units
- compositions are made : Ingredients Percentage by weight Reference I
- Example I Surfactant Linear alkylbenzene sulfonate 8 8 Tallow alkyl sulphate 2 2 Alkyl trimethylammonium chloride 1.5 1.5 Fatty alcohol (C12-C15) ethoxylate 5 - N-methyl N-1-deoxyglucityl C12 alkylamide - 5
- Builder/chelants Zeolite A 23 23 Copolymer of maleic and acrylic acid, sodium salt 5 5
- Bleach Sodium perborate 12 12 N,N,N,T-Tetraacetyl ethylene diamine 4 4 Perfume 0.5 0.5 0.5 Enzymes - - Savinase 1.6 1.6
- Softness system Smectite/montmorillonite clays 10.5 10.5 Glycerol 0.5 0.5 0.5 Polyethylene oxide 0 0 Buffer Carbonate 10.6 10.6 Silicate (2.0) 5 5 Admix and spray-on (suds suppression, miscel
- Example I The softness performance of Example I (with 5% C12 alkylamide base) 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 (reference II).
- the test conditions are identical to those described in example I.
- Softness performance was assessed after one and after four washing cycles : Again, a statistical significant better softness performance is observed with product containing alkylamide vs. the product containing ethoxylated nonionic surfactant.
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Claims (9)
- Waschmittelzusammensetzung, umfassend ein Polyhydroxyfettsäureamid-Tensid der Formel:
und ein Ton-Weichmachersystem. - Waschmittelzusammensetzung nach Anspruch 1, umfassend mindestens 1 Gew.-% des Polyhydroxyfettsäureamids.
- Waschmittelzusammensetzung nach Anspruch 1, wobei das Polyhydroxyfettsäureamid-Tensid die Formel (I) aufweist, worin R¹ Methyl ist, R² C₁₁-C₁₇-Alkyl oder -Alkenyl ist und Z ein von einem reduzierenden Zucker abgeleitetes Glycityl oder ein alkoxyliertes Derivat davon ist.
- Waschmittelzusammensetzung nach Anspruch 1, wobei das Ton-Weichmachersystem einen Ton in einer Menge von mindesten 0,5 Gew.-% der Waschmittelzusammensetzung umfaßt.
- Waschmittelzusammensetzung nach Anspruch 4, wobei der Ton ein Ton vom Smektit-Typ ist.
- Waschmittelzusammensetzung nach Anspruch 1, wobei das Ton-Weichmachersystem ein Ton-Flockungsmittel umfaßt.
- Waschmittelzusammensetzung nach Anspruch 1, wobei das Ton-Weichmachersystem ein Feuchthaltemittel umfaßt.
- Waschmittelzusammensetzung nach Anspruch 1, umfassend weiterhin ein oder mehrere Hilfstenside, gewählt aus der anionische, kationische und nichtionische Waschtenside und Mischungen hiervon umfassenden Gruppe.
- Waschmittelzusammensetzung nach Anspruch 8, wobei die nichtionischen Tenside in Anteilen von weniger als 4 Gew.-% der Waschmittelzusammensetzung vorliegen.
Priority Applications (15)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES91201773T ES2077154T3 (es) | 1991-07-08 | 1991-07-08 | Composiciones detergentes que contienen tensioactivos de amidas de polihidroxiacidos grasos y un sistema de suavizacion a base de arcilla. |
EP19910201773 EP0522206B1 (de) | 1991-07-08 | 1991-07-08 | Polyhydroxyfettsäureamidtenside und ein weichmachendes System auf Basis von Ton enthaltenden Waschmittelzusammensetzungen |
DE1991613259 DE69113259T2 (de) | 1991-07-08 | 1991-07-08 | Polyhydroxyfettsäureamidtenside und ein weichmachendes System auf Basis von Ton enthaltenden Waschmittelzusammensetzungen. |
HU9400051A HUT66853A (en) | 1991-07-08 | 1992-06-24 | Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system |
JP5502234A JPH06508876A (ja) | 1991-07-08 | 1992-06-24 | ポリヒドロキシ脂肪酸アミド界面活性剤と粘土柔軟化系とを含有する洗剤組成物 |
PCT/US1992/005269 WO1993001267A1 (en) | 1991-07-08 | 1992-06-24 | Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system |
CA 2113067 CA2113067C (en) | 1991-07-08 | 1992-06-24 | Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening sytem |
TR00615/92A TR26835A (tr) | 1991-07-08 | 1992-06-30 | Polihidroksi yagli ketleme sistemi |
