WO1997043388A2 - Composition detersive - Google Patents

Composition detersive Download PDF

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Publication number
WO1997043388A2
WO1997043388A2 PCT/US1997/008444 US9708444W WO9743388A2 WO 1997043388 A2 WO1997043388 A2 WO 1997043388A2 US 9708444 W US9708444 W US 9708444W WO 9743388 A2 WO9743388 A2 WO 9743388A2
Authority
WO
WIPO (PCT)
Prior art keywords
aqa
bis
surfactant
composition according
compositions
Prior art date
Application number
PCT/US1997/008444
Other languages
English (en)
Other versions
WO1997043388A3 (fr
Inventor
Kaori Asano
Jeffrey John Scheibel
Hajime Baba
Andre Cesar Baeck
Kaori Minamikawa
Richard Timothy Hartshorn
Speed, (Jones), Lynda, Anne
Rinko Katsuda
Frank Andrej Kvietok
Mark Hsiang-Kuen Mao
Michael Alan John Moss
Susumu Murata
Royohei Ohtani
Rajan Keshav Panandiker
Kakumanu Pramod
Khizar Mohamed Khan Sarnaik
Christian Arthur Jacques Kamiel Thoen
Kevin Lee Kott
Kenneth William Willman
Laura Cron
Thomas Anthony Cripe
John Downing Curry
Peter Robert Foley
Ian Martin Dodd
Sanjeev Krishnadas Manohar
Mitsuyo Okamoto
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP9541172A priority Critical patent/JPH11510554A/ja
Priority to EP97924766A priority patent/EP0912686A2/fr
Priority to BR9710678A priority patent/BR9710678A/pt
Publication of WO1997043388A2 publication Critical patent/WO1997043388A2/fr
Publication of WO1997043388A3 publication Critical patent/WO1997043388A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/005—Compositions containing perfumes; Compositions containing deodorants
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene 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
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising an enzyme, a non- AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.
  • laundry detergents and other cleaning compositions presents a considerable challenge, since modern compositions are required to remove a variety of soils and stains from diverse substrates.
  • laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashers all require the proper selection and combination of ingredients in order to function effectively.
  • such detergent compositions will contain one or more types of surfactants which are designed to loosen and remove different types of soils and stains. While a review of the literature would seem to indicate that a wide selection of surfactants and surfactant combinations are available to the detergent manufacturer, the reality is that many such ingredients are speciality chemicals which are not suitable in low unit cost items such as home-use laundry detergents.
  • soils and stains such as body soils, greasy/oily soils and certain food stains
  • soils comprise a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and
  • bis-alkoxylated quaternary ammonium (bis-AQA) compounds can be used in various detergent compositions to boost detergency performance on a variety of soil and stain types, particularly the hydrophobic soil types, commonly encountered.
  • compositions containing enzymes and a bis-AQA surfactant deliver not only superior cleaning and whiteness performance versus products containing either technology alone, but also provide improved fabric care.
  • the bis-AQA surfactants of the present invention provide substantial benefits to the formulator, over cationic surfactants previously known.
  • the bis-AQA surfactants used herein provide marked improvement in cleaning of "everyday" greasy/oily hydrophobic soils regularly encountered.
  • the bis-AQA surfactants are compatible with anionic surfactants commonly used in detergent compositions such as alkyl sulfate and alkyl benzene sulfonate; incompatibility with anionic components of the detergent composition has commonly been the limiting factor in the use of cationic surfactants to date.
  • Low levels (as low as 3 ppm in the laundering liquor) of bis-AQA surfactants gives rise to the benefits described herein.
  • Bis-AQA surfactants can be formulated over a broad pH range from 5 to 12.
  • the bis-AQA surfactants can be prepared as 30% (wt.) solutions which are pumpable, and therefore easy to handle in a
  • Bis-AQA surfactants with degrees of ethoxylation above 5 are sometimes present in a liquid form and can therefore be provided as 100% neat materials. In addition to their beneficial handling properties, the availability of bis-AQA surfactants as highly concentrated solutions provides a substantial economic advantage in transportation costs.
