WO1997034984A1 - Compositions detergentes contenant des agents sequestrants diaminoalkyle disulfosuccinate - Google Patents

Compositions detergentes contenant des agents sequestrants diaminoalkyle disulfosuccinate Download PDF

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Publication number
WO1997034984A1
WO1997034984A1 PCT/EP1997/001065 EP9701065W WO9734984A1 WO 1997034984 A1 WO1997034984 A1 WO 1997034984A1 EP 9701065 W EP9701065 W EP 9701065W WO 9734984 A1 WO9734984 A1 WO 9734984A1
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Prior art keywords
alkali metal
mixtures
weight
alkyl
sulfosuccinic acid
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PCT/EP1997/001065
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English (en)
Inventor
Eddie Nelson Gutierrez
Robert Charles Vermeer
Shang-Ren Wu
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Unilever Plc
Unilever N.V.
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Priority to AU18803/97A priority Critical patent/AU1880397A/en
Publication of WO1997034984A1 publication Critical patent/WO1997034984A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof

Definitions

  • the present invention relates to improved laundry detergent compositions. Specifically, it relates to laundry detergent compositions, substantially free of peroxygen bleach compounds, containing diaminoalkyl disulfosuccinates (DDSS) or its salts, which assist in the removal of food, beverage, and certain other organic stains from fabrics during the laundry process.
  • DDSS diaminoalkyl disulfosuccinates
  • DDSS can be used as a
  • detergent compositions substantially free of peroxygen bleach compounds which contain reduced levels of phosphorous-containing components, but which still exhibit excellent cleaning and stain removal performance Accordingly, it is an object of the present invention to provide novel laundry detergent compositions which exhibit improved stain and soil removal characteristics. It is another object of the present invention to provide novel laundry detergent compositions substantially free of peroxygen bleach compounds which still exhibit excellent cleaning and stain removal performance. It is a final object of the present invention to provide novel laundry detergent compositions which contain diamino alkyl di (sulfosuccinate) (DDSS), a nil-phosphorous chelant.
  • DDSS diamino alkyl di (sulfosuccinate)
  • aminopolycarboxylates as laundry detergent additives is generally disclosed in the art.
  • the prior art described laundry detergent compositions which include nitrilotriacetates (NTA), ethylenediamine- tetraacetates (EDTA) , diethylenetriaminepentaacetates (DTPA), and hydroxyethyl-ethylenediaminetriaacetates (HEDTA), triethylenetetraminehexaacetic acid (TTHA) and
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • U.S. Patent No. 4,560,492 discloses laundry detergent compositions containing an aluminosilicate or organic detergency builder and from about 0.5% to about 10% by weight of HEDTA.
  • suitable organic detergency builders disclosed includes aminopolycarboxylates such as NTA, EDTA, and DTPA.
  • U.S. Patent No. 4,397,776 discloses liquid laundry detergent compositions having a pH between 9 and 13, containing alpha-amme oxide surfactants and from about 0.01% to about 25% by weight of a heavy-metal chelating agent.
  • the preferred chelating agents include aminopolycarboxylates such as NTA, EDTA, DTPA, and HEDTA.
  • U.S. Patent No. 3,920,564 discloses softener/ detergent formulations containing surfactants, quaternary ammonium or diamine fabric softeners, and a builder salt selected from aminopolycarboxylates and/or sodium citrate.
  • suitable aminopolycarboxylates include NTA, EDTA, and HEDTA.
  • alkylbenzenesulfonate-containmg detergent compositions in which solubility is said to be improved by the addition of a mixture of EDTA and a solubilizmg agent selected from salts of N,N-d ⁇ (2-hydroxyethyl) glycine, iminodiacetic acid, NTA, and HEDTA.
  • a solubilizmg agent selected from salts of N,N-d ⁇ (2-hydroxyethyl) glycine, iminodiacetic acid, NTA, and HEDTA.
  • U.S. Patent No. 3,957,775 discloses methods of preparing monoammoalkyl sulfosuccmates and monoaminoalkyl
  • U.S. Patent No. 4,704,233 discloses detergent compositions containing ethylenediamme N-N' disuccinic acid (EDDS) and salts.
  • EDDS ethylenediamme N-N' disuccinic acid
  • compositions which include peroxygen bleaching agents which are useful in removing stain from the fabric by bleaching action.
  • the compositions of the present invention are substantially free of peroxygen bleaching agents and exhibit excellent stain removal
  • a detergent surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, zwitterionic surfactants, ampholytic surfactants, cationic surfactants, and mixtures thereof;
  • DDSS compounds of the present invention are of the general formula:
  • M is alkali or alkaline earth metal but preferably sodium; and wherein R 1 is optionally present as CHOH or CH 2 and R 2 is H. When R 1 is not present, the chain is simply an
  • ethylenediamine group connecting two sulfosuccinate groups and R 2 is methyl or hydrogen.
  • R 1 is not present and R 2 is hydrogen so that the two sulfosuccinate groups are connected by an
  • the compounds which may be included in the above general formula are the alkali metal or alkaline earth metal salts (preferably sodium salts) of
  • DDSS nil-phosphorus chelant
  • the amount of detergent surfactant included in the detergent compositions of the present invention can vary from about 1% to about 75% by weight of the composition depending upon the particular surfactant(ss ) used, the type of
  • composition to be formulated e.g., granular, liquid, etc.
  • the detergent e.g., granular, liquid, etc.
  • the detergent e.g., granular, liquid, etc.
  • surfactant(s) comprises from about 5% to about 60% by weight of the composition.
  • the detergent surfactant can be
  • nonionic, anionic, ampholytic, zwitterionic, or cationic can also be used.
  • Suitable nonionic surfactants are generally disclosed in U.S. Patent No. 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference.
