WO2000050549A2 - Compositions nettoyantes contenant des tensioactifs non ioniques selectionnes - Google Patents

Compositions nettoyantes contenant des tensioactifs non ioniques selectionnes Download PDF

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WO2000050549A2
WO2000050549A2 PCT/US2000/004185 US0004185W WO0050549A2 WO 2000050549 A2 WO2000050549 A2 WO 2000050549A2 US 0004185 W US0004185 W US 0004185W WO 0050549 A2 WO0050549 A2 WO 0050549A2
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surfactant
composition
compositions
surfactants
weight
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PCT/US2000/004185
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English (en)
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WO2000050549A3 (fr
Inventor
William Michael Scheper
Bernard William Kluesener
Mark Robert Sivik
Glenn Thomas Jordan, Iv
Philip Kyle Vinson
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The Procter & Gamble Company
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Priority to JP2000601113A priority Critical patent/JP2002537482A/ja
Priority to EP00913522A priority patent/EP1155106A2/fr
Priority to CA002362945A priority patent/CA2362945C/fr
Priority to AU34957/00A priority patent/AU3495700A/en
Publication of WO2000050549A2 publication Critical patent/WO2000050549A2/fr
Publication of WO2000050549A3 publication Critical patent/WO2000050549A3/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • 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
    • C11D1/721—End blocked ethers
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/596—Mixtures of surface active compounds

Definitions

  • the present invention relates to cleaning compositions containing nonionic surfactants selected to improve dissolution of solid products and improve rates of mixing with water of liquid products, while maintaining good physical attributes, good performance and biodegradability.
  • Nonionic surfactants such as alcohol ethoxylates, alkyl polyglycosides, and alkyl glucose amides are of considerable importance in detergent products. For example, under some conditions, nonionic surfactants aid cleaning of greasy soils and inhibit the formation of calcium soap.
  • conventional nonionic surfactants designed for effective cleaning in laundry products form liquid crystalline phases on mixing with water. These phases can hinder the rate of mixing with water and lead to undesirable optical properties of thin films on solution drying.
  • conventional nonionics sprayed on the surface of granules to achieve target density can give rise to poor granule dissolution and residue in horizontal axis machine dispensers.
  • Conventional nonionics formulated at high levels in liquid products can lead to poor rates of mixing with water and consumer concern.
  • Conventional nonionics in window and floor cleaners can form visible liquid crystalline films on drying that increase the effort required by the consumer to achieve a good results.
  • compositions having a selected nonionic surfactant employ the novel surfactants of the present invention, either alone or in combination with other surfactants, to provide improved dissolution of solid products like granules, improved rates of mixing with water for liquid products, and improved dry-down optical properties on hard surfaces, while at the same time providing acceptable cleaning performance, foaming properties and aesthetics.
  • a granular laundry detergent composition comp ⁇ ses: a) a butoxycapped nonionic surfactant; b) a conventional detergent additive; and c) a co-surfactant; wherein the composition is in the form of a granule with a bulk density of from about 100 g/1 to about 1400 g/1.
  • a nonaqueous heavy duty liquid (HDL) laundry detergent composition is provided.
  • the nonaqueous HDL composition m the form of a stable suspension of solid, substantially insoluble particulate mate ⁇ al dispersed throughout a structured, surfactant-contammg liquid phase, wherein the comp ⁇ ses' from about 55% to 98.9% by weight of the composition of a structured, surfactant- contammg liquid phase formed by combining: I) from about 1% to 80% by weight of said liquid phase of one or more nonaqueous organic diluents; and n) from about 20% to 99% by weight of said liquid phase of a surfactant system comp ⁇ sing surfactants selected from the group consisting of amonic, nonionic, catiomc surfactants and combinations thereof; wherein said surfactant system comp ⁇ ses at least about 10%, by weight of a butoxycapped nonionic surfactant.
  • an aqueous heavy duty liquid (HDL) laundry detergent composition comp ⁇ ses: a) a butoxycapped nonionic surfactant; b) an amide co-surfactant composition selected from the group consisting of alkyl polyhydroxy fatty acid amide, alkyl amidopropyl dimethyl amme and mixtures thereof; c) a conventional detergent additive; and d) an aqueous liquid earner.
  • the HDL compositions defined herein may also preferably comprise from about 1% to about 80% by weight of the composition of additional detergent ingredients such as builders, enzymes, colorants, bleaching agents, bleach activators, and other known ingredients.
  • adjuvants can be added in the form of particulate matenal which ranges in size from about 0.1 to about 1500 microns, which is substantially insoluble in the liquid phase and which is selected from the group consisting of peroxygen bleaching agents, bleach activators, colored speckles, organic detergent builders, inorganic alkalinity sources and mixtures thereof.
  • a light duty liquid (LDL) detergent composition comprises: a) a butoxycapped nonionic surfactant; b) a conventional detergent additive; c) a co-surfactant; wherein the composition is in the form of a liquid, gel, or hqui-gel and the pH (as measured as 10% aqueous solution) is from about 5.0 to about 12.5.
  • a hard surface cleaning composition comp ⁇ ses: a) a butoxy capped nonionic surfactant; b) a co-surfactant; c) a hard surface cleaning composition adjunct ingredient; wherein said composition is in the form of a liquid, gel or hqui-gel.
  • a shampoo, or personal cleansing composition comp ⁇ ses: a) a butoxycapped nonionic surfactant; b) a co-surfactant; c) a solvent d) a shampoo composition adjunct ingredient; wherein said composition is in the form of a liquid, gel or hqui-gel. All percentages, ratios and proportions herein are by weight of ingredients used to prepare the finished compositions unless otherwise specified. All documents cited herein are, m relevant part, incorporated herein by reference.
  • the present invention is directed toward a low-foaming nonionic surfactant for use in detergent compositions.
  • the disclosed compounds of the present invention may-also be employed m laundry and skm care compositions.
  • the essential nonionic surfactants of the present invention must have an X/Y number of greater than 1.00, preferably greater than 1.10, more preferably greater than 1.30. The determination of this X/Y number is desc ⁇ bed hereinafter. It has been surpnsmgly found that surfactants with an X/Y number greater than 1.00 demonstrate supe ⁇ or cleaning to nonionic surfactants with a X/Y number of 1.00 or less.
  • the nonionic surfactant contains a glyceryl ether group then the X/Y number is calculated exclusive of any possible dimers and t ⁇ mers. That is any dimers and t ⁇ mers present are not used to calculate the X/Y value for any nonionic surfactant containing a glyceryl ether group.
  • these surfactants provide suds control and in combination with the oxide surfactant provide a level of suds which is suitable for use m an ADW composition. Furthermore, the nonionic surfactant of the present invention have minimal negative interaction with the cleaning of the oxide surfactant.
  • Suitable surfactants include ethoxy and propoxy containing ether-capped poly(oxyalkylated) alcohol surfactants, ethoxy and butoxy containing ether-capped poly(oxyalkylated) alcohol surfactants, ethoxy and butoxy containing alkylalkoxylates, and ethoxy, propoxy and butoxy containing alkyalkoxylates.
  • the LFNI surfactant contains a glyceryl ether-group then it is preferred that the amount of any possible dimer or t ⁇ mer present be minimized. The amount of dimer and t ⁇ mer is minimized to levels such that these have minimal negative interaction with the cleaning of the oxide surfactant.
  • the amount of dimer and t ⁇ mer present in the glyceryl ether containing surfactant is dependent upon the process used to produce the surfactant.
  • the preferred method for minimizing or eliminating the formation of dimer and t ⁇ mer maybe controlled by the stoichiometry of the reactants or via typical pu ⁇ fication methods (e.g. Chromatography, crystallization, fictionahzation etc.).
  • One preferred LFNI of the present invention have the formula:
  • Rl(EO) a (PO) b (BO) c wherein Rl is a linear or branched C6 to C20 alkyl, preferably linear or branched C8 to C18 alkyl, more preferably linear or branched C9 to C16 alkyl; a is an integer from 2 to 30, preferably from 4 to 25, more preferably from 5 to 20 more preferably from 5 to 18; b is an integer from 0 to 30 preferably from 0 to 25, more preferably from 0 to 20, more preferably from 0 to 10; c is an integer from 1 to 10 preferably from 1 to 9, more preferably from 1 to 7, more preferably from 1 to 6.
  • Another preferred LFNI of the present invention has the formula: R 1 O[CH 2 CH(R3)0] m [CH 2 ] k CH(OH)[CH 2 ] J OR2 wherein R and R ⁇ are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R?
  • m is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; m is an integer having an average value from 1 to 40, wherein when m is 2 or greater R may be the same or different and k and j are integers having an average value of from 1 to 12; further wherein when m is 15 or greater and R ⁇ is H and methyl, at least four of R 3 are methyl, further wherein when m is 15 or greater and R-* includes H and from 1 to 3 methyl groups, then at least one R 3 is ethyl, propyl or butyl, further wherein R ⁇ can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof; wherein further, said surfactant has less than 30%, preferably less than 15% and most preferably less than 5% of dimers and t ⁇ mers of said nonionic surfactant.
  • R 1 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms
  • R 2 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, optionally containing from 1 to 5 hydroxy groups; and further optionally substituted with an ether group
  • R 3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms
  • e is an integer having an average value from 1 to 40, wherein R 2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof.
  • Suitable surfactants include, but are not limited to,
  • the LFNI surfactants of the present invention must all have a ratio of hydrophobic to hydrophihc, or "X/Y" number of greater than or equal to 1.00.
  • X/Y is defined as the sum of the protons attached to carbon atoms that are adjacent to oxygen.
  • Y is defined as the sum of all the protons attached to carbon atoms within said molecule that are non-adjacent to oxygen. That is,
  • X/Y can also be measured expenmentally from integration of the ⁇ NMR spectrum.
  • the "X" protons are represented as the peak area defined by the region of the spectrum from d
  • the "Y" protons are represented as the peak area defined from d 0.5 to 2.0 ppm.
  • X/Y is then calculated by dividing the peak area from 3.0 to 4.0 ppm by the peak area from 0.5 to
  • a laundry or cleaning adjunct is any mate ⁇ al required to transform a composition containing only the minimum essential ingredients into a composition useful for laundry or cleaning purposes, such as a LDL, HDL or shampoo.
  • laundry or cleaning adjuncts are easily recognizable to those of skill m the art as being absolutely characte ⁇ stic of laundry or cleaning products, especially of laundry or cleaning products intended for direct use by a consumer in a domestic environment. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used.
  • adjunct ingredients if used with bleach should have good stability therewith.
  • Certain preferred detergent compositions herein should be boron-free and/or phosphate-free as required by legislation.
  • Levels of adjuncts are from about 0.00001% to about 99.9%, by weight of the compositions.
  • Use levels of the overall compositions can vary widely depending on the intended application, ranging for example from a few ppm in solution to so- called “direct application” of the neat cleaning composition to the surface to be cleaned.
  • adjuncts include builders, co-surfactants, enzymes, polymers, bleaches, bleach activators, catalytic materials and the like excluding any mate ⁇ als already defined heremabove as part of the essential component of the inventive compositions
  • Other adjuncts herein can include diverse active ingredients or specialized mate ⁇ als, for example, dispersant polymers (e.g., from BASF Corp.