  • the bis-AQA surfactants are also compatible with various perfume ingredients, unlike some cationic surfactants known in the art .
  • One aspect of the present invention provides a means for enhancing the removal of greasy/oily soils by combining a lipase enzyme with an AQA surfactant.
  • Greasy/oily soils are comprised of a mixture of materials, including triglycerides.
  • triglycerides in the soil are convened by bacterial action to fatty acids; lipase enzymes can be used to convert any remaining triglycerides to fatty acids through-the-wash.
  • Fatty acids in the soil interact with the hardness ion in the wash water (e.g. Mg 2 + and Ca 2 + ions) to form insoluble magnesium/calcium fatty acid salts or lime- soaps.
  • Lime-soaps precipitate from the wash solution forming a layer of lime-soap deposit on the fabric. Successive washing results in the build-up of lime-soap deposits which entrap particulate dirt, hinder soil removal and enhance retension of soil residues on the fabric after the wash.
  • the glue acts as an ideal substrate for deposition/retention of greasy /oily hydrophobic body soils (e.g. , on collars and pillowcases).
  • the combined cellulytic/bis-AQA system also provides softness and fabric care benefits vs. either the cationic or enzyme alone, by effective depilling and ungluing of worn fibres.
  • U.S. Patent 5,441,541 issued August 15, 1995, to A. Mehreteab and F. J. Loprest, relates to anionic/cationic surfactant mixtures.
  • U.K. 2,040,990 issued 3 Sept., 1980, to A. P. Murphy, R.J.M. Smith and M. P. Brooks, relates to ethoxylated cationics in laundry detergents.
  • the present invention provides a composition
  • a composition comprising or prepared by combining an enzyme, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula: wherein R 1 is a linear, branched or substituted C 8 -C 18 alkyl, alkenyl, aryl, aikaryl, ether or glycityl ether moiety, R 2 is a C 1 -C 3 alkyl moiety, R 3 and R 4 can vary independently and are selected from hydrogen, methyl and ethyl, X is an anion, and A and A' can vary
  • compositions of the present invention include enzymes as essential components.
  • Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
  • Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • proteases 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.
  • AU Anson units
  • Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
  • protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE ® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo.
  • suitable proteases include ALCALASE ® and SAVINASE ® from Novo and MAXATASE ® from International Bio-Synthetics, Inc. , The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985.
  • protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • Other preferred proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • an especially preferred protease is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in 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, + 166, + 195, + 197, +204, +206, + 210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A.
  • Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes include, for example, ⁇ -amylases described in GB 1 ,296,839 to Novo;
  • FUNGAMYL ® from Novo is especially useful.
  • Engineering of enzymes for improved stability e.g., oxidative stability, is known. See, for example J. Biological Chem. , Vol. 260, No. 11, June 1985, pp. 6518-6521.
  • Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL ® in commercial use in 1993.
  • oxidative stability e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10
  • thermal stability e.g., at common wash temperatures such as 60°C
  • alkaline stability e.g., at a pH from 8 to 11 , measured versus the above-identified reference-point amylase.
  • Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability -enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly preferred amylases herein have the
  • particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL ® .
  • Other particularly preferred oxidative stability enhanced amylase include those described 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 chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • amylase enzymes include those described in WO 95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056.
  • Specific amylase enzymes for use in the detergent compositions of the present invention include ⁇ -amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl ® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas ® ⁇ -amylase activity assay.
  • compositions at a level from 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
  • U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS- 2.247.832.
  • CAREZYME ® and CELLUZYME ® are especially useful. See also WO 9117243 to Novo.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P. " Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co. , Tagata, Japan;
  • Chromobacter viscosum lipases from U.S. Biochemical Corp. , U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • LIPOLASE ® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.