  • Classes of useful nonionic surfactants include: 1. The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the ethylene oxide being present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of phenol; dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and dnsooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
  • Commercially available nonionic surfactants of this type include Igepal CO-630, marketed by the GAF Corporation; and Triton X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
  • the condensation products of aliphatic alcohols with from about 1 to 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 4 to about 10 moles of ethylene oxide per mole of alcohol.
  • Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol with about 10 moles of ethylene oxide per mole of alcohol; and the condensation product of coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms) with about 9 moles of ethylene oxide. Examples of
  • nonionic surfactants of this type include Tergitol 15-S-9 (the condensation product of C 11 -C 15 linear alcohol with 9 moles ethylene oxide), marketed by Union Carbide Corporation; Neodol 45-9 (the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide, Neodol 23-6.5 (the condensation product of C 12 -C 13 linear alcohol with 6.5 moles of ethylene oxide), Neodol 45-7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide), and Neodol 45-4 (the condensation product of C 14 -C 15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company. 3.
  • Tergitol 15-S-9 the condensation product of C 11 -C 15 linear alcohol with 9 moles ethylene oxide
  • Neodol 45-9 the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide
  • Neodol 23-6.5 the condensation product of C 12 -C 13 linear alcohol with 6.5 moles
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of these compounds has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially available Pluronic surfactants, marketed by Wyandotte Chemical Corporation.
  • the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine consist of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the
  • condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
  • nonionic surfactant include certain of the commercially available Tetronic compounds, marketed by Wyandotte Chemical Corporation. 5.
  • Semi-polar nonionic surfactants which include water- soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms;
  • water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • Preferred semi-polar nonionic detergent surfactants are the amine oxide surfactants having the formula:
  • R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms
  • R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof
  • x is from 0 to about 3
  • each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • Preferred amine oxide surfactants are C 10 -C 18
  • alkyldimethylamine oxides and C 8 -C 12
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose, and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4- , and/or 6- positions on the preceding saccharide units.
  • the preferred alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10,
  • alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
  • alkylpolyglycosides have the formula:
  • R 2 O(C n H 2 n O) t (glycosyl) x
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 11 ⁇ 2 to about 10, preferably from about 11 ⁇ 2. to about 3, most preferably from about 1.6 to about 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 predominately the 2-position. 7.
  • the fatty acid amide surfactants having the formula: wherein R 6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each, R 7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and — (C 2 H 4 O) x H where x varies from about 1 to about 3.
  • Preferred amides are C 8 -C 20 ammonia amides
  • R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2- hydroxypropyl, 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 31 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 15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative (preferably
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • raw materials high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mixture of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials
  • 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 3 to 5, (inclusive) and R' is H or a cyclic or aliphatic
  • glycityls wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
  • R' can be, for example, N-methyl, N- ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxypropyl.
  • 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.
  • the N-alkoxy and N-aryloxy polyhydroxy fatty acid amide surfactants having the formula:
  • R is C 7 -C 21 hydrocarbyl, preferably C 9 -C 17 hydrocarbyl, including straight-chain (preferred), branched- chain alkyl and alkenyl, as well as substituted alkyl and alkenyl, e.g., 12-hydroxy oleic, or mixtures thereof;
  • R 1 is C 2 -C 8 hydrocarbyl including straight-chain, branched-chain and cyclic (including aryl), and is preferably C 2 -C 4 alkylene, i.e., -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - and -CH 2 (CH 2 ) 2 CH 2 -;
  • R 2 is C 1 -C 8 straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxy-hydrocarbyl, and is preferably C 1 -C 4 alkyl or phenyl; and
  • Z is a
  • polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • raw materials high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • 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, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or
  • polysaccharide and alkoxylated derivatives thereof.
  • Most preferred are glycityls wherein n is 4, particularly -CH 2 - (CHOH) 4 -CH 2 OH.
  • nonlimiting examples of the amine substituents group -R 1 O-R 2 can be, for example: 2-methoxyethyl-, 3-methoxy-propyl-, 4-methoxybutyl-, 5- methoxypentyl-, 6-methoxyhexyl-, 2-ethoxy-ethyl-,
  • R-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, ricinolamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1- deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1- deoxymannityl, 1-deoxymaltotriotityl, etc.
  • Aldobionamides are defined as the amide of an aldobionic acid (or aldobionolactone) and an aldobionic acid is a sugar substance (e.g., any cyclic sugar comprising at least two saccharide units ) wherein the aldehyde group (generally found at the C 1 position of the sugar) has been replaced by a carboxylic acid, which upon drying cyclizes to an aldobionic acid (or aldobionolactone) and an aldobionic acid is a sugar substance (e.g., any cyclic sugar comprising at least two saccharide units ) wherein the aldehyde group (generally found at the C 1 position of the sugar) has been replaced by a carboxylic acid, which upon drying cyclizes to an aldobionic acid (or aldobionolactone) and an aldobionic acid is a sugar substance (e.g., any cyclic sugar comprising at least two saccharide units ) wherein the aldehyde group
  • An aldobionamide may be based on compounds comprising two saccharide units (e.g., lactobionamides or maltobionamides, etc.) or they may be based on compounds comprising more than two saccharide units (e.g., maltotrionamides), as long as the terminal sugar in the polysaccharide has an aldehyde group.
  • an aldobionamide must have at least two saccharide units and cannot be linear.
  • (disaccharides) which may be used include cellobionamides, melibionamides and gentiobionamides.