  • the surfactant system of the compositions according to the present invention may further comp ⁇ se additional surfactants, herein also referred to as co-surfactants, preferably selected from: aniomc surfactants, preferably selected from the group of alkyl alkoxylated sulfates, alkyl sulfates, alkyl disulfates, and/or linear alkyl benzenesulfonate surfactants; catiomc surfactants, preferably selected from quaternary ammonium surfactants; nonionic surfactants, preferably alkyl ethoxylates, alkyl polyglucosides, polyhydroxy fatty acid amides, and/or amine or amine oxide surfactants; amphote ⁇ c surfactants, preferably selected from betames and/or polycarboxylates (for example polyglycmates); and zwitte ⁇ onic surfactants.
  • aniomc surfactants preferably selected from the group of alkyl alkoxylated s
  • a wide range of these co-surfactants can be used in the cleaning compositions of the present invention.
  • a typical listing of anionic, nonionic, ampholytic and zwitte ⁇ onic classes, and species of these co-surfactants, is given m US Patent 3,664,961 issued to Noms on May 23, 1972 Amphote ⁇ c surfactants are also descnbed m detail in "Amphote ⁇ c Surfactants, Second Edition", E.G. Lomax, Editor (published 1996, by Marcel Dekker, Inc.). Suitable surfactants can be found in U.S. Patent applications Se ⁇ al Nos. 60/032,035 (Docket No.
  • compositions of the present invention preferably comprise from about 0.01% to about 55%, more preferably from about 0.1% to about 45%, more preferably from about 0.25% to about 30%o, more preferably from about 0.5% to about 20%, by weight of co-surfactants.
  • Selected co-surfactants are further identified as follows.
  • Nonlimiting examples of anionic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight, include the conventional Ci -C ⁇ g alkyl benzene sulfonates ("LAS") and primary, branched-chain and random Ci ()-C 2 o alkyl sulfates ("AS"), the C ⁇ ⁇ ) -C ⁇ g secondary (2,3) alkyl sulfates of the formula CH 3 (CH ) x (CHOS0 3 " M + ) CH 3 and CH 3
  • LAS Ci -C ⁇ g alkyl benzene sulfonates
  • AS branched-chain and random Ci ()-C 2 o alkyl sulfates
  • x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Cjo-Ci g alpha-sulfonated fatty acid esters, the Cjo-Cig sulfated alkyl polyglycosides, the Ci Q -Ci g alkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates), and Ci ⁇ - i g alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates).
  • AE X S especially EO 1-7 ethoxy sulfates
  • C j 2-C ⁇ betaines and sulfobetaines can also be included in the overall compositions.
  • C ⁇ o-C 2 o conventional soaps may also be used. If high sudsing is desired, the branched-chain Ci Q -Cjg soaps may be used.
  • Other conventional useful anionic co-surfactants are listed in standard texts.
  • alkyl ester sulfonate surfactants including linear esters of Cg-C 2 ⁇ carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous S0 3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • dianionics are surfactants which have at least two anionic groups present on the surfactant molecule.
  • dianionic surfactants are further described in copending U.S. Serial No. 60/020,503 (Docket No. 6160P), 60/020,772 (Docket No. 6161P), 60/020,928 (Docket No. 6158P), 60/020,832 (Docket No. 6159P) and 60/020,773 (Docket No. 6162P) all filed on June 28, 1996, and 60/023,539 (Docket No. 6192P), 60/023493 (Docket No. 6194P), 60/023,540 (Docket No. 6193P) and 60/023,527 (Docket No. 6195P) filed on August 8th, 1996, the disclosures of which are incorporated herein by reference.
  • the surfactant may be a branched alkyl sulfate, branched alkyl alkoxylate, or branched alkyl alkoxylate sulfate.
  • These surfactants are further described in No. 60/061,971, Attorney docket No 6881P October 14, 1997, No. 60/061,975, Attorney docket No 6882P October 14, 1997, No. 60/062,086, Attorney docket No 6883P October 14, 1997, No. 60/061,916, Attorney docket No 6884P October 14, 1997, No. 60/061,970, Attorney docket No 6885P October 14, 1997, No. 60/062,407, Attorney docket No 6886P October 14, 1997,.
  • the surfactant may be a modified alkylbenzene sulfonate surfactants, or MLAS.
  • MLAS modified alkylbenzene sulfonate surfactants
  • Suitable MLAS surfactants can be found in U.S. Patent applications Serial Nos. 60/053,319 filed on July 21 1997 (Docket No. 6766P), 60/053,318 filed on July 21 1997 (Docket No. 6767P), 60/053,321 filed on July 21 1997 (Docket No. 6768P), 60/053,209 filed on July 21 1997 (Docket No. 6769P), 60/053,328 filed on July 21 1997 (Docket No. 6770P),. 60/053,186 filed on July 21 1997 (Docket No.
  • anionic surfactants useful in the LDL of the present invention are preferably selected from the group consisting of, linear alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof.
  • An effective amount typically from about 0.5% to about 90%, preferably about 5% to about 50%, more preferably from about 10 to about 30%, by weight of anionic detersive surfactant can be used in the LDL compositions of the present invention
  • the laundry detergent compositions of the present invention typically compnse from about 0.1% to about 50%, preferably from about 1% to about 40% by weight of an anionic surfactant.
  • an anionic surfactant typically compnse from about 0.1% to about 50%, preferably from about 1% to about 40% by weight of an anionic surfactant.
  • Nonlimitmg examples of nonionic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C jQ -Ci g glycerol ethers, and the like.
  • AE alkoxylated alcohols
  • PFAA's polyhydroxy fatty acid amides
  • APG's alkyl polyglycosides
  • C jQ -Ci g glycerol ethers C jQ -Ci g glycerol ethers
  • nonionic surfactants of this type include TergitofT 15-S-9 (the condensation product of C1 -C15 linear alcohol with 9 moles ethylene oxide) and 24-L-6 NMW (the condensation product of C j2 -Ci4 pnmary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45.9 ( me condensation product of C 1 4-C15 linear alcohol with 9 moles of ethylene oxide), Neodol ⁇ ⁇ 23-3 (the condensation product of C j -C ⁇ 3 linear alcohol with 3 moles of ethylene oxide), Neodol ⁇ M 45-7 (the condensation product of C j 4-C
  • Another class of preferred nonionic co-surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
  • R! is H, or C 1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
  • R2 IS C5_ 3 1 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated de ⁇ vative thereof
  • Typical examples include the C ⁇ -Cj and C ⁇ 2 -Cj4 N-methylglucamides. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.
  • alkylpolysaccha ⁇ des such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986.
  • Preferred alkylpolyglycosides have the formula
  • R2 ⁇ (C n H 2n 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 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably de ⁇ ved from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and their 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-pos ⁇ t ⁇ on, preferably predominately the 2-pos ⁇ t ⁇ on.
  • Compounds of this type and their use detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present m an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include Igepal ⁇ M CO-630, marketed by the GAP Corporation; and TntonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • alkylphenol alkoxylates e.g., alkyl phenol ethoxylates.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • 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 PluromcTM surfactants, marketed by BASF.
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamme 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.
  • Examples of this type of nonionic surfactant include certain of the commercially available TetromcTM compounds, marketed by BASF.
  • compositions of the present invention may comprise amine oxide m accordance with the general formula I: Rl(EO) x (PO) y (BO) z N(0)(CH 2 R') 2 .qH 2 0 (I).
  • Rl(EO) x (PO) y (BO) z N(0)(CH 2 R') 2 .qH 2 0 (I).
  • R' is preferably selected from hydrogen, methyl and -CH 2 OH.
  • R* is a p ⁇ mary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R ⁇ is a p ⁇ mary alkyl moiety.
  • R! IS a hydrocarbyl moiety having chamlength of from about 8 to about 18.
  • R ⁇ may be somewhat longer, having a chamlength in the range C ⁇ 2 -C 4.
  • the invention also encompasses amme oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R ⁇ is a pnmary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • amme oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • amine oxides herein are solutions at ambient temperature.
  • Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • R' is H
  • R' is CH OH
  • hexadecylbis(2-hydroxyethyl)amine oxide such as hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide, dodecyldimethylamine oxide dihydrate.
  • Preferred amines for use herein include amines according to the formula:
  • Rj is a C5-C12 alkyl group
  • n is from about 2 to about 4
  • X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent
  • R 3 and R4 are individually selected from H, C1-C4 alkyl, or (CH -CH 2 -0(R5)) wherein R5 is H or methyl.
  • These preferred amines include the following:
  • the amine is described by the formula:
  • Particularly preferred amines include those selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-Cj 2 bis(hydroxyethyl)amine, Cg-Cj bis(hydroxyisopropyl)amine, and Cg-Cj 2 amido-propyl dimethyl amine, and mixtures.
  • Cationic Co-surfactants Nonlimiting examples of cationic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight include the choline ester-type quats and alkoxylated quaternary ammonium (AQA) surfactant compounds, and the like.
  • Cationic co-surfactants useful as a component of the surfactant system is a cationic cholme ester-type quat surfactant which are preferably water dispersible compounds having surfactant properties and comprise at least one ester (i.e. -COO-) linkage and at least one catiomcally charged group.
  • Suitable cationic ester surfactants, including chohne ester surfactants have for example been disclosed in U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529.
  • Cationic ester surfactants include those having the formula:
  • Rj is a C5-G31 linear or branched alkyl, alkenyl or alkaryl chain or M " .N + (RgR7Rg)(CH 2 ) s ;
  • X and Y independently, are selected from the group consisting of COO r OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group;
  • R 2 , R 3 , R4, R ⁇ , R7 and Rg are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
  • R5 is independently H or a C j -C 3 alkyl group; wherein the values of m, n, s and t independently he m the range of from 0 to 8, the value of
  • R 2 , R 3 and R4 are independently selected from CH 3 and -CH 2 CH 2 OH.
  • M is selected from the group consisting of hahde, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chlo ⁇ de, bromide or iodide.
  • Preferred water dispersible cationic ester surfactants are the cholme esters having the formula:
  • R ⁇ is a C ⁇ 1 -Ci 9 linear or branched alkyl chain.
  • the particularly preferred chohne esters may be prepared by the direct este ⁇ fication of a fatty acid of the desired chain length with dimethylaminoethanol, m the presence of an acid catalyst.
  • the reaction product is then quatermzed with a methyl hahde, preferably in the presence of a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as Ci Q-Cjg fatty alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole forming the desired cationic mate ⁇ al.
  • They may also be prepared by the direct este ⁇ fication of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst mate ⁇ al.
  • the reaction product is then quatermzed with t ⁇ methylamme, forming the desired cationic matenal.
  • these cationic ester surfactant are hydrolysable under the conditions of a laundry wash method.
  • AQA compounds alkoxylated quaternary ammonium surfactant compounds
  • R* is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms
  • R2 is an alkyl group containing from one to three carbon atoms, preferably methyl
  • R 3 and R ⁇ can vary independently and are selected from hydrogen (preferred), methyl and ethyl
  • X " is an anion such as chlonde, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C1 -C4 alkoxy, especially ethoxy (i.e., -CH 2 CH 2 0-), propoxy, butoxy and mixed ethoxy/propoxy; p is from 0 to about 30, preferably 1 to about 4 and q is from 0 to about 30, preferably 1 to about 4, and most preferably to about 4; preferably both p and q are 1. See also EP 2,084, published May 30, 1979, by The Procter & Gamble Company, which describes cationic co-surfactants of this type which are also useful herein..
  • the levels of the AQA surfactants used to prepare finished laundry detergent compositions typically range from about 0.1% to about 5%, preferably from about 0.45% to about 2.5%, by weight.
  • Heavy duty liquid detergent compositions herein, especially those designed for fab ⁇ c launde ⁇ ng, may also comprise a non-aqueous carrier medium as described in more detail hereinafter.