  • D96L lipase variant
  • the present invention provides the benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions containing the bis-AQA surfactants in the manner disclosed herein, especially when the D96L is used at levels in the range of 50 LU to 8500 LU per liter of wash solution.
  • Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g. , percarbonate, perborate, hydrogen peroxide, etc. , for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
  • oxygen sources e.g. , percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO
  • Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S.
  • R 1 is a linear, branched or substituted alkyl, alkenyl, aryl. aikaryl, ether or glycityl ether moiety containing from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably from 8 tol4 carbon atoms;
  • R 2 is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl;
  • R 3 and R 4 can vary independently and are selected from the group consisiting of hydrogen (preferred), methyl and ethyl;
  • X- is an anion such as chloride, bromide, methyl sulfate, sulfate, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C 1 -C 4 alkoxy, especially ethoxy, propoxy, butoxy and mixtures thereof; p is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferable 1 to 4 and q is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferably 1 to 4 Most preferably both p and q are 1.
  • the levels of the bis-AQA surfactants used to prepare finished laundry detergent compositions can range from 0.1 % to 5% , typically from 0.45% to 2.5%, by weight.
  • percarbonate bleach is in the range of from 1:100 to 5 :1 , preferably from 1 :60 to 2 :1 , most preferably from 1 : 20 to 1:1.
  • the present invention employs an "effective amount" of the bis-AQA surfactants to improve the performance of cleaning compositions which contain other optional
  • an "effective amount" of the bis-AQA surfactants herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the performance of the cleaning composition against at least some of the target soils and stains.
  • an effective amount of the bis-AQA surfactants herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the performance of the cleaning composition against at least some of the target soils and stains.
  • the formulator will use sufficient bis-AQA to at least directionally improve cleaning performance against such stains.
  • the formulator will use sufficient bis-AQA to at least directionally improve cleaning performance against such soil.
  • the bis-AQA surfactants may be used in combination with other detersive surfactants at levels which are effective for achieving at least a directional improvement in cleaning performance.
  • usage levels can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the type of washing machine.
  • a wash cycle of 10 to 14 minutes and a wash water temperature of 10°C to 50°C it is preferred to include from 2 ppm to 50 ppm, preferably from 5 ppm to 25 ppm, of the bis-AQA surfactant in the wash liquor.
  • this translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.1 % to 3.2%, preferably 0.3% to 1.5 % , for a heavy-duty liquid laundry detergent.
  • a wash cycle of 8 to 15 minutes and a wash water temperature of 5°C to 25°C it is preferred to include from 1.67 ppm to 66.67 ppm, preferably from 3 ppm to 6 ppm, of the bis-AQA surfactant in the wash liquor.
  • this translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.25% to 10% , preferably 1.5% to 2% , for a heavy-duty liquid laundry detergent.
  • the amount of bis-AQA surfactant used in a machine- wash laundering context can vary, depending on the habits and practices of the user, the type of washing machine.
  • one heretofore unappreciated advantage of the bis-AQA surfactants is their ability to provide at least directional improvements in performance over a spectrum of soils and stains even when used at relatively low levels with respect to the other surfactants (generally anionics or
  • anionic/nonionic mixtures in the finished compositions. This is to be distinguished from other compositions of the art wherein various cationic surfactants are used with anionic surfactants at or near stoichiometric levels.
  • the weight ratio of bis-AQA: anionic surfactant in laundry compositions is in the range from
  • the weight ratio of bis-AQA:mixed anionic/nonionic is in the range from 1 :80 to 1 :2, preferably 1:50 to 1 :8.
  • the weight ratio of the bis-AQA surfactant to other surfactants present in such compositions is low, i.e., sub-stoichiometric in the case of anionics.
  • such cleaning compositions comprise bis-AQA/surfactant ratios as noted immediately above for machine-use laundry compositions.
  • the bis-alkoxylated cationics herein have sufficient solubility that they can be used in combination with mixed surfactant systems which are quite low in nonionic surfactants and which contain, for example, alkyl sulfate surfactants.