  • aldobionamide which may be used for purposes of the invention is the disaccharide
  • R 1 and R 2 are the same or different and are selected from the group consisting of hydrogen; an aliphatic hydrocarbon radical (e.g., alkyl groups and alkene groups which groups may contain heteroatoms such as N, O or S or alkoxylated alkyl chains such as ethoxylated or propoxylated alkyl groups, preferably an alkyl group having 6 to 24, preferably 8 to 18 carbons; an aromatic radical (including substituted or unsubstituted aryl groups and arenes); a cycloaliphatic radical; an amino acid ester, ether amines and mixtures thereof. It should be noted that R 1 and R 2 cannot be hydrogen at the same time.
  • an aliphatic hydrocarbon radical e.g., alkyl groups and alkene groups which groups may contain heteroatoms such as N, O or S or alkoxylated alkyl chains such as ethoxylated or propoxylated alkyl groups, preferably an alkyl group having 6 to 24, preferably 8 to 18
  • Anionic surfactants suitable for use in the present invention are generally disclosed in U.S. Patent No.
  • Classes of useful anionic surfactants include :
  • Ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms.
  • Preferred alkali metal soaps are sodium laurate, sodium cocoate, sodium stearate, sodium oleate and potassium palmitate as well as fatty alcohol ether methylcarboxylates and their salts.
  • Water-soluble salts preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl” is the alkyl portion of acyl groups).
  • anionic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohol (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patent No. 2,220,099, Guenther et al., issued November 5, 1940, and U.S. Patent No. 2,477,383, Lewis, issued December 26, 1946.
  • Especially useful are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to about 13, abbreviated as C 11 -C 13 LAS.
  • anionic surfactants of this type are the alkyl polyalkoxylate sulfates, particularly those in which the alkyl group contains from about 8 to about 22, preferably from about 12 to about 18 carbon atoms, and wherein the polyalkoxylate chain contains from about 1 to about 15 ethoxylate and/or propoxylate moieties, preferably from about 1 to about 3 ethoxylate moieties.
  • alkyl polyalkoxylate sulfates particularly those in which the alkyl group contains from about 8 to about 22, preferably from about 12 to about 18 carbon atoms, and wherein the polyalkoxylate chain contains from about 1 to about 15 ethoxylate and/or propoxylate moieties, preferably from about 1 to about 3 ethoxylate moieties.
  • anionic surfactants of this type include sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 15 units of ethylene oxide per molecule and wherein the alkyl group contains from about 8 to about 22 carbon atoms.
  • water-soluble salts of esters of alpha sulfonated fatty acids containing from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to about 24 carbon atoms; and beta alkyloxy alkane sulfonates
  • alkane moiety containing from about 1 to about 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety as well as primary alkane sulfonates, secondary alkane sulfonates, ⁇ -sulfo fatty acid esters, sulfosuccinic acid alkyl esters, acylaminoalkane sulfonates (Taurides),
  • Particularly preferred surfactants for use herein include alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy sulfates and mixtures thereof. Mixtures of these anionic surfactants with a nonionic surfactant selected from the group consisting of C 10 -C 20 alcohols ethoxylated with an average of from about 4 to about 10 moles of ethylene oxide per mole of alcohol are particularly preferred.
  • Anionic phosphate surfactants such as the alkyl phosphates and alkyl ether phosphates.
  • Ampholytic 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 or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one of the aliphatic substituents contains an anionic water- solubilizing group, e.g., carboxy, sulfonate or sulfate. See U.S. Patent No. 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38 through column 22, line 48, incorporated herein by reference, for examples of ampholytic surfactants useful herein. D. Zwitterionic SurfactantsL
  • Zwitterionic 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 sultonium compounds. See U.S. Patent No. 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38 through column 22, line 48, incorporated herein by reference, for examples of zwitterionic surfactants useful herein.
  • Cationic surfactants can also be included in detergent compositions of the present invention.
  • Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds.
  • Suitable anions are halides, methyl sulfate and hydroxide.
  • Tertiary amines can have characteristics similar to cationic surfactants at washing solutions pH values less than about 8.5.
  • Suitable cationic surfactants include the quaternary ammonium 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 independently selected from the group consisting of
  • each R 4 is independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl, ring structures formed by joining the two R 4 groups,
  • R 6 is any hexose or hexose polymer having a molecular weight less than about
  • R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is not more than about 18, each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
  • Preferred examples of the above compounds are the alkyl quaternary ammonium surfactants, especially the monolong chain alkyl surfactants described in the above formula when R 5 is selected from the same groups as R 4 .
  • preferred quaternary ammonium surfactants are the chloride, bromide, and methylsulfate C 8 -C 16 alkyl trimethylammonium salts, C 8 -C 16 alkyl di (hydroxy-ethyl)methylammonium salts, the C 8 -C 16 alkyloxypropyltrimethylammonium salts.
  • chloride, bromide, and methylsulfate C 8 -C 16 alkyl trimethylammonium salts C 8 -C 16 alkyl di (hydroxy-ethyl)methylammonium salts
  • the C 8 -C 16 alkyloxypropyltrimethylammonium salts the C 8 -C 16 alkyloxypropyltrimethylammonium salts.
  • methylsulfate are particularly preferred.
  • a more complete disclosure of cationic surfactants useful herein can be found in U.S. Patent No. 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.
  • Detergent compositions of the present invention contain inorganic and/or organic detergent builders to assist in mineral hardness control. These builders comprise from about 5% to about 80% by weight of the compositions. Built liquid formulations preferably comprise from about 7% to about 30% by weight of detergent builder, while built granular
  • formulations preferably comprise from about 10% to about 50% by weight of detergent builder.
  • Suitable detergent builders include crystalline
  • alummosilicate ion exchange materials having the formula:
  • the aluminosilicate ion exchange builder materials are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
  • the preferred crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
  • More preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
  • particle size diameter represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline aluminosilicate ion exchange materials are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg.
  • the aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6/grains/gallon/minute/gram/ gallon, based on calcium ion hardness.
  • Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/galIon/ minute/gram/galIon.
  • the amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange capacity of at least about 50 mg eq CaCo 3 /g (12mg Mg++/g) and a Mg++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
  • 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 No. 3,985,669, Krummel et al., issued October 12, 1976, incorporated herein by reference.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula:
  • detergency builders useful in the present invention include the alkali metal silicates, alkali metal carbonates, phosphates, polyphosphates, phosphonates, polyphosphonic acids, C 10-18 alkyl monocarboxylic acids, polycarboxylic acids, alkali metal ammonium or substituted ammonium salts thereof and mixtures thereof.
  • alkali metal especially sodium, salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphate having a degree of polymerization of from about 6 to about 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene-1,1-diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane 1,1,2-triphosphonic acid.
  • Other suitable phosphorus builder compounds are disclosed in U.S. Patent No. 3,159,571, Diehl, issued
  • compositions of the invention can be formulated using minimum levels or in the complete absence of phosphonates and phosphates.
  • the DDSS sequestrants will provide improved stain and soil removal benefits in the presence and absence of phosphonate and/or phosphate builders or chelants.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a mole ratio of SiO 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • Useful water-soluble, nonphosphorus organic builders include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and
  • polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • the organic detergent builder component which may be used herein does not comprise diaminoalkyl di (sulfosuccinate) (DDSS) or salts thereof.
  • mesaconic acid fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • a class of useful phosphorus-free detergent builder materials have been found to be 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
  • ether polycarboxylates useful as builders in the present invention are those having the general formula:
  • A is H or OH ;
  • B is H or
  • X is H or a salt-forming cation.
  • a and B are both H, then the compound is oxydisuccinic 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. If A is H and B is
  • TDS tartrate disuccinic acid
  • mixtures of TMS and TDS in a weight ratio of TMS to TDS of from about 97:3 to about 20:80.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, s ⁇ ch as those described in U.S. Patent Nos. 3,923,679; 3,835,163;
  • 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 about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C 1-4 alkyl or C 1-4 substituted alkyl (preferably R is hydrogen).
  • detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent No. 4,566,984, Bush, issued January 28, 1986, incorporated herein by
  • Other useful builders include the C 5 -C 20 alkyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • Useful builders also include sodium and potassium
  • polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent No. 4,144,226, Crutchfield et al., issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together, under polymerization
  • an ester of glyoxylic acid and a polymerization initiator 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.
  • Especially useful detergency builders include the C 10 -C 18 alkyl monocarboxylic (fatty) acids and salts thereof. These fatty acids can be derived from animal and vegetable fats and oils, such as tallow, coconut oil and palm oil. Suitable saturated fatty acids can also be synthetically prepared
  • Particularly preferred C 10 -C 18 alkyl monocarboxylic acids are saturated coconut fatty acids, palm kernel fatty acids, and mixtures thereof.
  • seeded builder mixtures are 3:1 wt. mixtures of sodium carbonate and calcium
  • Diaminoalkyl Di sulfosuccinates
  • SMA sulfomaleic anhydride
  • SMA is a much more reactive electrophile than maleic anhydride and will therefore react rapidly with nucleophiles (such as amines, diamines and the like) under aqueous Michael
  • Diamine derivatives such as ethylenediamine, 1,3- propylenediamine, 1,2-propylenediamine, 2-hydroxy-1,3- propylenediamine and the like add rapidly to either the sodium or calcium salts of SMA.
  • Ethylenediamine di (sulfosuccinate) (EDDSS) has eight ligands for binding which make this material a good builder.
  • Amino based sulfosuccinates are produced by reacting either an amine or amine carboxylate((s) with the sulfomaleate at pHs of about 9-12 at about 25-30°C.
  • Either calcium or sodium salts or mixtures of both can be employed, however, it is more convenient to use the sodium salt because the amine builders appear to complex calcium strongly, which build detergent systems.
  • the method of the invention produces a mixture of (RS), (SR), (RR), (SS), optical isomers. This is due to the presence of four asymmetric carbon atoms.
  • compositions of the invention comprise the (SS) isomer of DDSS.
  • the DDSS sequestrants of the invention may be prepared by the following process:
  • the process involves running the reaction at a sufficient temperature for a sufficient time to form the final product while maintaining the above parameters.
  • the alkali or alkaline earth metal hydroxide which are employed in the process of the invention are selected from the group consisting of sodium, potassium, lithium, barium, strontium, magnesium, calcium hydroxide and the like, or mixtures thereof.
  • the most preferred alkali metal hydroxide for use in this invention is sodium hydroxide.
  • the formation of the DDSS salt of the present invention is conducted at high concentration in aqueous media to afford efficacy and high throughput.
  • the amount of water present may vary from about 55% to about 95% by weight of the reaction mixture and is preferably sufficient to permit the reaction to proceed effectively.
  • the reactants of the starting mixture for the process are combined in water using physical agitation.
  • the alkali or alkaline earth metal hydroxide or mixtures thereof are mixed with an aqueous mixture of the alkyldiamine and sulfomaleate derivative(s) with rapid agitation.
  • the reaction is
  • the reaction temperature for the process is preferably at room temperature which is usually about 25°C or cooler.
  • the reaction temperature is maintained for at least 2 hours and preferably no longer than about 5 hours at temperatures ranging from about 20°C to about 50°C.
  • the aqueous reaction product typically contains a mixture of DDSS, alkyldiamine and sulfomaleate.
  • reaction products obtained by the process of the invention contain the alkali or alkaline earth metal or mixture of salts of DDSS and may be worked up and further purified by methods known in the art.
  • the reaction product can be concentrated by removal of water to the desired extent.
  • Water removal can, for example, involve complete drying of the reaction product mixture, e.g., by spray drying, so that the DDSS salt is recovered in solid or granular form for powdered detergent applications.