  • the shampoo compositions of the present invention typically can comp ⁇ se the following ingredients, components, or limitations descnbed herein.
  • water soluble refers to any material that is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% m water, i.e. distilled or equivalent, at 25°C.
  • the shampoo compositions of the present invention contain a shampoo composition adjunct ingredient which is preferably selected from anti-dandruff agents (preferably platelet py ⁇ dmethione salt crystals, sulfur, octopirox, selenium sulfide, ketoconazole and py ⁇ dmethione salts), co-surfactants (preferably selected from anionic surfactant, nonionic surfactant, cationic surfactant, amphote ⁇ c surfactant, zwitte ⁇ onic surfactants, and mixtures thereof), sihcone haif conditioning agent, polyalkylene glycols, suspending agent, water, water soluble cationic polymenc conditioning agents, hydrocarbon conditioning agents, foam boosters, preservatives, thickeners, cosurfactants, dyes, perfumes, solvents, styling polymers, anti-static agents, deposition polymers, styling polymers and solvent, dispersed phase polymers, non-volatile hydrocarbons conditioning agents, sihcone conditioning agents, suspending agent, cationic spreading agents phase
  • compositions of the present invention can also be in the form of LDL compositions
  • LDL compositions include additives typically used in LDL formulations, such as diamines, divalent ions, suds boosting polymers, soil release polymers, polymenc dispersants, polysaccha ⁇ des, abrasives, bacte ⁇ cides, tarnish inhibitors, builders, enzymes, dyes, perfumes, thickeners, antioxidants, processing aids, suds boosters, buffers, antifungal or mildew control agents, insect repellants, anti-corrosive aids, and chelants.
  • additives typically used in LDL formulations such as diamines, divalent ions, suds boosting polymers, soil release polymers, polymenc dispersants, polysaccha ⁇ des, abrasives, bacte ⁇ cides, tarnish inhibitors, builders, enzymes, dyes, perfumes, thickeners, antioxidants, processing aids, suds boosters, buffers, antifungal or mild
  • the composition will preferably contain at least about 0.1%, more preferably at least about 0.2%, even more preferably, at least about 0.25%, even more preferably still, at least about 0.5% by weight of said composition of diamme.
  • the composition will also preferably contain no more than about 15%, more preferably no more than about 10%, even more preferably, no more than about 6%, even more preferably, no more than about 5%, even more preferably still, no more than about 1.5% by weight of said composition of diamme.
  • compositions of the present invention be "malodor" free. That is, that the odor of the headspace does not generate a negative olfactory response from the consumer.
  • Preferred organic diamines are those in which pKl and pK2 are in the range of about 8.0 to about 11.5, preferably in the range of about 8.4 to about 11, even more preferably from about 8.6 to about 10.75.
  • mate ⁇ als are the p ⁇ mary/p ⁇ mary diamines with alkylene spacers ranging from C4 to C8. In general, it is believed that p ⁇ mary diammes are preferred over secondary and tertiary diamines.
  • pKal and pKa2 are quantities of a type collectively known to those skilled in the art as “pKa” pKa is used herein in the same manner as is commonly known to people skilled m the art of chemistry. Values referenced herein can be obtained from literature, such as from “C ⁇ tical Stability Constants: Volume 2, Amines” by Smith and Martel, Plenum Press, NY and London, 1975 Additional information on pKa's can be obtained from relevant company literature, such as information supplied by Dupont, a supplier of diammes. More detailed information of pKa's can be found in US Pat App No.
  • the diammes useful herein can be defined by the following structure:
  • R 2 _5 are independently selected from H, methyl, -CH 3 CH 2 , and ethylene oxides;
  • C x and C v are independently selected from methylene groups or branched alkyl groups where x+y is from about 3 to about 6; and
  • A is optionally present and is selected from electron donating or withdrawing moieties chosen to adjust the diamine pKa's to the desired range. If A is present, then x and y must both be 1 or greater.
  • the preferred diamines can be those with a molecular weight less than or equal to 400 g/mol. It is preferred that these diamines have the formula: wherein each R 6 is independently selected from the group consisting of hydrogen, C1-C4 linear or branched alkyl, alkyleneoxy having the formula:
  • R ⁇ is C -C4 linear or branched alkylene, and mixtures thereof;
  • R is hydrogen, C1-C4 alkyl, and mixtures thereof;
  • m is from 1 to about 10;
  • X is a unit selected from:
  • diamme III) mixtures of (1) and (11) provided said diamme has a pK a of at least about 8.
  • preferred diammes include the following: dimethyl ammopropyl amme, 1,6-hexane diamine, 1,3 propane diamme, 2-methyl 1,5 pentane diamine, 1,3-Pentaned ⁇ am ⁇ ne, 1,3-d ⁇ am ⁇ nobutane, 1 ,2-b ⁇ s(2-am ⁇ noethoxy)ethane, Isophorone diamme, l,3-b ⁇ s(methylam ⁇ ne)-cyclohexane and mixtures thereof.
  • compositions of the present invention may optionally contain a polymenc suds stabilizer. These polymenc suds stabilizers provide extended suds volume and suds duration without sacnficmg the grease cutting ability of the liquid detergent compositions. These polymenc suds stabilizers are selected from:
  • R is hydrogen, C1-C6 alkyl, and mixtures thereof, provided that the ratio of (ii) to (i) is from about 2 to 1 to about 1 to 2;
  • the molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from about 1,000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, more preferably from about 10,000 to about 750,000, more preferably from about 20,000 to about 500,000, even more preferably from about 35,000 to about 200,000.
  • the polymeric suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • a salt either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • One preferred polymeric suds stabilizer is (N,N-dimethylamino)alkyl acrylate esters, namely
  • the polymeric suds booster may be present in the composition from about 0.01% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.1 % to about 5%, by weight.
  • Suitable polymeric suds stabilizers including protenacious suds stabilizers and zwitterionic suds stabilizers, can be found in PCT/US98/24853 filed November 20, 1998 (Docket No. 6938), PCT/US98/24707 filed November 20, 1998(Docket No. 6939), PCT/US98/24699 filed November 20, 1998(Docket No. 6943), and PCT/US98/24852 filed November 20, 1998(Docket No. 6944). Also suitable are the cationic copolymer stabilizers, which can be found in US Patent 4454060.
  • Enzymes - Detergent compositions of the present invention may further comp ⁇ se one or more enzymes which provide cleaning performance benefits.
  • Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectmases, xylanases, reductases, oxidases, phenoloxidases, hpoxygenases, hgninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, hpase, cutmase and/or cellulase. Enzymes when present in the compositions, at from about 0.0001% to about 5% of active enzyme by weight of the detergent composition.
  • proteolytic Enzyme can be of animal, vegetable or microorganism (preferred) ongm.
  • the proteases for use m the detergent compositions herein " include (but are not limited to) trypsin, subtihsm, chymotrypsin and elastase-type proteases.
  • Preferred for use herein are subtihsm-type proteolytic enzymes.
  • Particularly preferred is bacterial se ⁇ ne proteolytic enzyme obtained from Bacillus subti s and/or Bacillus hchemformis.
  • Suitable proteolytic enzymes include Novo Indust ⁇ A/S Alcalase® (preferred), Esperase®'
  • proteolytic enzymes are also modified bacte ⁇ al se ⁇ ne proteases, such as those made by Genencor International, Inc. (San Francisco, California) which are desc ⁇ bed m European Patent 251,446B, granted December 28, 1994 (particularly pages 17, 24 and 98) and which are also called herein "Protease B”.
  • proteases are sold under the tradenames: P ⁇ mase, Durazym, Opticlean and Optimase.
  • Preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Indust ⁇ A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred.
  • proteases described in our co-pending application USSN 08/136,797 can be included m the detergent composition of the invention.
  • Another preferred protease referred to as "Protease D” is a carbonyl hydrolase vanant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different ammo acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also m combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156,
  • Protease enzyme may be mco ⁇ orated into the compositions in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Amylase - Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
  • Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk).
  • the enzymes may be of any suitable ongin, such as vegetable, animal, bactenal, fungal and yeast ongin.
  • Amylase enzymes are normally mco ⁇ orated m the detergent composition at levels from 0.0001% to 2%, preferably from about 0.0001% to about 0.5%, more preferably from about 0.0005% to about 0.1%, even more preferably from about 0.001% to about 0.05% of active enzyme by weight of the detergent composition.
  • Amylase enzymes also include those desc ⁇ bed W095/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056.
  • amylase enzyme is NATALASE® available from Novo Nordisk.
  • amylases suitable herein include, for example, ⁇ -amylases desc ⁇ bed in GB 1,296,839 to Novo; RAPID ASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo FUNGAMYL® from Novo is especially useful.
  • Particularly preferred amylases herein include amylase vanants having additional modification in the immediate parent as desc ⁇ bed in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®.
  • Other particularly preferred oxidative stability enhanced amylase include those desc ⁇ bed in WO 9418314 to Genencor International and WO 9402597 to Novo.
  • Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimenc, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • carbohydrase enzymes which impart antimicrobial activity may also be included in the present invention.
  • Such enzymes include endoglycosidase, Type II endoglycosidase and glucosidase as disclosed m U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843 and 5,356,803 the disclosures of which are herein inco ⁇ orated by reference.
  • other enzymes having antimicrobial activity may be employed as well including peroxidases, oxidases and va ⁇ ous other enzymes.
  • an enzyme stabilization system into the compositions of the present invention when any enzyme is present m the composition.
  • Va ⁇ ous carbohydrase enzymes which impart antimicrobial activity may also be included in the present invention.
  • Such enzymes include endoglycosidase, Type JJ endoglycosidase and " glucosidase as disclosed m U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843 and 5,356,803 the disclosures of which are herein inco ⁇ orated by reference.
  • other enzymes having antimicrobial activity may be employed as well including peroxidases, oxidases and va ⁇ ous other enzymes.
  • Peroxidase enzymes can be used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are typically used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates du ⁇ ng wash operations to other substrates m the wash solution.
  • oxygen sources e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are typically used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates du ⁇ ng wash operations to other substrates m the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, hgninase, and haloperoxidase such as chloro- and bromo- peroxidase.
  • Peroxidase-contammg 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.
  • the present invention encompasses peroxidase-free automatic dishwashing composition embodiments.
  • the enzymes may be inco ⁇ orated into detergent compositions herein m the form of suspensions, "marumes” or “pnlls".
  • Another suitable type of enzyme comprises those m the form of slurries of enzymes m nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL” or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP.”
  • Enzymes added to the compositions herein m the form of conventional enzyme prills are especially preferred for use herein.
  • Such p ⁇ lls will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition.
  • P ⁇ lls m the compositions of the present invention have been found, in compa ⁇ son with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time.
  • compositions which utilize enzyme p ⁇ lls need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are inco ⁇ orated into aqueous liquid detergents.
  • non-aqueous liquid detergent compositions herein will typically compnse from about 0.001% to 5%, preferably from about 0.01% to 1% by weight, of a commercial enzyme preparation.
  • Protease enzymes for example, 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.
  • Enzyme Stabilizing System The enzyme-containing compositions herein may optionally also compnse from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes.
  • Such stabilizing systems can, for example, compnse calcium ion, bone acid, propylene glycol, short chain carboxyhc acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
  • Perfumes - Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like.
  • Finished perfumes can compnse extremely complex mixtures of such ingredients. Finished perfumes typically comprise from about 0.01% to about 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comp ⁇ se from about 0.0001% to about 90% of a finished perfume composition.