  • Reaction temperatures are typically in the range of 100-230°C. Reaction pressures are 50-1000 psig.
  • a base preferably sodium hydroxide, can be used to react with the HSO4-generated during the reaction, or an excess of the amine can be employed to also react with the acid.
  • the mole ratio of amine to alkyl sulfate is typically from 10: 1 to 1 : 1.5; preferably from 5: 1 to 1 : 1.1 ; more preferably from 2: 1 to 1 : 1.
  • the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble.
  • the second step of the process is conducted under conventional reaction conditions. Further ethoxylation and quaternization to provide bis-AQA surfactants are conducted under standard reaction conditions.
  • the funnel is shaken well for a few minutes and then allowed mixture to separate.
  • the lower chloroform layer is drained and the chloroform is evaporated off to obtain product.
  • the product is then reacted with 1 molar equivalent of ethylene oxide in the absence of base catalyst at 120-130°C to produce the desired final product.
  • the bis-substituted amines prepared in the foregoing Syntheses can be further ethoxylated in standard fashion. Quaternization with an alkyl halide to form the bis-AQA surfactants herein is routine. According to the foregoing, the following are nonlimiting, specific illustrations of bis-AQA surfactants used herein. It is to be understood that the degree of alkoxylation noted herein for the bis-AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically yield mixtures of materials with differing degrees of ethoxylation. Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "EO2.5", "EO3.5" .
  • R 1 is C 8 -C 18 hydrocarbyl and mixtures thereof, preferably C 8 , C 10 , C 12 , C 14 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • bis-AQA surfactants useful herein include compounds of the formula:
  • R 1 is C 8 -C 18 hydrocarbyl, preferably C 8 -C 14 alkyl, independently p is 1 to 3 and q is 1 to 3, R 2 is C 1 -C 3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • compositions of the present invention preferably further comprise a non-AQA surfactant.
  • Non-AQA surfactants may include essentially any anionic, nonionic or additional cationic surfactant.
  • Nonlimiting examples of anionic surfactants useful herein typically at levels from 1 % to 55%, by weight, include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS") and primary ("AS"), branched-chain and random C 10 -C 20 alkyl sulfates, the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 -M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 -M + ) CH 2 CH 3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 12 -C 18 alpha-sulfonated fatty acid esters, the C 10 -C 18 sulfated polyglycosides, the C 10 -C 18 alkyl
  • C 12 -C 18 betaines and sulfobetaines can also be included in the overall compositions.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used.
  • Other conventional useful surfactants are listed in standard texts.
  • Nonionic Surfactants typically at levels from 1 % to 55% , by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C 10 -C 18 glycerol ethers.
  • AE alkoxylated alcohols
  • PFAA's polyhydroxy fatty acid amides
  • APG's alkyl polyglycosides
  • C 10 -C 18 glycerol ethers C 10 -C 18 glycerol ethers.
  • condensation products of primary and secondary aliphatic alcohols with from 1 to 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
  • nonionic surfactants of this type include: TergitolTM 15-S-9 (the condensation product of C 1 1 -C 15 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the condensation product of C 12 -C 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45.9 (the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C 12 -C 13 linear alcohol with 3 moles of ethylene oxide),
  • NeodolTM 45.7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45.5 (the condensation product of C 14 -C 15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; KyroTM EOB (the condensation product of C 13 -C 15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA O3O or O5O (the condensation product of C 12 -C 14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst.
  • the preferred range of HLB in these AE nonionic surfactants is from 8-11 and most preferred from 8-10. Condensates with propylene oxide and butylene oxides may also be used.
  • R 1 is methyl
  • R 2 is a straight C 11 -15 alkyl or C 15-17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • Typical examples include the C 12 -C 18 and C 12 -C 14 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.
  • alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substimted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g. , between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkylpolyglycosides have the formula: R 2 O(C n H 2n O) t (glycosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkyIphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
  • the additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
  • 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 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from 2 to 25 moles, more preferably from 3 tol5 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company.