PT10064492A PT100644A (pt) | 1991-07-08 | 1992-06-30 | Composicoes detergentes para lavagem de roupa que contem um agente tensio-activo de polihidroxiamida de acido gordo e um sistema de amaciamento de argila |
IE922133A IE922133A1 (en) | 1991-07-08 | 1992-07-01 | Detergent compositions containing polyhydroxy fatty acid¹amide surfactants and a clay softening system |
IN579DE1992 IN186294B (de) | 1991-07-08 | 1992-07-01 | |
MX9203995A MX9203995A (es) | 1991-07-08 | 1992-07-07 | Composiciones detergentes que contienen agentes tensioactivos de amida de acido graso polihidroxilico y un sistema suavizador de arcilla. |
MA22868A MA22585A1 (fr) | 1991-07-08 | 1992-07-07 | Compositions detergentes contenant des tensioactifs de type amide d'acide gras polyhydroxyle et un systeme adoucissant a base d'angle. |
CN92109294A CN1037452C (zh) | 1991-07-08 | 1992-07-08 | 含有多羟基脂肪酸酰胺表面活性剂和粘土软化系的洗涤混合物 |
TW81105902A TW216802B (de) | 1991-07-08 | 1992-07-25 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP19910201773 EP0522206B1 (de) | 1991-07-08 | 1991-07-08 | Polyhydroxyfettsäureamidtenside und ein weichmachendes System auf Basis von Ton enthaltenden Waschmittelzusammensetzungen |
Publications (2)
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EP0522206A1 EP0522206A1 (de) | 1993-01-13 |
EP0522206B1 true EP0522206B1 (de) | 1995-09-20 |
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EP19910201773 Expired - Lifetime EP0522206B1 (de) | 1991-07-08 | 1991-07-08 | Polyhydroxyfettsäureamidtenside und ein weichmachendes System auf Basis von Ton enthaltenden Waschmittelzusammensetzungen |
Country Status (15)
Country | Link |
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EP (1) | EP0522206B1 (de) |
JP (1) | JPH06508876A (de) |
CN (1) | CN1037452C (de) |
CA (1) | CA2113067C (de) |
DE (1) | DE69113259T2 (de) |
ES (1) | ES2077154T3 (de) |
HU (1) | HUT66853A (de) |
IE (1) | IE922133A1 (de) |
IN (1) | IN186294B (de) |
MA (1) | MA22585A1 (de) |
MX (1) | MX9203995A (de) |
PT (1) | PT100644A (de) |
TR (1) | TR26835A (de) |
TW (1) | TW216802B (de) |
WO (1) | WO1993001267A1 (de) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0593406A1 (de) * | 1992-10-13 | 1994-04-20 | The Procter & Gamble Company | Nichtwässrige flüssige Waschmittelzusammensetzungen |
GB9303721D0 (en) * | 1993-02-24 | 1993-04-14 | Unilever Plc | Detergent composition |
EP0628624A1 (de) | 1993-06-09 | 1994-12-14 | The Procter & Gamble Company | Protease enthaltende Waschmittelzusammensetzungen mit Zusätzen zur Verhinderung der Farbstoffübertragung |
JPH08511826A (ja) * | 1993-06-25 | 1996-12-10 | ザ、プロクター、エンド、ギャンブル、カンパニー | リパーゼとノナノイルオキシベンゼンスルホン酸ナトリウムとを含有する粒状洗濯洗剤組成物 |
US5604197A (en) * | 1993-07-22 | 1997-02-18 | The Procter & Gamble Company | Softening through the wash compositions |
EP0635563A1 (de) * | 1993-07-22 | 1995-01-25 | The Procter & Gamble Company | Zusammensetzungen zur Verhinderung der Farbstoffübertragung mit Wascheweichspülmittel |
ES2109471T3 (es) * | 1993-07-23 | 1998-01-16 | Procter & Gamble | Composiciones detergentes que inhiben la transferencia de colorantes. |
DE69319237T2 (de) * | 1993-07-23 | 1999-02-25 | The Procter & Gamble Co., Cincinnati, Ohio | Die Farbstoffübertragung hemmende Waschmittelzusammensetzungen |
WO1995033038A1 (en) * | 1994-06-01 | 1995-12-07 | The Procter & Gamble Company | Sarcosinate with clay softeners in laundry compositions |
DE4430085C2 (de) * | 1994-08-25 | 1997-02-27 | Henkel Kgaa | Haarshampoos |
ES2185645T3 (es) * | 1994-12-29 | 2003-05-01 | Procter & Gamble | Composiciones detergentes para la colada que suavizan durante el lavadodurante el lavado. |
EP0919608A1 (de) * | 1997-11-25 | 1999-06-02 | The Procter & Gamble Company | Verwendung einer Polyhydroyfettsäureamidverbindung als Weichmacherverbindung |