  • Chelating Agents may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of ammo carboxylates, ammo phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these matenals is due m part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminet ⁇ acetates, nit ⁇ lo-t ⁇ -acetates, ethylenediamme tetrapro-pnonates, tnethylenetetraammehexacetates, diethylenetnamine- pentaacetates, and ethanoldiglycmes, 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 lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediammetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful m the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-d ⁇ hydroxy-3,5-d ⁇ sulfobenzene.
  • a preferred biodegradable chelator for use herein is ethylenediamme disuccinate
  • compositions herein may also contain water-soluble methyl glycme diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder.
  • MGDA water-soluble methyl glycme diacetic acid
  • weak builders such as citrate can also be used as chelating agents.
  • these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will compnse from about 0.1% to about 3.0% by weight of such compositions.
  • compositions of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes.
  • a composition with a pH greater than 7 it preferably should contain a buffenng agent capable of providing a generally more alkaline pH in the composition and m dilute solutions, i.e., about 0.1% to 0.4% by weight aqueous solution, of the composition.
  • the pKa value of this buffenng agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as descnbed above).
  • the pKa of the buffenng agent should be from about 7 to about 10. Under these conditions the buffenng agent most effectively controls the pH while using the least amount thereof.
  • the buffenng agent may be an active detergent m its own ⁇ ght, or it may be a low molecular weight, organic or inorganic matenal that is used in this composition solely for maintaining an alkaline pH.
  • Preferred buffenng agents for compositions of this invention are nitrogen-containmg matenals.
  • Some examples are amino acids such as lysine or lower alcohol amines like mono-, di-, and tn-ethanolamme.
  • nitrogen-containmg buffenng agents are Tn(hydroxymethyl)am ⁇ no methane (HOCH2)3CNH3 (TRIS), 2-ammo-2 -ethyl- 1,3- propanediol, 2-ammo-2-methyl-propanol, 2-am ⁇ no-2 -methyl- 1,3-propanol, disodium glutamate, N-methyl diethanolamide, 1,3-d ⁇ am ⁇ no-propanol N,N'-tetra-methyl-l,3-d ⁇ am ⁇ no-2-propanol, N,N- b ⁇ s(2-hydroxyethyl)glycme (bicine) and N-t ⁇ s (hydroxymethyl)methyl glycine (t ⁇ cine).
  • Tn(hydroxymethyl)am ⁇ no methane (HOCH2)3CNH3 Tn(hydroxymethyl)am ⁇ no methane (HOCH2)3CNH3 (TRIS)
  • Useful inorganic buffers/alkalinity sources include the alkali metal carbonates and alkali metal phosphates, e.g., sodium carbonate, sodium polyphosphate.
  • alkali metal carbonates and alkali metal phosphates e.g., sodium carbonate, sodium polyphosphate.
  • alkali metal carbonates and alkali metal phosphates e.g., sodium carbonate, sodium polyphosphate.
  • McCutcheon's EMULSIFEERS AND DETERGENTS North Amencan Edition, 1997, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971 both of which are inco ⁇ orated herein by reference.
  • the buffenng agent if used, is present in the compositions of the invention herein at a level of from about 0.1 % to 15%, preferably from about 1% to 10%, most preferably from about 2% to 8%, by weight of the composition.
  • Bleaching Compounds Bleaching Agents and Bleach Activators The granular detergent compositions herein preferably further contain a bleach and/or a bleach activators.
  • the granular bleaching detergent compositions herein will contain a bleach and a bleach activator.
  • Bleaches agents will typically, when present, be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric launde ⁇ ng. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaches used herein can be any of the bleaches useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning pu ⁇ oses that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • bleaches that can be used without rest ⁇ ction encompasses percarboxyhc acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylammo-4-oxoperoxybutync acid and diperoxydodecanedioic acid.
  • Such bleaches are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaches also include 6-nonylammo-6-oxoperoxycapro ⁇ c acid as descnbed in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach compnses dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from vanous commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaches can also be used.
  • Peroxygen bleaches, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., dunng the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Va ⁇ ous nonhmiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamme
  • Bleach activators useful herein include amides, lmides, esters and anhydrides. Commonly at least one substituted or unsubstituted acyl moiety is present, covalently connected to a leaving group as in the structure R-C(0)-L.
  • bleach activators are combined with a source of hydrogen peroxide, such as the perborates or percarbonates, in a single product. Conveniently, the single product leads to in situ production in aqueous solution (i.e., during the washing process) of the percarboxyhc acid corresponding to the bleach activator.
  • the product itself can be hydrous, for example a powder, provided that water is controlled in amount and mobility such that storage stability is acceptable.
  • the product can be an anhydrous solid or liquid.
  • the bleach activator or oxygen bleach is inco ⁇ orated in a pretreatment product, such as a stain stick; soiled, pretreated substrates can then be exposed to further treatments, for example of a hydrogen peroxide source.
  • a pretreatment product such as a stain stick
  • soiled, pretreated substrates can then be exposed to further treatments, for example of a hydrogen peroxide source.
  • the atom in the leaving group connecting to the peracid-formmg acyl moiety R(C)0- is most typically O or N.
  • Bleach activators can have non-charged, positively or negatively charged peracid-forming moieties and/or noncharged, positively or negatively charged leaving groups.
  • One or more peracid-formmg moieties or leav g-groups can be present.
  • bleach activators can be substituted with electron-donating or electron-releasing moieties either in the leavmg-group or in the peracid-formmg moiety or moieties, changing their reactivity and making them more or less suited to particular pH or wash conditions.
  • electron-withdrawing groups such as N0 2 improve the efficacy of bleach activators intended for use m mild-pH (e.g., from about 7.5- to about 9.5) wash conditions.
  • Cationic bleach activators include quaternary carbamate-, quaternary carbonate-, quaternary ester- and quaternary amide- types, de ve ⁇ ng a range of cationic peroxyimidic, peroxycarbonic or peroxycarboxyhc acids to the wash.
  • An analogous but non-catiomc palette of bleach activators is available when quaternary derivatives are not desired.
  • cationic activators include quaternary ammonium-substituted activators of WO 96-06915, U S. 4,751,015 and 4,397,757, EP-A-284292, EP-A-331,229 and EP-A-03520.
  • cationic nitnles as disclosed in EP-A-303,520 and m European Patent Specification 458,396 and 464,880.
  • Other nit ⁇ le types have electron-withdrawing substituents as descnbed m U.S. 5,591,378.
  • bleach activator disclosures include GB 836,988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; U.S. Pat. Nos. 1,246,339; 3,332,882; 4,128,494, 4,412,934 and 4,675,393, and the phenol sulfonate ester of alkanoyl ammoacids disclosed in U.S. 5,523,434.
  • Suitable bleach activators include any acetylated diamme types, whether hydrophilic or hydrophobic in character.
  • preferred classes include the esters, including acyl phenol sulfonates, acyl alkyl phenol sulfonates or acyl oxybenzenesulfonates (OBS leavmg- group); the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitnles.
  • esters including acyl phenol sulfonates, acyl alkyl phenol sulfonates or acyl oxybenzenesulfonates (OBS leavmg- group); the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitnles.
  • Preferred bleach activators include N,N,N'N'-tetraacetyl ethylene diamme (TAED) or any of its close relatives including the tnacetyl or other unsymmet ⁇ cal denvatives.
  • TAED and the acetylated carbohydrates such as glucose pentaacetate and tetraacetyl xylose are preferred hydrophilic bleach activators.
  • acetyl tnethyl citrate a liquid, also has some utility, as does phenyl benzoate.
  • Preferred hydrophobic bleach activators include sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), N-(alkanoyl)am ⁇ noalkanoyloxy benzene sulfonates, such as 4-[N- (nonanoyl)ammohexanoyloxy]-benzene sulfonate or (NACA-OBS) as descnbed in US Patent 5,534,642 and in EPA 0 355 384 Al, substituted amide types desc ⁇ bed m detail hereinafter, such as activators related to NAPAA, and activators related to certain lmidoperacid bleaches, for example as desc ⁇ bed in U.S.
  • Patent 5,061,807 issued October 29, 1991 and assigned to Hoechst Aktiengesellschaft of Frankfurt, Germany and Japanese Laid-Open Patent Application (Kokai) No. 4-28799.
  • Another group of peracids and bleach activators herein are those denvable from acyclic lmidoperoxycarboxyhc acids and salts thereof, See US Patent 5415796, and cyclic lmidoperoxycarboxyhc acids and salts thereof, see US patents 5,061,807, 5,132,431, 5,6542,69, 5,246,620, 5,419,864 and 5,438,147.
  • bleach activators include sod ⁇ um-4-benzoyloxy benzene sulfonate (SBOBS); sodium- 1 -methyl-2-benzoyloxy benzene-4-sulphonate; sod ⁇ um-4-methyl-3- benzoyloxy benzoate (SPCC); tnmethyl ammonium toluyloxy-benzene sulfonate; or sodium 3,5,5-t ⁇ methyl hexanoyloxybenzene sulfonate (STHOBS).
  • Bleach activators may be used in an amount of up to 20%, preferably from 0.1-10% by weight, of the composition, though higher levels, 40% or more, are acceptable, for example in highly concentrated bleach additive product forms or forms intended for appliance automated dosing.
  • bleaching results can be obtained from bleaching systems having with m-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5.
  • activators with electron- withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
  • Alkalis and buffenng agents can be used to secure such pH.
  • Acyl lactam activators are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639). See also U.S. 4,545,784 which discloses acyl caprolactams, including benzoyl caprolactam adsorbed into sodium perborate.
  • NOBS, lactam activators, imide activators or amide-functional activators are desirably combined with hydrophilic activators such as TAED, typically at weight ratios of hydrophobic activator : TAED in the range of 1 :5 to 5.1, preferably about 1 :1.
  • hydrophilic activators such as TAED
  • Other suitable lactam activators are alpha-modified, see WO 96-22350 Al, July 25, 1996.
  • Lactam activators, especially the more hydrophobic types are desirably used in combination with TAED, typically at weight ratios of amido-de ⁇ ved or caprolactam activators : TAED in the range of 1 :5 to 5: 1, preferably about 1: 1.
  • TAED typically at weight ratios of amido-de ⁇ ved or caprolactam activators : TAED in the range of 1 :5 to 5: 1, preferably about 1: 1.
  • bleach activators having cyclic amidine leavmg- group disclosed in U
  • Nonhmiting examples of additional activators useful herein are to be found in U.S. 4,915,854, U.S. 4,412,934 and 4,634,551.
  • the hydrophobic activator nonanoyloxybenzene sulfonate (NOBS) and the hydrophilic tetraacetyl ethylene diamme (TAED) activator are typical, and mixtures thereof can also be used.
  • Additional activators useful herein include those of U.S. 5,545,349, which is also inco ⁇ orated herein by reference.
  • Bleaches other than oxygen bleaching agents are also known m the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaches such as the sulfonated zinc and/or aluminum phthalocyanmes. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zmc phthalocyamne.
  • Bleach Catalysts are also known m the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaches such as the sulfonated zinc and/or aluminum phthalocyanmes. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleache
  • compositions and methods utilize metal-containmg bleach catalysts that are effective for use m ADD compositions.
  • Preferred are manganese and cobalt- contammg bleach catalysts.
  • Preferred cobalt catalysts of this type have the formula:
  • the preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH )5Cl] Y y , and especially [Co(NH )5Cl]Cl .