  • alkylphenol alkoxy lates 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 1500 to 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 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide.
  • examples of compounds of this type include certain of the commercially-available PluronicTM 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 ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from 40% to 80% by weight of polyoxyethylene and has a molecular weight of from 5,000 to 11,000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF. Additional Cationic surfactants
  • Suitable cationic surfactants are preferably water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Other suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No s 4228042, 4239660 and 4260529.
  • Optional Detergent Ingredients The following illustrates various other optional ingredients which may be used in the compositions of this invention, but is not intended to be limiting thereof.
  • Enzyme Stabilizing System The enzyme-containing compositions herein preferably also comprise from 0.001 % to
  • 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, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic 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.
  • One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from 1 to 30, preferably from 2 to 20, more preferably from 8 to 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated.
  • Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3 % by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
  • Stabilizing systems of certain cleaning compositions may further comprise from 0 to 10% , preferably from 0.01 % to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during dish- or fabric-washing, can be relatively large;
  • Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
  • the detergent compositions herein may optionally comprise a bleaching agent.
  • bleaching agents will typically be at levels of from 1 % to 30% , more typically from 5% to 20% , of the detergent composition, especially for fabric laundering.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes 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.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta- chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents 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 bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551 , issued January 6, 1987 to Burns et al.
  • Peroxygen bleaching agents 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
  • OXONE manufactured commercially by DuPont
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1 ,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • Bleaching agents other than oxygen bleaching agents are also known in the an and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalo- cyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25% , by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • Mixtures of bleaching agents can also be used.
  • Bleach Activator Bleach activators are preferred components of an oxygen bleach containing detergent composition. Bleach activator when present are typically present at levels of from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator. Peroxygen bleaching agents, the perborates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e. , during the washing process) of the peroxy acid or peracid corresponding to the bleach activator.
  • Various nonlimiting 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.
  • nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U. S. 4,634.551 for other typical bleaches and activators useful herein.
  • bleach activators of the above formulae include (6-octanamido- caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido- caproyl) oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551 , incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5- trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perbor
  • Bleach Catalyst Bleach catalysts are optional components of the compositions of the present invention.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621 , U.S. Pat. 5,244,594; U.S. Pat. 5, 194,416; U.S. Pat. 5, 114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1 ,4,7- trimethyl-1 ,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1 ,4,7-trimethyl-1 ,4,7- triazacyclononane) 2 -(ClO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4 ) 4 , Mn III- Mn IV 4 (u-O) 1 (u-OAc) 2 -(1,4,7-trimethyl-1 ,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7- trimethyl-1,4,7-triazacyclononane)- (OCH 3 ) 3
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech. , (1983), 2, pages 1-94.
  • the most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH 3 ) 5 OAc] T y , wherein "OAc" represents an acetate moiety and "T y " is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH 3 ) 5 OAc]Cl 2 ; as well as [Co(NH 3 ) 5 OAc](OAc) 2 ;
  • compositions and cleaning processes herein can be adjusted to provide on the order of at least one pan per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm to 10 ppm, and most preferably from 0.1 ppm to 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical automatic dishwashing compositions herein will comprise from 0.0005% to 0.2% , more preferably from 0.004% to 0.08% , of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.
  • Detergent builders can optionally but preferably be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces.
  • Builders can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering 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.
  • Built detergents typically comprise at least 1 % builder.
  • Liquid formulations typically comprise 5% to 50% , more typically 5 % to 35% of builder.
  • Granular formulations typically comprise from 10% to 80% , more typically 15% to 50% builder by weight of the detergent composition.
  • Lower or higher levels of builders are not excluded. For example, certain detergent additive or high-surfactant formulations can be unbuilt.
  • Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
  • silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non-structured-liquid types
  • borates e.g., for pH-buffering purposes
  • sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing detergent compositions.