  • the sodium salt of DDSS can be obtained in the form of aqueous liquid which may be utilized directly for the preparation of liquid detergent compositions or liquid laundry additive products of the various types.
  • compositions of the invention contain, as an essential component, from about 0.1% to about 50%, preferably from about 0.2% to about 25%, more preferably from about 0.3% to about 15%, of diaminoalkyl di (sulfosuccinate) (DDSS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof.
  • DDSS compounds for granular detergent compositions are the free acid and the corresponding sodium salt forms as well as mixtures thereof. Examples of such preferred sodium salts of DDSS include NaDDSS, Na 2 DDSS, Na 3 DDSS, Na 4 DDSS, Na 5 DDSS, Na 6 DDSS, wherein Na is sodium.
  • Preferred DDSS compounds for liquid detergent compositions are the free acid and the corresponding substituted ammonium or potassium salt forms thereof.
  • Examples of such preferred salts of DDSS include (MEA) DDSS, (MEA) 2 DDSS, (MEA) 3 DDSS, (MEA) 4 DDSS, (MEA) 5 DDSS, (MEA) 6 DDSS, (TEA)DDSS, (TEA) 2 DDSS, (TEA) 3 DDSS, (TEA) 4 DDSS, (TEA) 5 DDSS, (TEA) JDDSS, (DEA) 4 DDSS, (K) 4 DDSS and the like, wherein MEA is monoethanolamine, DEA is diethanolamine, TEA is triethanolamine and K is potassium.
  • the chelant/sequestrant, DDSS possess excellent stain removal characteristics, especially on polyphenolic stains such as tea, coffee, blueberry, morello juice, strawberry and the like. DDSS was found to provide stain removal of
  • compositions herein can optionally include one or more additional detersive materials or other ingredients for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • additional detersive materials or other ingredients for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • additional detersive materials or other ingredients for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • additional detersive materials or other ingredients for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for examples, and for the
  • the enzymes to be incorporated include
  • proteases amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the
  • compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01% - 1%, by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • proteases are the subtilisins which are obtained from particular strains of B.subtilis and
  • protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • Proteolytic enzymes suitable for removing protein-based stains include those sold under the
  • proteases include Protease A (See European Patent Application No. 130 756 published January 9, 1985) and Protease B (See European Patent Application Serial No. 87303761.8 filed April 28, 1987, and European Patent Application No. 130 756, Bott et al., published January 9, 1985).
  • Amylases include, for example, a-amylases described in
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent No. 4,435,307, Barbesgoard et al., issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
  • Suitable cellulases are also disclosed in GB A-2.075.028; GB A- 2.095.275 and DE-OS-2.247.832.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent
  • Mano-P Lipase P
  • lipases include Amano-CES, lipases ex
  • Chromobacter viscosum e.g., Chromobacter viscosum var, lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., USA and Disoynth Co., The
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e., to prevent transfer of dyes or pigments removed from
  • Peroxidase enzymes are known in the art, and include, for examples, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromoperoxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989 by O. Kirk, assigned to Novo Industries A/S.
  • Enzvme Stabilizers The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used). Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species: See Severson, U.S. 4,537,706, cited above. Typical detergents, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more
  • any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
  • a small amount of calcium ion is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor.
  • natural water hardness may suffice.
  • compositions herein may comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the composition.
  • compositions herein may also optionally, but
  • borate-type stabilizers especially borate-type stabilizers.
  • stabilizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and
  • hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the
  • hydrophilic segments This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segments does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50%
  • hydrophobe components comprising (i) C 3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise
  • C 3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C 4 -C 6 alkylene or oxy C 4 -C 6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably poly(vinyl acetate), having a degree of polymerization of at least 2 or (iv) C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether cellulose derivatives, or mixture therein, and such cellulose derivatives are
  • the polyoxyethylene segments of (a) (i) will have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C 4 -C 6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent No. 4,721,580, issued January 26, 1988, to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow).
  • Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose; See U.S. Patent No. 4,000,093, issued December 28, 1976, to Nicol et al.
  • Soil release agents characterized by poly (vinyl ester) hydrophobe segments include graft copolymers of poly (vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly (vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly (vinyl ester) hydrophobe segments include graft copolymers of poly (vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly (vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • European Patent No. 4,000,093, issued December 28, 1976 to Nicol
  • soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent No. 3,959,230 to
  • Another polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10- 15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also, U.S. Patent No. 4,702,857, issued October 27, 1987 to Gosselink.
  • Another polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and
  • soil release agents also include the soil release agents of U.S. Patent No. 4,877,896, issued October 31, 1989 to Maldonado et al., which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters. If utilized, soil release agents will generally comprise from about 0.01% to about 10.0% by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • Co-chelating Agents may also optionally contain one or more iron and/or manganese co-chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates. N- hydroxyethylethylenediaminetriacetates, nitrilo-triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexa- acetates, diethylenetriaminepentaacetates,
  • ethylenediaminedisuccinate and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent
  • compositions and include ethylenediaminetetrakis
  • amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent No. 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfo- benzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • the chelating agents comprise from about 0.1% to about 3.0% by weight of such composition.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water- soluble ethoxylated amines.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent No. 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds disclosed in European Patent Application 111 965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111 984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112 592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred antiredeposition agent includes the carboxymethyl cellulose (CMC) materials. These materials are well known in the art.
  • CMC carboxymethyl cellulose
  • Polymeric Dispersing Agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric
  • polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967.
  • 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
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble
  • PEG polyethylene glycol
  • 100,000 preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzo-thiphene- 5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S.
  • These brighteners include the PHORWHITE series of brighteners from Verona.
  • Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM;
  • Ciba-Geigy available from Ciba-Geigy; Arctic White CC and Artie White
  • compositions of the present invention are compositions of the present invention. Suds suppression can be of particular importance under conditions such as those found in European-style front loading laundry washing
  • the monocarboxylic fatty acids and soluble salts therein typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non- surfactant suds suppressors.
  • hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1 8 -C 40 ketones (e.g., stearone), etc.
  • suds inhibitors include N- alkylated amino triazines such as tri- to hexa-aIkylmelamines or di- to tetraalkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room
  • Hydrocarbon suds suppressors are described, for example, in U.S. Patent No. 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin”, as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • silicone suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent No. 4,265,779, issued May 5, 1981 to Gandolfo et al . and European Patent
  • Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs at 25°C;
  • siloxane resin composed of (CH 3 ) 3 SiO 1 ⁇ 2 units of SiO 2 units in a ratio of from (CH 3 ) 3 SiO 1 ⁇ 2 units and to SiO 2 units of from about 0.6:1 to about 1.2:1;
  • the solvent for a continuous phase is made up of certain silicone suds suppressor used herein.
  • the primary silicone suds suppressor is branched/crosslinked and not linear.
  • silicone suds suppressor which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (c), to form silanolates; (2) at least one nonionic silicone
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene
  • glycol/polypropylene glycol all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • polyethylene/polypropylene copolymers herein have a
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene
  • glycol/polypropylene glycol preferably PPG 200/PEG 300.
  • Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene
  • glycol copolymer of polyethylene-polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101. Other suds suppressors useful herein comprise the
  • secondary alcohols e.g., 2-alkyl alkanols
  • silicone oils such as the silicones disclosed in U.S. 4,798,679; 4,075,118 and EP 150 872.
  • the secondary alcohols include the C 6 -C 16 alkyl alcohols having a C 1 -C 16 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount".
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds
  • silicone suds suppressors will be present typically in amounts up to about 5%, by weight, of the detergent composition.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2% by weight of the
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • compositions herein can also be used with a variety of other adjunct ingredients which provide still other benefits in various compositions within the scope of this invention.
  • the following illustrates a variety of such adjunct ingredients, but is not intended to be limiting therein.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent No. 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with the fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners, as disclosed, for example, in U.S. Patent No. 4,375,416, Crisp et al., March 1, 1983, and U.S. Patent No. 4,291,071, Harris et al., issued
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N- vinylpyrrolidone and N-vinylimidazole, manganese
  • these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
  • polyamine N-oxide polymers More specifically, the polyamine N-oxide polymers
  • R-A x -P units having the following structural formula: R-A x -P; wherein P is a polymerizable unit to which an N-0 group can be attached or the N-0 group can form part of the polymerizable unit or the N-0 group can be attached to both units;
  • A is one of the following
  • Preferred polyamine N- oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures:
  • R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters,
  • polyethers polyamide, polyimides, polyacrylates and mixtures thereof.
  • These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
  • the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization.
  • the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred
  • PVPVI poly(vinylpyridine-N- oxide) which has an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A- 256,696, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • the detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R 1 is anilino
  • R 2 is N-2-bis- hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxy-ethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopai-UNPA-GX by Ciba-Geigy
  • Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R 1 is anilino
  • R 2 is N-2- hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]-2,2'- stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R 1 is anilino
  • R 2 is
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]- 2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • the detergent compositions of the present invention are substantially free of any peroxygen compounds.
  • substantially free means that the detergent compositions contain less than about 0.01%, preferably less than about 0.005%, by weight of a peroxygen compound.
  • peroxygen compounds commonly used in bleaching solutions include hydrogen peroxide and its derivatives, such as alkali metal peroxides and superoxides, perborates, persulfates; and peracids, such as persulfonic acid,
  • peracetic acid peroxy mono-phosphoric acid and their water- soluble salts, especially their alkali metal, ammonium or organic amine salts; and urea-hydrogen peroxide addition product.
  • inhibitors include dyes, fillers, carriers, germicides, pH-adjusting agents, perfumes, static control agents, thickening agents, abrasive agents, viscosity control agents,
  • solubilizing/clarifying agents sunscreens/UV absorbers, phase regulants, foam boosting/stabilizing agents,
  • antioxidants metal ions, buffering agents, color speckles, encapsulation agents, deflocculating polymers, skin
  • compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C 13-15 ethoxylated alcohol EO(7) nonionic surfactant.
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • Many additional essential and optional ingredients that are useful in the present invention are those described in McCutcheon's, Detergents and Emulsifiers (vol. 1) and
  • Powdered detergent composition might contain the following by weight: (1) 1-75% detergent surfactant system;
  • a preferred powdered detergent composition might contain the following by weight:
  • a liquid detergent composition might contain the following by weight:
  • a preferred liquid detergent composition might contain the following by weight: (1) 5-60% detergent surfactant system;
  • the DDSS chelant/sequestrant and its salts of the present invention are useful in a variety of detergent, personal product, cosmetic, oral hygiene, food, pharmacological and industrial compositions which are available in many types and forms.
  • Preferred compositions are detergent compositions.
  • a classification according to detergent type would consist of heavy-duty detergent powders, heavy-duty detergent liquids, light-duty liquids (dishwashing liquids),
  • a classification according to personal product type would consist of hair care products, bath products, cleansing products, skin care products, shaving products and
  • hair care products include, but are not limited to rinses, conditioners, shampoos, conditioning shampoos, antidandruff shampoos, antilice shampoos, coloring shampoos, curl maintenance shampoos, baby shampoos, herbal shampoos, hair loss prevention shampoos, hair
  • bath products include, but are not limited to bath oils, foam or bubble bathes, therapeutic bathes, after bath products, after bath splash products and the like.