  • cobalt pentaamine acetate salts having the formula [Co(NH 3 )5 ⁇ Ac] T y , wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH 3 )5 ⁇ Ac]Cl ; as well as [Co(NH 3 ) 5 OAc](OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ; [Co(NH 3 ) 5 OAc](S0 4 ); [Co-
  • the cleaning compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species m the wash liquor.
  • typical automatic dishwashing compositions herein will compnse from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst by weight of the cleaning compositions.
  • Builders - Builders can operate via a vanety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offe ⁇ ng a surface " more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned.
  • Builder level can vary widely depending upon end use and physical form of the composition. For example, high-surfactant formulations can be unbuilt.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will compnse at least about 0.1%, preferably from about 1% to about 90%, more preferably from about 5% to about 80%, even more preferably from about 10% to about 40% by weight, of the detergent builder. Lower or higher levels of builder, however, are not excluded.
  • Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di-, tn-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomenc or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
  • phosphates and polyphosphates especially the sodium salts
  • carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate organic mono-, di-, tn-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomenc or water-soluble low mole
  • Builder mixtures sometimes termed “builder systems” can be used and typically compnse two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers, though these latter mate ⁇ als are generally accounted for separately when descnbmg quantities of matenals herein.
  • preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60:1 to about 1:80.
  • Certain preferred granular detergents have said ratio in the range 0.90: 1.0 to 4.0: 1.0, more preferably from 0.95: 1.0 to 3.0:1.0.
  • P-containing detergent builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.
  • phosphorus-based builders can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used though such materials are more commonly used in a low-level mode as chelants or stabilizers.
  • Phosphate detergent builders for use in granular compositions are well known. They include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates). Phosphate builder sources are described in detail in Kirk Othmer, 3rd Edition, Vol. 17, pp. 426-472 and in "Advanced Inorganic Chemistry” by Cotton and Wilkinson, pp. 394- 400 (John Wiley and Sons, Inc.; 1972).
  • Preferred levels of phosphate builders herein are from about 10% to about 75%, preferably from about 15% to about 50%, of phosphate builder.
  • Phosphate builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Builders are typically used in automatic dishwashing to assist in the removal of particulate soils.
  • Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na 2 C0 3 .CaC0 when anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds.
  • Various grades and types of sodium carbonate and sodium sesquicarbonate may be used, certain of which are particularly useful as carriers for other ingredients, especially detersive surfactants.
  • Suitable organic detergent builders include polycarboxylate compounds, including water- soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred
  • Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccmate, see Berg, U.S. 3,128,287, Ap ⁇ l 7, 1964, and Lamberti et al, U.S.
  • Suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhyd ⁇ de with ethylene or vmyl methyl ether; 1, 3, 5-t ⁇ hydroxy benzene-2, 4, 6-tnsulphon ⁇ c acid; carboxymethyloxysuccimc acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamme tetraacetic acid and mt ⁇ lotnacetic acid; as well as melhtic acid, succimc acid, oxydisuccmic acid, polymaleic acid, benzene 1,3,5- tncarboxyhc acid, carboxymethyloxysuccimc acid, and soluble salts thereof.
  • Citrates e.g., citnc acid and soluble salts thereof are important carboxylate builders due to availability from renewable resources and biodegradability. Citrates can also be used m the present granular compositions, especially in combination with zeolite and/or layered silicates Citrates can also be used in combination with zeolite, the hereafter mentioned BRJTESIL types, and/or layered silicate builders. Oxydisuccinates are also useful in such compositions and combinations. Oxydisuccinates are also especially useful in such compositions and combinations.
  • alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 - hydroxy-l,l-d ⁇ phos ⁇ honate and other known phosphonates, e.g., those of U.S. 3,159,581, 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable antiscahng properties.
  • detersive surfactants or their short-chain homologs also have a builder action
  • these matenals are summed up as detersive surfactants.
  • Preferred types for builder functionality are illustrated by: 3,3-d ⁇ carboxy-4-oxa-l,6-hexaned ⁇ oates and the related compounds disclosed m U.S. 4,566,984, Bush, January 28, 1986.
  • Succimc acid builders include the C5-O20 alkyl and alkenyl succimc acids and salts thereof.
  • Succmate builders also include: laurylsuccmate, mynstylsuccinate, palmitylsuccmate, 2-dodecenylsucc ⁇ nate (preferred), 2-pentadecenylsuccmate, and the like.
  • Lauryl-succinates are described m European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C 12 -C j g monocarboxy c acids, can also be inco ⁇ orated into the compositions as surfactant/builder matenals alone or in combination with the aforementioned builders, especially citrate and/or the succmate builders, to provide additional builder activity but are generally not desired.
  • fatty acids will generally result in a diminution of sudsmg in laundry compositions, which may need to be taken into account by the formulator.
  • Fatty acids or their salts are undesirable m Automatic Dishwashing (ADD) embodiments in situations wherein soap scums can form and be deposited on dishware.
  • ADD Automatic Dishwashing
  • Other suitable polycarboxylates are disclosed m U.S. 4,144,226, Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.
  • Other types of inorganic builder materials which can be used have the formula (M x ) x Ca y
  • a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred.
  • noncarbonate anions include those selected from the group consisting of chlonde, sulfate, fluo ⁇ de, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof.
  • Preferred builders of this type in their simplest forms are selected from the group consisting of Na 2 Ca(C0 3 ) 2 , K 2 Ca(C0 3 ) 2 , Na 2 Ca 2 (C0 3 ) 3 , NaKCa(C0 3 ) 2 , NaKCa 2 (C0 3 ) 3 , K 2 Ca 2 (C0 3 ) 3 , and combinations thereof.
  • An especially preferred matenal for the builder desc ⁇ bed herein is Na 2 Ca(C0 ) 2 m any of its crystalline modifications.
  • Suitable builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any one or combinations of the following minerals: Afghamte, Andersomte, AshcroftineY, Beyente, Borca ⁇ te, Burbankite, Butschl ⁇ te, Cancnnite, Carbocernaite, Carletomte, Davyne, DonnayiteY, Fairchildite, Fer ⁇ su ⁇ te, Franzmite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettne ⁇ te, Khanneshite, LepersonniteGd, Liottite, MckelveyiteY, Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Schrockingente, Shortite, Sunte, Tumsite, Tuscanite, Tyrohte, Vishnevite, and Zem
  • Suitable silicate builders include water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amo ⁇ hous-solid or non- structured-liquid types.
  • alkali metal silicates particularly those liquids and solids having a Si0 2 :Na 2 0 ratio in the range 1.6:1 to 3.2: 1, including, particularly for automatic dishwashing pu ⁇ oses, solid hydrous 2-ratio silicates marketed by PQ Co ⁇ . under the tradename BRLTESIL®, e.g., BRITESIL H20; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck.
  • NaSKS-6 is a crystalline layered aluminium-free ⁇ -Na 2 Si ⁇ 5 mo ⁇ hology silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See preparative methods in German DE-A-3 ,417,649 and DE- A-3, 742,043.
  • Other layered silicates such as those having the general formula NaMSi x 0 2x + j yH 2 0 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein.
  • Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the ⁇ , ⁇ and ⁇ layer- silicate forms.
  • Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.
  • crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM O ySi0 .zM'0 wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995.
  • Aluminosilicate builders are especially useful in granular compositions, but can also be inco ⁇ orated in liquids, pastes or gels.
  • Suitable for the present pu ⁇ oses are those having empirical formula: [M z (AlO 2 ) z (Si0 2 ) v ]-xH 2 0 wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
  • Aluminosilicates can be crystalline or amo ⁇ hous, naturally-occurring or synthetically derived. An aluminosilicate production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Detergent builders other than silicates can be used in the compositions herein to assist in controlling mineral hardness. They can be used in conjunction with or instead of aluminosilicates and silicates. Inorganic as well as organic builders can be used. Builders are used in automatic dishwashing to assist m the removal of particulate soils.
  • Inorganic or non-phosphate-contammg detergent builders include, but are not limited to, phosphonates, phytic acid, carbonates (including bicarbonates and sesquicarbonates), sulfates, citrate, zeolite, and aluminosilicates.
  • Aluminosilicate builders may be used m the present compositions though are not preferred for automatic dishwashing detergents. (See U.S. Pat. 4,605,509 for examples of preferred aluminosilicates.)
  • Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empincal formula: Na 2 0 Al 2 0 3 xS ⁇ 0 z yH 0 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 about 0.5, and x is an integer from about 15 to about 264.
  • aluminosilicate ion exchange mate ⁇ als are commercially available. These aluminosilicates can be crystalline or amo ⁇ hous in structure and can be naturally-occur ⁇ ng aluminosilicates or synthetically denved. A method for producing aluminosilicate ion exchange matenals is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange matenals useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange matenal has the formula: Na ⁇ 2 [(A10 2 ) ⁇ 2 (Si0 2 ) ⁇ 2 ]-xH 2 0 wherein x is from about 20 to about 30, especially about 27. This matenal is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Individual particles can desirably be even smaller than 0.1 micron to further assist kinetics of exchange through maximization of surface area.
  • High surface area also increases utility of aluminosilicates as adsorbents for surfactants, especially in granular compositions.
  • Aggregates of aluminosilicate particles may be useful, a single aggregate having dimensions tailored to minimize segregation in granular compositions, while the aggregate particle remains dispersible to submicron individual particles du ⁇ ng the wash.
  • compositions according to the present invention may optionally comprise one or more soil release agents.
  • 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 the laundry cycle and , thus, serve as an anchor for the hydrophilic segments. This can enable stains occuring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • soil release agents will generally comprise from about 0.01% to about 10% preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3% by weight, of the composition.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.
  • 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 polymenc dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate mate ⁇ als can be prepared by polymenzmg or copolyme ⁇ zmg suitable unsaturated monomers, preferably m their acid form.
  • Unsaturated monome ⁇ c acids that can be polymerized to form suitable polymenc polycarboxylates include acrylic acid, maleic acid (or maleic anhyd ⁇ de), fumanc acid, ltacomc acid, aconitic acid, mesaconic acid, citracomc acid and methylenemalomc acid.
  • the presence in the polymenc polycarboxylates herein or monome ⁇ c segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymenc polycarboxylates can be denved from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymenzed 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, m Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
  • Acryhc/maleic-based copolymers may also be used as a preferred component of the dispersmg/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 about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • 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.
  • 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 mate ⁇ als which are desc ⁇ bed in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also descnbes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acryhc/vmyl alcohol te ⁇ olymers.
  • Such mate ⁇ als are also disclosed in EP 193,360, including, for example, the 45/45/10 te ⁇ olymer of acryhc/maleic/vmyl alcohol.
  • PEG polyethylene glycol
  • PEG polyethylene glycol
  • Typical molecular weight ranges for these pu ⁇ oses range from about 500 to about
  • 100,000 preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially m conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • Bnghtener - Any optical b ⁇ ghteners or other b ⁇ ghtenmg or whitening agents known in the art can be inco ⁇ orated at levels typically from about 0.01% to about 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical b ⁇ ghteners which may be useful in the " present invention can be classified into subgroups, which include, but are not necessarily limited to, denvatives of stilbene, pyrazolme, coumann, carboxylic acid, methinecyanmes, d ⁇ benzoth ⁇ ophene-5,5-d ⁇ ox ⁇ de, azoles, 5- and 6-membered- ⁇ ng heterocycles, and other miscellaneous agents.
  • b ⁇ ghteners examples include those identified m U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These b ⁇ ghteners include the PHORWHLTE senes of bnghteners from Verona.