GB2352245A (en) * | 1999-07-22 | 2001-01-24 | Procter & Gamble | Detergent compositions |
DE19948671A1 (de) * | 1999-10-08 | 2001-04-19 | Cognis Deutschland Gmbh | Waschmittel |
JP6085454B2 (ja) * | 2012-11-29 | 2017-02-22 | 株式会社ミルボン | 洗浄剤 |
EP3085761A1 (de) * | 2015-04-20 | 2016-10-26 | Hayata Kimya Sanayi Anonim Sirketi | Waschmittel für den einsatz in zusammenwaschen von weissen und farbigen stoffen |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2703798A (en) * | 1950-05-25 | 1955-03-08 | Commercial Solvents Corp | Detergents from nu-monoalkyl-glucamines |
US2662073A (en) * | 1951-04-27 | 1953-12-08 | Charles L Mehltretter | Gluconamides |
BE557103A (de) * | 1956-05-14 | |||
US2982737A (en) * | 1957-05-27 | 1961-05-02 | Rohm & Haas | Detergent bars |
SE319156B (de) * | 1966-08-01 | 1970-01-12 | Henkel & Cie Gmbh | |
DK130418A (de) * | 1967-07-19 | |||
ZA734721B (en) * | 1972-07-14 | 1974-03-27 | Procter & Gamble | Detergent compositions |
US3852211A (en) * | 1972-08-09 | 1974-12-03 | Procter & Gamble | Detergent compositions |
US3915882A (en) * | 1972-11-10 | 1975-10-28 | Procter & Gamble | Soap compositions |
WO1983004412A1 (en) * | 1982-06-11 | 1983-12-22 | National Research Development Corporation | Amphipathic compounds |
DE3538451A1 (de) * | 1985-10-29 | 1987-05-07 | Sueddeutsche Zucker Ag | Fettsaeureamide von aminopolyolen als nichtionogene tenside |
DE3711776A1 (de) * | 1987-04-08 | 1988-10-27 | Huels Chemische Werke Ag | Verwendung von n-polyhydroxyalkylfettsaeureamiden als verdickungsmittel fuer fluessige waessrige tensidsysteme |
DE3887020T2 (de) * | 1987-07-14 | 1994-06-09 | Procter & Gamble | Detergenszusammensetzungen. |
US4844821A (en) * | 1988-02-10 | 1989-07-04 | The Procter & Gamble Company | Stable liquid laundry detergent/fabric conditioning composition |
EP0387426B1 (de) * | 1988-12-21 | 1996-10-02 | The Procter & Gamble Company | Textil-Wäscheweichmacher, enthaltend natürlichen Hektoritten |
-
1991
- 1991-07-08 DE DE1991613259 patent/DE69113259T2/de not_active Expired - Fee Related
- 1991-07-08 EP EP19910201773 patent/EP0522206B1/de not_active Expired - Lifetime
- 1991-07-08 ES ES91201773T patent/ES2077154T3/es not_active Expired - Lifetime
-
1992
- 1992-06-24 CA CA 2113067 patent/CA2113067C/en not_active Expired - Fee Related
- 1992-06-24 HU HU9400051A patent/HUT66853A/hu unknown
- 1992-06-24 WO PCT/US1992/005269 patent/WO1993001267A1/en active Application Filing
- 1992-06-24 JP JP5502234A patent/JPH06508876A/ja active Pending
- 1992-06-30 TR TR00615/92A patent/TR26835A/xx unknown
- 1992-06-30 PT PT10064492A patent/PT100644A/pt not_active Application Discontinuation
- 1992-07-01 IE IE922133A patent/IE922133A1/en not_active Application Discontinuation
- 1992-07-01 IN IN579DE1992 patent/IN186294B/en unknown
- 1992-07-07 MX MX9203995A patent/MX9203995A/es not_active IP Right Cessation
- 1992-07-07 MA MA22868A patent/MA22585A1/fr unknown
- 1992-07-08 CN CN92109294A patent/CN1037452C/zh not_active Expired - Fee Related
- 1992-07-25 TW TW81105902A patent/TW216802B/zh active
Also Published As
Publication number | Publication date |
---|---|
TW216802B (de) | 1993-12-01 |
CN1070223A (zh) | 1993-03-24 |
DE69113259D1 (de) | 1995-10-26 |
CN1037452C (zh) | 1998-02-18 |
DE69113259T2 (de) | 1996-05-15 |
MA22585A1 (fr) | 1993-04-01 |
TR26835A (tr) | 1994-08-12 |
WO1993001267A1 (en) | 1993-01-21 |
EP0522206A1 (de) | 1993-01-13 |
MX9203995A (es) | 1993-04-30 |
JPH06508876A (ja) | 1994-10-06 |
IN186294B (de) | 2001-07-28 |
PT100644A (pt) | 1993-09-30 |
HU9400051D0 (en) | 1994-05-30 |
CA2113067C (en) | 1997-12-16 |
HUT66853A (en) | 1995-01-30 |
IE922133A1 (en) | 1993-01-13 |
CA2113067A1 (en) | 1993-01-21 |
ES2077154T3 (es) | 1995-11-16 |
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