  • cleansing products include, but are not limited to shower cleansers, shower gels, body shampoos, hand/body/ facial cleansers, abrasive scrub cleansing
  • Examples of skin care products include, but are not limited to hand/body/ facial lotions, sunscreen products, tanning products, self-tanning products, aftersun products, masking products, lipsticks, lip gloss products, rejuvenating products, antiaging products, antiwrinkle products,
  • Examples of shaving products include, but are not limited to shaving creams, aftershave products, preshave products and the like.
  • Examples of deodorant/antiperspirant products include, but are not limited to deodorant products, antiperspirant products and the like.
  • a classification according to oral hygiene type would consist of, but is not limited to mouthwashes, pre-brushing dental rinses, post-brushing rinses, dental sprays, dental creams, toothpastes, toothpaste gels, toothpowders, dental cleansers, dental flosses, chewing gums, lozenges and the like.
  • the DDSS chelant/sequestrant of the present invention are also useful in softening compositions such as liquid fabric softeners, fabric softening rinses, fabric softening sheets, tissue papers, paper towels, facial tissues, sanitary
  • a classification according to composition form would consist of aerosols, liquids, gels, creams, lotions, sprays, pastes, roll-on, stick, tablet, powdered and bar form.
  • DDSS chelant/sequestrant and its salts of the present invention are useful in a variety of other compositions as above. More specifically, DDSS is useful as chelants of heavy metal and hardness ions, scale inhibiting agents, corrosion inhibiting agents, deflocculating/dispensing agents, stain removal agents, bleach stabilizing agents, protecting agents of peroxygen labile ingredients,
  • DDSS chelant/sequestrant and its salts of the present invention are also useful for certain industrial applications such as acid cleaners, aluminum etching, boiler cleaning, water treatment, bottle washing, cement modification, dairy cleaners, desalination, electrochemical machining,
  • the present invention may provide: a) from about 5% to about 60% by weight of a detergent surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, and mixtures thereof; b) from about 10% to about 50% by weight of a detergency builder selected from the group consisting of alkali metal silicates, alkali metal carbonates, alkali metal phosphates, alkali metal polyphosphonic acids, C 8 -C 18 alkyl monocarboxylic acids, polycarboxylic acids, alkali metal, ammonium or substituted ammonium salts thereof, and mixtures thereof; and c) from about 0.2% to about 25% by weight diaminoalkyl di (sulfosuccinic acid), or alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof, or mixtures thereof.
  • a detergent surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, and mixtures thereof
  • Granular detergent compositions embodying the present invention can be formed by conventional techniques, i.e., by slurrying the individual components in water and then
  • Granular particles atomizing and spray-drying the resultant mixtures, or by pan or drum agglomeration of the ingredients.
  • formulations preferably comprise from about 5% to about 60% of detergent surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, and mixtures thereof.
  • the diaminoalkyl di (sulfosuccinic acid) component is selected from the group consisting of
  • Liquid compositions of the present invention can contain water and other solvents.
  • Lower molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol, are suitable.
  • Monohydric alcohols are preferred for solubilizing the surfactant, but polyols containing from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups can be used and can provide improved enzyme stability (if enzymes are included in the composition).
  • polyols include propylene glycol, ethylene glycol, glycerine and 1,2 propanediol. Ethanol is a particularly preferred alcohol.
  • the liquid compositions preferably comprise from about 5% to about 60% of detergent surfactant, about 7% to about 30% of builder and about 0.1 to 50%, preferably about 0.2% to about 25% diaminoalkyl di (sulfosuccinic acid) or salts thereof.
  • Useful detergency builders in liquid compositions include the alkali metal silicates, alkali metal carbonates,
  • polyphosphonic acids C 10 -C 18 alkyl monocarboxylic acids, polycarboxylic acids, alkali metal, ammonium or substituted ammonium salts thereof, and mixtures thereof.
  • detergency builders are selected from the group consisting of C 10 -C 18 alkyl monocarboxylic acids, polycarboxylic acids and mixtures thereof.
  • the composition includes about 10% to about 28% by weight of detergency builder selected from the group consisting of C 8 -C 18 alkylmonocarboxylic acids, polycarboxylic acids, and mixtures thereof.
  • preferred liquid compositions contain from 5% to about 18% by weight, preferably from about 8% to about 18% of a C 8 -C 18 preferably a C 10 -C 18 monocarboxylic (fatty) acid and from about 0.2% to about 10% of a polycarboxylic acid, preferably citric acid, or a salt thereof, and provides a solution pH of from about 6 to about 10 at 1.0%
  • liquid compositions are substantially free of inorganic phosphates or phosphonates. As used in this context “substantially free” means that the liquid
  • compositions contain less than about 0.5% by weight of an inorganic phosphate- or phosphonate-containing compound.
  • Preferred liquid compositions comprise a di (sulfosuccinic acid) component selected from the group consisting of
  • detergent compositions of the invention are ethylenediamine di(sulfosuccinic acid), 2-hydroxy-1, 3- propylenediamine di(sulfosuccinic acid), 1,3-propylenediamine di(sulfosuccinic acid), 1,2-propylenediamine di(sulfosuccinic acid; or the potassium salts or substituted ammonium salts thereof; and mixtures thereof.
  • the detergent compositions of the invention are
  • typical laundry wash water solutions comprise from about 0.1% to about 5% by weight of the detergent compositions of the invention. Fabrics to be laundered are agitated in these solutions to effect cleaning and stain removal.
  • the detergent compositions of the present invention may be in any of the usual physical forms, such as powders, beads, flakes, bars, tablets, noodles, liquids, pastes and the like.
  • the detergent compositions are prepared and utilized in the conventional manner.