  • Tmopal UNPA Tmopal CBS and Tmopal 5BM
  • Ciba-Geigy available from Ciba-Geigy
  • Artie White CC and Artie White CWD the 2-(4-styryl-phenyl)-2H-naptho[l,2- d]tnazoles
  • 4,4'-b ⁇ s(styryl)b ⁇ sphenyls and the ammo- coumanns.
  • these bnghteners include 4-methyl-7-d ⁇ ethyl- ammo coumann; 1 ,2-b ⁇ s(benz ⁇ m ⁇ dazol-2-yl)ethylene; 1 ,3-d ⁇ phenyl-pyrazohnes; 2,5-b ⁇ s(benzoxazol-2-yl)th ⁇ ophene; 2-styryl-naptho[l,2-d]oxazole; and 2-(st ⁇ lben-4-yl)-2H-naphtho[l,2-d]tnazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.
  • compositions of the present invention may also include one or more mate ⁇ als effective for inhibiting the transfer of dyes from one fab ⁇ c to another dunng the cleaning process.
  • dye transfer inhibiting agents include polyvmyl pyrrohdone polymers, polyamine N-oxide polymers, copolymers of N-vmylpyrrohdone and N-vinyhmidazole, manganese phthalocyamne, peroxidases, and mixtures thereof. If used, 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%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-0 group can be represented by the following general structures:
  • 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.
  • 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. However, 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. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • Copolymers of N-vmylpyrrohdone and N-vmyhmidazole polymers are also preferred for use herein.
  • the 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 average molecular weight range is determined by light scattering as desc ⁇ bed in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vmyhmidazole to N-vmylpyrrohdone 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.
  • the present invention compositions also may employ a polyvmylpyrrohdone (“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 polyvmylpyrrohdone
  • 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.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered m wash solutions is from about 2: 1 to about 50:1, and more preferably from about 3:1 to about 10: 1.
  • compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical b ⁇ ghteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comp ⁇ se from about 0.01% to 1% by weight of such optical b ⁇ ghteners.
  • hydrophilic optical bnghteners useful m the present invention are those having the structural formula:
  • R ⁇ is selected from anihno, N-2-b ⁇ s-hydroxyethyl and NH-2-hydroxyethyl
  • R 2 is selected from N-2-b ⁇ s-hydroxyethyl, N-2-hydroxyethyl-N-methylammo, mo ⁇ hilmo, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R ⁇ is anihno
  • R 2 is N-2-b ⁇ s-hydroxyethyl and M is a cation such as sodium
  • the bnghtener is 4,4',-b ⁇ s[(4-an ⁇ l ⁇ no-6-(N-2-b ⁇ s-hydroxyethyl)-s-t ⁇ az ⁇ ne-2- yl)ammo]-2,2'-st ⁇ lbened ⁇ sulfon ⁇ c acid and disodium salt.
  • This particular bnghtener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Co ⁇ oration.
  • T opal-UNPA-GX is the preferred hydrophilic optical bnghtener useful in the detergent compositions herein.
  • R ⁇ is anihno
  • R 2 is N-2-hydroxyethyl-N-2-methylammo and
  • M is a cation such as sodium
  • the bnghtener is 4,4'-bis[(4-amhno-6-(N-2-hydroxyethyl-N- methylam ⁇ no)-s-t ⁇ azme-2-yl)am ⁇ no]2,2'-st ⁇ lbened ⁇ sulfon ⁇ c acid disodium salt.
  • This particular bnghtener species is commercially marketed under the tradename Tmopal 5BM-GX by Ciba- Geigy Co ⁇ oration.
  • R ⁇ is anihno
  • R is mo ⁇ hihno
  • M is a cation such as sodium
  • the bnghtener is 4,4'-b ⁇ s[(4-an ⁇ hno-6-mo ⁇ h ⁇ l ⁇ no-s-tnazme-2-yl)am ⁇ no]2,2'- stilbenedisulfomc acid, sodium salt.
  • This particular bnghtener species is commercially marketed under the tradename Tmopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • the specific optical bnghtener species selected for use m the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymenc dye transfer inhibiting agents hereinbefore descnbed.
  • the combination of such selected polymenc mate ⁇ als (e.g., PVNO and/or PVPVI) with such selected optical b ⁇ ghteners (e.g., Tmopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two granular composition components when used alone
  • such b ⁇ ghteners work this way because they have high affinity for fab ⁇ cs in the wash solution and therefore deposit relatively quick on these fabncs.
  • exhaustion coefficient is in general as the ratio of a) the bnghtener matenal deposited on fabnc to b) the initial bnghtener concentration m the wash liquor.
  • B ⁇ ghteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer m the context of the present invention.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be inco ⁇ orated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor 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.
  • compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ⁇ ⁇ - ⁇ Q ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine 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 temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 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.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethyl- siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Sihcone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • sihcone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Sihcone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Bagmski et al, issued March 24, 1987.
  • An exemplary sihcone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the pnmary sihcone suds suppressor is branched/crosshnked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comp ⁇ se from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said sihcone uds suppressor, which comp ⁇ ses (1) a nonaqueous emulsion of a pnmary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a sihcone resin-producing sihcone compound, (c) a finely divided filler matenal, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic sihcone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropy
  • 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.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • 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
  • 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 L 101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with 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 -C ⁇ ⁇ alkyl alcohols having a C j -C j g chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5 : 1.
  • suds should not form to the extent that they overflow the washing machine.
  • 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 granular detergent for use in automatic laundry washing machines.
  • compositions herein may comprise from 0% to about 10% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein 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 p ⁇ ma ⁇ ly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • sihcone 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 m amounts ranging from about 0.1% to about 2%, by weight, of the composition.
  • 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.
  • Alkoxylated Polycarboxylates Alkoxylated Polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are desc ⁇ bed in WO 91/08281 and PCT 90/01815 at p. 4 et seq., inco ⁇ orated herein by reference. Chemically, these matenals compnse polyacrylates having one ethoxy side-cham pef every 7-8 acrylate units. The side-chains are of the formula -(CH CH 2 0) m (CH 2 ) n CH 3 wherein m is 2-3 and n is 6-12.
  • the side-chains are ester-linked to the polyacrylate "backbone” to provide a "comb” polymer type structure.
  • the molecular weight can vary, but is typically m the range of about 2000 to about 50,000.
  • Such alkoxylated polycarboxylates can compnse from about 0.05% to about 10%), by weight, of the compositions herein.
  • Fabnc Softeners Va ⁇ ous through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known m 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 fabnc softener benefits concurrently with fabnc cleaning.
  • Clay softeners can be used m combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, C ⁇ sp et al, March 1, 1983 and U.S. Patent 4,291,071, Hams et al, issued September 22, 1981. NON-AQUEOUS BASED HEAVY DUTY LIQUID DETERGENTS SURFACTANT-CONTAINING LIQUID PHASE
  • the present invention comp ⁇ ses non-aqueous, liquid, heavy-duty detergent compositions m the form of a stable suspension of solid, substantially insoluble particulate mate ⁇ al dispersed throughout a structured, surfactant-contammg liquid phase.
  • the detergent composition comp ⁇ ses from about 49% to 99.95% by weight of the composition of a structured, surfactant- contammg liquid phase formed by combining: l) from about 1% to 80% by weight of said liquid phase of one or more nonaqueous organic diluents; and n) from about 20%> to 99% by weight of said liquid phase of a surfactant system comprising surfactants selected from the group consisting of anionic, nonionic, cationic surfactants and combinations thereof.
  • the surfactant-contammg, non-aqueous liquid phase of the present invention will generally comprise from about 52% to about 98.9%o by weight of the detergent compositions herein. More preferably, this liquid phase is surfactant-structured and will comprise from about 55% > to 98% by weight of the compositions. Most preferably, this non-aqueous liquid phase will compnse from about 55%) to 70%> by weight of the compositions herein.
  • Such a surfactant-contammg liquid phase will frequently have a density of from about 0 6 to 1.4 g/cc, more preferably from about 0 9 to 1.3 g/cc.
  • the liquid phase of the detergent compositions herein is preferably formed from one or more non-aqueous organic diluents into which is mixed a surfactant structunng agent which is preferably a specific type of anionic surfactant-contammg powder.
  • a surfactant structunng agent which is preferably a specific type of anionic surfactant-contammg powder.
  • the major component of the liquid phase of the HDL compositions herein compnses one or more non-aqueous organic diluents.
  • the non-aqueous organic diluents used in this invention may be either surface active, i.e., surfactant, liquids or non-aqueous, non-surfactant liquids referred to herein as non-aqueous solvents.
  • the term "solvent” is used herein to connote the non-surfactant, non-aqueous liquid portion of the compositions herein. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvent" -containing liquid phase, other components will be present as particulate mate ⁇ al dispersed within the "solvent" -containing liquid phase. Thus the term “solvent” is not meant to require that the solvent mate ⁇ al be capable of actually dissolving all of the detergent composition components added thereto.
  • the non-aqueous liquid diluent component will generally comp ⁇ se from about 50% to 100%, more preferably from about 50% to 80%, most preferably from about 55% to 75%, of a structured, surfactant-contammg liquid phase.
  • the liquid phase of the compositions herein, i.e., the non-aqueous liquid diluent component will compnse both non-aqueous liquid surfactants and non-surfactant non-aqueous solvents.
  • Non-aqueous Surfactant Liquids Suitable types of non-aqueous surfactant liquids which can be used to form the liquid phase of the compositions herein include the alkoxylated alcohols, ethylene oxide (EO)-propylene oxide (PO) block polymers, polyhydroxy fatty acid amides, alkylpolysacchandes, and the like. Such normally liquid surfactants are those having an HLB ranging from 10 to 16. Most preferred of the surfactant liquids are the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula:
  • R* is a Cg - Cjg alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.
  • R* is an alkyl group, which may be pnmary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol mate ⁇ als useful in the liquid phase will frequently have a hydrophilic-hpophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this mate ⁇ al will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophilic-hpophilic balance
  • fatty alcohol alkoxylates useful in or as the non-aqueous liquid phase of the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide.
  • Such mate ⁇ als have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms m its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated pnmary C j - C] 3 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9-C1 1 pnmary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename.
  • Dobanol 91-5 is an ethoxylated C9-C1 ⁇ fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C ⁇ -Ci 5 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S- 9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Co ⁇ oration.
  • the former is a mixed ethoxylation product of C ⁇ ⁇ to C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Alcohol ethoxylates useful m the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 1 1. Such products have also been commercially marketed by Shell Chemical Company. If alcohol alkoxylate nonionic surfactant is utilized as part of the non-aqueous liquid phase in the detergent compositions herein, it will preferably be present to the extent of from about 1% to 60%) of the composition structured liquid phase. More preferably, the alcohol alkoxylate component will comprise about 5% to 40% of the structured liquid phase.
  • an alcohol alkoxylate component will comprise from about 5% to 35% of the detergent composition structured liquid phase. Utilization of alcohol alkoxylate in these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of from about 1% to 60% by weight, more preferably from about 2% to 40% by weight, and most preferably from about 5% to 25% by weight, of the composition.
  • Another type of non-aqueous surfactant liquid which may be utilized in this invention are the ethylene oxide (EO) - propylene oxide (PO) block polymers. Matenals of this type are well known nonionic surfactants which have been marketed under the tradename Pluronic.
  • non-aqueous surfactant liquid useful in the compositions herein compnses polyhydroxy fatty acid amide surfactants, which have been defined herein before. If present, the polyhydroxy fatty acid amide surfactants are preferably present m a concentration of from about 0.1 to about 8%.
  • the amount of total liquid surfactant in the preferred surfactant-structured, non-aqueous liquid phase herein will be determined by the type and amounts of other composition components and by the desired composition properties.
  • the liquid surfactant can compnse from about 35%> to 70% of the non-aqueous liquid phase of the compositions herein. More preferably, the liquid surfactant will comp ⁇ se from about 50% to 65% of a non-aqueous structured liquid phase.
  • Non-surfactant non-aqueous Organic Solvents The liquid phase of the HDL compositions herein may also compnse one or more non-surfactant, non-aqueous organic solvents. Such non- surfactant non-aqueous liquids are preferably those of low polarity.
  • low-polarity liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate matenal used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • relatively polar solvents such as ethanol are preferably not utilized.
  • Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include non-vicmal C4-Cg alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
  • a preferred type of non-aqueous, low-polarity solvent for use in the compositions herein compnses the non-vicinal C ⁇ -Cg branched or straight chain alkylene glycols.
  • Matenals of this type include hexylene glycol (4-methyl-2,4-pentaned ⁇ ol), 1 ,6-hexaned ⁇ ol, 1,3-butylene glycol and 1,4-butylene glycol.
  • Hexylene glycol is the most preferred.
  • non-aqueous, low-polanty solvent for use herein compnses the mono-, di-, tn-, or tetra- C 2 -C alkylene glycol mono C -Cg alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-propanol (BPP) are especially preferred.
  • PEGs polyethylene glycols
  • non-polar, non-aqueous solvent compnses lower molecular weight methyl esters.
  • Such matenals are those of the general formula: R ⁇ -C(0)-OCH 3 wherein R! ranges from 1 to about 18.
  • suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the non-aqueous, generally low-polanty, non-surfactant organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein.
  • a solvent component is preferably utilized in an amount of from about 1 % to 70% by weight of the liquid phase.
  • a non-aqueous, low-polanty, non-surfactant solvent will compnse from about 10% to 60% by weight of a structured liquid phase, most preferably from about 20% to 50% by weight, of a structured liquid phase of the composition.
  • Utilization of non-surfactant solvent in these concentrations in the liquid phase corresponds to a non-surfactant solvent concentration in the total composition of from about 1% to 50%> by weight, more preferably from about 5% to 40%) by weight, and most preferably from about 10% to 30% > by weight, of the composition.
  • the ratio of surfactant to non-surfactant liquids e.g., the ratio of alcohol alkoxylate to low pola ⁇ ty solvent, within a structured, surfactant-contammg liquid phase can be used to vary the rheological properties of the detergent compositions eventually formed.
  • the weight ratio of surfactant liquid to non-surfactant organic solvent will range about 50:1 to 1:50. More preferably, this ratio will range from about 3: 1 to 1:3, most preferably from about 2: 1 to 1 :2.
  • the non-aqueous liquid phase of the HDL compositions of this invention is prepared by combining with the non-aqueous organic liquid diluents hereinbefore desc ⁇ bed a surfactant which is generally, but not necessa ⁇ ly, selected to add structure to the non-aqueous liquid phase of the detergent compositions herein.
  • Structuring surfactants can be of the anionic, nonionic, cationic, and/or amphotenc types.
  • Preferred structunng surfactants are the anionic surfactants such as the alkyl sulfates, linear alkyl benzene sulfonate (LAS), the alkyl polyalkxylate sulfates and the linear alkyl benzene sulfonates.
  • anionic surfactant matenal which may be optionally added to the detergent compositions herein as structurant compnses carboxylate-type anionics.
  • Carboxylate-type anionics include the CiQ-Cj alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and the CJO-CI g sarcosinates, especially oleoyl sarcosmate.
  • Structunng anionic surfactants will generally compnse from about 1% to 30% by weight of the compositions herein.
  • one preferred type of structuring anionic surfactant compnses p ⁇ mary or secondary alkyl sulfate anionic surfactants.
  • Such surfactants are those produced by the sulfation of higher Cg-C 2 ⁇ fatty alcohols.
  • the most preferred type of anionic surfactant for use as a structurant in the HDL compositions herein compnses the linear alkyl benzene sulfonate (LAS) surfactants.
  • LAS linear alkyl benzene sulfonate
  • SOLID PARTICULATE MATERIALS The non-aqueous HDL compositions herein preferably comprise from about 0.01% to 50% by weight, more preferably from about 0.2% to 30% by weight, of solid phase particulate material which is dispersed and suspended within the liquid phase. Generally such particulate material will range in size from about 0.1 to 1500 microns, more preferably from about 0.1 to 900 microns. Most preferably, such material will range in size from about 5 to 200 microns.
  • the particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the non-aqueous liquid phase of the composition.
  • the types of particulate materials which can be utilized are described are peroxygen bleaching agent, organic builder, inorganic alkalinity source (preferably include water-soluble alkali metal carbonates, bicarbonates, borates, pyrophosphates, orthophosphates, polyphosphates phosphonates, silicates and metasilicates), colored speckles and mixtures therof.
  • the present invention also comprises aqueous based liquid detergent compositions.
  • the aqueous liquid detergent compositions preferably comprise from about 10% to about 98%, preferably from about 30% to about 95%, by weight of an aqueous liquid carrier which is preferably water.
  • the aqueous liquid detergent compositions of the present invention comprise a surfactant system which preferably contains one or more detersive co- surfactants in addition to the branched surfactants disclosed above.
  • the additional co-surfactants can be selected from nonionic detersive surfactant, anionic detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive surfactant, and mixtures thereof.
  • the surfactant system typically comprises from about 5% to about 70%>, preferably from about 15% to about 30%, by weight of the detergent composition. These surfactants are hereinbefore described.
  • OTHER OPTIONAL HDL COMPOSITION COMPONENTS In addition to the liquid and solid phase components as hereinbefore described, the aqueous and non-aqueous based detergent compositions can, and preferably will, contain various other optional components. Such optional components may be in either liquid or solid form. The optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in the form of fine particles or droplets.
  • Suitable optional material includes for example chelating agents, enzymes, builders, bleach catalysts, bleach activators, thickeners, viscosity control agents and/or dispersing agents suds boosters, liquid bleach activator, dye transfer inhibitors, solvents, suds suppressors, structure elasticizing agent, anti redeposition agents, to exemplify but a few possible optional ingredients.
  • Some of the materials which may optionally be utilized in the compositions herein are described in greater detail. Further details on suitable adjunct ingredients to HDL compositions, meythods of prepanng same and use in the compositions can be found in m U.S. Patent applications Serial Nos. 60/062,087 (Docket No 6876P), and 60/061,924 (Docket No. 6877P),
  • the detergent compositions will further preferably compnse one or more detersive adjuncts selected from the following: electrolytes (such as sodium chloride), polysacchandes, abrasives, bactencides, tarnish inhibitors, dyes, antifungal or mildew control agents, insect repellents, perfumes, hydrotropes, thickeners, processing aids, suds boosters, anti- corrosive aids, stabilizers and antioxidants.
  • electrolytes such as sodium chloride
  • polysacchandes such as sodium chloride
  • abrasives such as sodium chloride
  • bactencides such as sodium chloride
  • tarnish inhibitors such as sodium chloride
  • dyes such as sodium chloride
  • antifungal or mildew control agents such as sodium chloride
  • insect repellents such as sodium chloride
  • perfumes such as sodium chloride
  • hydrotropes such as sodium chloride
  • thickeners such as sodium chloride
  • processing aids such as sodium chloride
  • suds boosters such as the CJ Q- IO alkanolamides can be inco ⁇ orated into the compositions, typically at 1%-10% levels.
  • the C JO- C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsmg adjunct surfactants such as the amme oxides, beta es and sultames noted above is also advantageous.
  • An antioxidant can be optionally added to the detergent compositions of the present invention.
  • They can be any conventional antioxidant used m detergent compositions, such as 2,6- d ⁇ -tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolam ⁇ ne(MEA), diethanolamine, t ⁇ ethanolamine, etc. It is preferred that the antioxidant, when present, be present in the composition from about 0.001% to about 5% by weight.
  • Va ⁇ ous detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • 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 ⁇ 3 .i 5 ethoxylated alcohol (EO 7) nonionic surfactant.
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stimng in silicone oil (va ⁇ ous sihcone oil viscosities m the range of 500-12,500 can be used).
  • the resulting si cone oil dispersion is emulsified or otherwise added to the final detergent matnx.
  • 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.
  • compositions may optionally comprises a hydrotrope Suitable hydrotropes include sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluene sulfonic acid, naphthalene sulfomc acid, cumene sulfomc acid, xylene sulfonic acid.
  • Suitable hydrotropes include sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluene sulfonic acid, naphthalene sulfomc acid, cumene sulfomc acid, xylene sulfonic acid.
  • LDL compositions which comprise a non-aqueous carrier medium can be prepared according to the disclosures of U.S. Patents 4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673, GB-A-2,158,838; GB-A-2,195,125, GB-A-2, 195,649; U.S 4,988,462; U.S. 5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A- 540,090 (5/5/93); U.S.
  • Such compositions can contain various particulate detersive ingredients stably suspended therein.
  • Such non-aqueous compositions thus compnse a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as descnbed in more detail hereinafter and m the cited references.
  • the LDL compositions of this invention can be used to form aqueous washing solutions for use hand dishwashing. Generally, an effective amount of such LDL compositions is added to water to form such aqueous cleaning or soaking solutions The aqueous solution so formed is then contacted with the dishware, tableware, and cooking utensils.
  • An effective amount of the LDL compositions herein added to water to form aqueous cleaning solutions can comprise amounts sufficient to form from about 500 to 20,000 ppm of composition m aqueous solution. More preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be provided in aqueous cleaning liquor.
  • the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm m diameter.
  • mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a senes of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the granular laundry compositions m accordance with the present invention typically has a bulk density of from 100 g/htre to 1400 g/htre, more preferably from 300 g/htre to 1200 g/htre, from 650 g/htre to 1000 g/htre.
  • High Density Detergent Composition Processes Various means and equipment are available to prepare high density (i.e., greater than about 550, preferably greater than about 650, grams/liter or "g/1"), high solubility, free-flowing, granular detergent compositions according to the present invention. Current commercial practice in the field employs spray-drying towers to manufacture granular laundry detergents which often have a density less than about 500 g/1.
  • an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of about 175°C to about 225°C.
  • spray drying is used as part of the overall process herein, additional or alternative process steps as described hereinafter must be used to obtain the level of density (i.e., > 650 g/1) required by modern compact, low dosage detergent products.
  • spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers.
  • a suitable high speed mixer/densifier for this process is a device marketed under the tradename "Lodige CB 30" or "L ⁇ dige CB 30 Recycler” which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon.
  • the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100- 2500 ⁇ m to provide thorough mixing/densification.
  • Another process step which can be used to densify further spray-dried granules involves treating the spray-dried granules in a moderate speed mixer/densifier.
  • Equipment such as that marketed under the tradename "L ⁇ dige KM" (Series 300 or 600) or “Lodige Ploughshare” mixer/densifiers are suitable for this process step.
  • Such equipment is typically operated at 40- 160 ⁇ m,
  • the residence time of the detergent ingredients in the moderate speed mixer/densifier is from about 0.1 to 12 minutes conveniently measured by dividing the steady state mixer/densifier weight by the throughput (e.g., Kg/hr).
  • Other useful equipment includes the device which is available under the tradename "Drais K-T 160".