  • the wash solutions thereof desirably have a pH from about 6 to about 12, preferably from about 7 to about 11, more preferably from about 7.5 to about 8.5.
  • the material obtained is sulfomaleic anhydride and is used in Examples 1 to 5.
  • sulfomaleic anhydride 0.1 mole of sulfomaleic anhydride is dissolved in about 50 ml of water and stirred. 0.3 mole of sodium bicarbonate is then added to a pH of about 9 and the solution is cooled to maintain it at about 25°C (room temperature). 0.05 mole of ethylenediamine is added with continued agitation and the pH is maintained at 11 by addition of sodium hydroxide if necessary. The temperature is still maintained at 25°C.
  • sulfomaleic anhydride 0.1 mole of sulfomaleic anhydride is dissolved in about 50ml of water and stirred. 0.3 mole of sodium bicarbonate is then added to a pH of about 9 and the solution is cooled to maintain it at about 25°C (room temperature). 0.05 mole of 2-hydroxy-1,3-propylenediamine is added with continued agitation and the pH is maintained at 11 by addition of sodium hydroxide if necessary. The temperature is still maintained at 25°C. After five hours of reaction time, the solution is evaporated to dryness on a Buchi rotovapor and dried in an oven. The material obtained is hexasodium 2- hydroxy-1,3-propylenediamine di(sulfosuccinate))
  • sulfomaleic anhydride 0.1 mole of sulfomaleic anhydride is dissolved in about 50 ml of water and stirred. 0.3 mole of sodium bicarbonate is then added to a pH of about 9 and the solution is cooled to maintain it at about 25°C (room temperature). 0.05 mole of 1,3-propylenediamine is added with continued agitation and the pH is maintained at 11 by addition of sodium hydroxide if necessary. The temperature is still maintained at 25°C. After five hours of reaction time, the solution is evaporated to dryness on a Buchi rotovapor and dried in an oven. The material obtained is hexasodium 1,2-propylenediamine
  • sulfomaleic anhydride 0.1 mole of sulfomaleic anhydride is dissolved in about 50 ml of water and stirred. 0.3 mole of sodium bicarbonate is then added to a pH of about 9 and the solution is cooled to maintain it at about 25°C (room temperature). 0.025 mole of ethylenediamine and 0.025 mole of 2-hydroxy-1,3- propylenediamine are added with continued agitation and the pH is maintained at 11 by addition of sodium hydroxide if necessary. The temperature is still maintained at 25°C.
  • a detergent composition was prepared containing EDDSS and compared to identical compositions containing either NTA, EDTA, DTPMP or DETPA.
  • NTA EDTA
  • DTPMP DETPA
  • the latter chelates, EDTA, DTPMP and DETPA are not readily biodegradable.
  • the structure of the chelants are as follows: N
  • a great number of test methods have been developed to determine the performance of detergents and various detergent ingredients.
  • a preferred, well-accepted test method involves applying various soils uniformly to a standard cloth under strict specifications yielding an "artificially soiled test cloth", which is then washed under controlled conditions in a Terg-o-tometer (washing machine simulator). The detergency of the sequestrant is assessed electronically using a reflectometer (Colorgard 2000). Before washing, the initial reflectance value of the soiled test cloth is measured (front and back) giving a value which is represented as reflectance- soiled (R s ).
  • Sequestrant a. EDDSS (The invention)
  • Sequestrant Concentration 1 - 20% by weight of the liquid detergent formulation.
  • a heavy duty liquid detergent was prepared according to standard procedures containing various levels of EDDSS (1- 20%). This was compared to identical compositions containing either NTA, EDTA, DTPMP, or DETPA. The test was performed in a terg-o-tometer.
  • the heavy duty liquid detergent is as follows:
  • PC-10 Oil/pigment/milk

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Abstract

Compositions détergentes, exemptes de composés de blanchiment à peroxygène, contenant un tensioactif, un adjuvant et 0,1 % à 50 % en poids de diaminoalkyle disulfosuccinate (DDSS) ou de ses sels. Ces compositions permettent de supprimer plus facilement les taches organiques, en particulier, les taches polyphénoliques, tels que jus de cassis, jus de mûre, jus de myrtille, vin rouge, tomate, fraise, pêche, mangue, thé et café. On a également constaté des améliorations sur certaines taches non polyphénoliques, telles que sang, herbe, noir de carbone, huile d'olive et épinard.
PCT/EP1997/001065 1996-03-21 1997-03-03 Compositions detergentes contenant des agents sequestrants diaminoalkyle disulfosuccinate WO1997034984A1 (fr)

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US08/620,690 1996-03-21

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3683014A (en) * 1970-10-14 1972-08-08 Ethyl Corp Derivatives of 2-amino-3-sulfopropionic acid
US3989700A (en) * 1971-06-25 1976-11-02 Lever Brothers Company Sulfosuccinate derivatives as detergent builders
US5472642A (en) * 1994-12-22 1995-12-05 Lever Brothers Company, Division Of Conopco Inc. Diaminoalkyl di(sulfosuccinates) and their use as builders
WO1996006908A1 (fr) * 1994-08-26 1996-03-07 The Procter & Gamble Company Ethylenediamine disuccinate utilise comme detergent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3683014A (en) * 1970-10-14 1972-08-08 Ethyl Corp Derivatives of 2-amino-3-sulfopropionic acid
US3989700A (en) * 1971-06-25 1976-11-02 Lever Brothers Company Sulfosuccinate derivatives as detergent builders
WO1996006908A1 (fr) * 1994-08-26 1996-03-07 The Procter & Gamble Company Ethylenediamine disuccinate utilise comme detergent
US5472642A (en) * 1994-12-22 1995-12-05 Lever Brothers Company, Division Of Conopco Inc. Diaminoalkyl di(sulfosuccinates) and their use as builders

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