  • This process step which employs a moderate speed mixer/densifier can be used by itself or sequentially with the aforementioned high speed mixer/densifier (e.g. Lodige CB) to achieve the desired density.
  • a moderate speed mixer/densifier e.g. Lodige KM
  • the aforementioned high speed mixer/densifier e.g. Lodige CB
  • Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942. While it may be more suitable to use the high speed mixer/densifier followed by the low speed mixer/densifier, the reverse sequential mixer/densifier configuration also can be used.
  • va ⁇ ous parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-d ⁇ ed granules in the process of the invention.
  • va ⁇ ous parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-d ⁇ ed granules in the process of the invention.
  • the formulator can eliminate the spray-drymg step by feeding, in either a continuous or batch mode, starting detergent ingredients directly into mixing equipment that is commercially available.
  • One particularly preferred embodiment involves charging a surfactant paste and an anhydrous matenal into a high speed mixer/densifier (e.g. Lodige CB) followed by a moderate speed mixer/densifier (e.g. Lodige KM) to form high density detergent agglomerates.
  • a high speed mixer/densifier e.g. Lodige CB
  • a moderate speed mixer/densifier e.g. Lodige KM
  • Patent 5,486,303 issued January 23, 1996.
  • the liquid/solids ratio of the starting detergent ingredients in such a process can be selected to obtain high density agglomerates that are more free flowing and cnsp. See Capeci et al, U.S. Patent 5,565,137, issued October 15, 1996.
  • the process may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer/densifiers for further agglomeration or build-up.
  • the oversized particles produced by this process can be sent to gnndmg apparatus and then fed back to the mixing/densifymg equipment.
  • These additional recycle process steps facilitate build-up agglomeration of the starting detergent ingredients resulting in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density (> 550 g/1) See Capeci et al, U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996.
  • a high density detergent composition using a fluidized bed mixer.
  • the vanous ingredients of the finished composition are combined in an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide the finished detergent granules.
  • this process can optionally include the step of mixing the slurry using the aforementioned Lodige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can be used in such processes.
  • Another suitable process which can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic mate ⁇ al (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier so as to form particles containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients.
  • a high speed mixer/densifier e.g. L ⁇ dige KM
  • a moderate speed mixer/densifier e.g. L ⁇ dige KM
  • high density detergent compositions according to the invention can be produced by blending conventional or densified spray-d ⁇ ed detergent granules with detergent agglomerates in vanous proportions (e.g. a 60:40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein.
  • vanous proportions e.g. a 60:40 weight ratio of granules to agglomerates
  • Additional adjunct ingredients such as enzymes, perfumes, b ⁇ ghteners and the like can be sprayed or admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein.
  • Machine laundry methods herein typically comp ⁇ se treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
  • an effective amount of the detergent composition it is here meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • surfactants are used herein in detergent compositions, preferably in combination with other detersive surfactants, at levels which are effective for achieving at least a directional improvement m cleaning performance.
  • usage levels can vary widely, depending not only on the type and seventy of the soils and stams, but also on the wash water temperature, the volume of wash water and the type of washing machine.
  • Conventional Surface Cleansing Additive The hard surface cleaner composition of the present invention additionally contain a conventional surface cleansing additive.
  • the conventional surface cleansing additive are present from about 0.001%) to about 99.9% by weight.
  • conventional surface cleansing additive will be present from at least about 0.5%), more preferably, at least about 1%, even more preferably at least about 2%, by weight. Additionally, the conventional surface cleansing additives can also be present at least about 5%, at least about 8% and at least about 10%, by weight but it is more preferable that the conventional surface cleansing additive be present in at least about 2% by weight. Furthermore, the conventional surface cleansing additive will be preferably present m the hard surface composition at preferably at less than about 45%, more preferably less than about 40%, even more preferably less than about 35%, even more preferably less than about 30%, even more preferably less than about 20%, by weight.
  • This conventional surface cleansing additive is selected from the group compnsmg liquid earner, co-surfactant (preferably anionic; nonionic; cat ⁇ on ⁇ c;ampohte ⁇ c; zwittenomc; and mixtures thereof), builder, co-solvent, polymeric additive (preferably polyalkoxylene glycol; PVP homopolymers or copolymers thereof; polycarboxylate; sulfonated polystyrene polymer; and mixtures thereof), pH adjusting material, hydrotropes; and mixtures thereof.
  • suitable conventional surface cleansing additives can be found m US Pat App Nos. 60/061,970, Attorney docket No 6885P October 14, 1997, and 60/062,407, Attorney docket No 6886P October 14, 1997, both of which are inco ⁇ orated herein by reference.
  • Packaging for the compositions preferably anionic; nonionic; cat ⁇ on ⁇ c;ampohte ⁇ c; zwittenomc; and mixtures thereof
  • compositions can be packaged m any suitable container including those constructed from paper, cardboard, plastic matenals and any suitable laminates.
  • a preferred packaging execution is descnbed in European Application No. 94921505.7.
  • the compositions herein may be packaged in a va ⁇ ety of suitable detergent packaging known to those skilled m the art.
  • the liquid compositions are preferably packaged in conventional detergent plastic bottles.
  • Neodol 91-8 (30.00 g, 58.7 mmol) is placed into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, pressure equalizing dropping funnel, reflux condenser, internal thermometer and argon mlet, and dned under vacuum at 75 °C. After releasing the vacuum with argon, sodium metal (0.03 g, 1.2 mmol) is placed into the flask and the mixture heated and stirred at 140 °C until all sodium is consumed.
  • 1 ,2-Epoxybutane (12.71 g, 176.2 mmol) is then added dropwise at a rate so as to keep the reaction temperature at >120 °C, with a target of 140 °C. After all of the 1 ,2-epoxybutane is added and reflux g has ceased, the mixture is stirred and heated an additional 3 h at 140°C. The 140 °C mixture is then placed under vacuum for 15 min to remove any traces of 1 ,2-epoxybutane. A light brown liquid is isolated. NMR is consistent with the desired compound.
  • Neodol 91-8 (30.00 g, 58.7 mmol) is placed into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon mlet, and dned under vacuum at 75°C. After cooling to ambient and releasing the vacuum with argon, methylene chlonde (12ml) and 2-methyl- 1-butene (4.53 g, 64.6 mmol) are added. Then boron t ⁇ fluonde diethyl etherate (0.83 g, 5.9 mmol) is added all at once. This mixture is stirred 5 days at ambient.
  • Anhydrous tetrahydrofuran (250 ml) and 60%> sodium hyd ⁇ de (8.22 g, 205.6 mmol) are placed into a 500 ml three-necked round-bottomed flask, fitted with a magnetic stirrer, pressure equalizing dropping funnel, internal thermometer and argon mlet. After cooling the mixture to 0 °C, Neodol 91-8 (35.00 g, 68.5 mmol) is added dropwise over 10 minutes. After warming to ambient, the mixture is stirred for 2 h. 1-Iodopentane (33.93 g, 171.3 mmol) is added dropwise over 10 minutes.
  • Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and
  • PB1 Anhydrous sodium perborate bleach of nominal formula NaB0 2 .H 2 0 2 NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
  • TPK Fatty Acid
  • NaSKS-6 Crystalline layered silicate of formula ⁇ -Na Si 2 ⁇ 5 Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between
  • PAE ethoxylated tetraethylene pentamine
  • Photoactivated bleach Sulfonated Zinc Phthalocyanine bleach encapsulated in dextrin soluble polymer HEDP 1,1-hydroxyethane diphosphonic acid SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephthaloyl backbone
  • Non-limiting examples of bleach-containing nonaqueous liquid laundry detergent are prepared as follows. Preparation of LAS Powder for Use as a Structurant
  • NaLAS powder is produced by taking a slurry of NaLAS in water (approximately 40-50% active) combined with dissolved sodium sulfate (3-15%) and hydrotrope, sodium sulfosuccinate (1-3%)). The hydrotrope and sulfate are used to improve the characteristics of the dry powder.
  • a drum dryer is used to dry the slurry into a flake. When the NaLAS is dried with the sodium sulfate, two distinct phases are created within the flake. The insoluble phase creates a network structure of aggregate small particles (0.4-2 um) which allows the finished non-aqueous detergent product to stably suspend solids.
  • the NaLAS powder prepared according to this example has the following makeup shown in Table I.
  • Non-aqueous based heavy duty liquid laundry detergent compositions which comprise the capped nonionic surfactants of the present invention are presented below.
  • compositions are stable, anhydrous heavy-duty liquid laundry detergents which provide excellent rates of mixing with water as well as good stain and soil removal performance when used in normal fabric laundering operations.
  • EXAMPLE 9 Hand Dishwashing Liquid compositions
  • Dimethicone is a 40(gum)/60(fluid) weight ratio blend of SE-76 dimethicone gum available from General Electric Silicones Division and a dimethicone fluid having a viscosity of 350 centistokes.
  • laundry detergent compositions are prepared in accord with the invention:
  • laundry detergent compositions are prepared in accord with the invention:
  • laundry detergent compositions are prepared in accord with the invention:
  • compositions were made by mixing the listed ingredients in the listed proportions. These compositions were used neat to clean marble and dilute to clean lacquered wooden floors. Excellent cleaning and surface safety performance was observed.

Abstract

La présente invention concerne une composition nettoyante qui comprend un tensioactif non ionique.
PCT/US2000/004185 1999-02-22 2000-02-18 Compositions nettoyantes contenant des tensioactifs non ioniques selectionnes WO2000050549A2 (fr)

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JP2000601113A JP2002537482A (ja) 1999-02-22 2000-02-18 選択されたノニオン性界面活性剤を含有するクリーニング組成物
EP00913522A EP1155106A2 (fr) 1999-02-22 2000-02-18 Compositions nettoyantes contenant des tensioactifs non ioniques selectionnes
CA002362945A CA2362945C (fr) 1999-02-22 2000-02-18 Compositions nettoyantes contenant des tensioactifs non ioniques selectionnes
AU34957/00A AU3495700A (en) 1999-02-22 2000-02-18 Cleaning compositions containing selected nonionic surfactants

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US6365785B1 (en) * 1997-08-02 2002-04-02 Therprocter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
EP1882029A2 (fr) * 2005-05-20 2008-01-30 Rhodia Inc. Compositions tensioactives structurees
WO2011079459A1 (fr) * 2009-12-31 2011-07-07 Rhodia (China) Co., Ltd. Association de polymère et de tensioactif pour lessive améliorée
WO2014088554A1 (fr) * 2012-12-04 2014-06-12 Colgate-Palmolive Company Composition démaquillante
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JP6071789B2 (ja) * 2013-07-19 2017-02-01 ライオン株式会社 拭き取り用の液体洗浄剤
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WO2001048131A3 (fr) * 1999-12-24 2001-11-22 Cognis Deutschland Gmbh Granulats de tensioactifs presentant une plus grande vitesse de dissolution
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WO2001055288A1 (fr) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh & Co. Kg Agents de rincage
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WO2011079459A1 (fr) * 2009-12-31 2011-07-07 Rhodia (China) Co., Ltd. Association de polymère et de tensioactif pour lessive améliorée
WO2014088554A1 (fr) * 2012-12-04 2014-06-12 Colgate-Palmolive Company Composition démaquillante
US9861565B2 (en) 2012-12-04 2018-01-09 Colgate-Palmolive Company Cleansing composition
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AU3495700A (en) 2000-09-14
CA2362945A1 (fr) 2000-08-31
JP2002537482A (ja) 2002-11-05
WO2000050549A3 (fr) 2000-11-02
EP1155106A2 (fr) 2001-11-21

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