  • Builder mixtures sometimes termed “builder systems” can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein.
  • preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from 60: 1 to 1 :80.
  • Certain preferred laundry 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
  • NaSKS-6 is a crystalline layered aluminium-free ⁇ -Na 2 SiO 5 morphology 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 O 2x + 1 ⁇ yH 2 O 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.
  • crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM 2 O ⁇ ySiO 2 .zM'O 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,
  • 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 CO 3 .CaCO 3 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 or for use in synthetic detergent bars.
  • Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels. Suitable for the present purposes are those having empirical formula: [M 2 (AlO 2 ) z (SiO 2 ) v ] ⁇ xH 2 O 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 amorphous, 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.
  • Suitable organic detergent builders include polycarboxylate compounds, including water- soluble nonsurfactant dicarboxy lates and tricarboxy lates. 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 oxydisuccinate, see Berg, U.S. 3, 128,287, April 7, 1964, and Lamberti et al, U.S. 3,635,830, January 18, 1972; "TMS/TDS" builders of U.S.
  • citric acid and soluble salts thereof are important carboxylate builders e.g. , for heavy duty liquid detergents, due to availability from renewable resources and biodegradability.
  • Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates.
  • 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-1, 1-diphosphonate 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 antiscaling properties.
  • Succinate builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate.
  • Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C 12 - C 18 monocarboxylic acids, can also be incorporated into the compositions as surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity.
  • Other suitable polycarboxylates are disclosed in 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.
  • Mineral Builders Waters of hydration or anions other than carbonate may be added provided that the overall charge is balanced or neutral.
  • 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 chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof.
  • NaKCa 2 (CO 3 ) 3 K 2 Ca 2 (CO 3 ) 3 , and combinations thereof.
  • An especially preferred material for the builder described herein is Na 2 Ca(CO 3 ) 2 in 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:sammlungite, Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite,
  • Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with SRA to be more easily cleaned in later washing procedures.
  • SRA's can include a variety of charged, e.g. , anionic or even cationic (see U.S.
  • ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterification/ oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1 ,2- propylene/polyoxyethylene terephthalate polyesters of U.S.
  • DMT dimethyl terephthalate
  • PG ,2-propylene glycol
  • Gosselink et al for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG "), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, Me- capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end- capped terephthalate esters of U.S.
  • Gosselink et al 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g. , PEG 3400.
  • Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
  • SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany.
  • Other SRA's are polyesters with repeat units containing 10-15% by weight of ethylene terephthalate together with 90-80% by weight of
  • polyoxyethylene terephthalate derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • Commercial examples include ZELCON 5126 from Dupont and
  • SRA is an oligomer having empirical formula (CAP) 2 (EG/PG) 5 (T) 5 (SIP) 1 which comprises terephthaloyl (T), sulfoisophthaloyl (SEP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5: 1 to about 10: 1, and two end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • CAP empirical formula
  • Said SRA preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabiliser, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene- sulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis pot, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.
  • Suitable monomers for the above SRA include Na 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na- dimethyl 5- sulfoisophthalate, EG and PG.
  • oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from me group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof Preferred of such esters are those of empirical formula.
  • SEG and CAP monomers for the above esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate (“SEG”), Na-2- ⁇ 2-(2-hydroxyethoxy) ethoxy ⁇ ethanesulfonate (“SE3”) and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol.
  • Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2- hydroxyethoxy)ethoxy ⁇ ethanesulfonate and/or sodium 2-[2- ⁇ 2-(2-hydroxyethoxy)- ethoxy ⁇ ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -O 3 S[CH 2 CH 2 O]3.5)- and B is a unit from glycenn and the mole ratio EG/PG is about 1.7- 1 as measured by conventional gas chromatography after complete hydrolysis.
  • SRA's include (I) nonionic terephthalates using diisocyanate coupling agents to link up polymeric ester structures, see U S 4,201 ,824, Violland et al. and U.S 4,240,918 Lagasse et al; (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With a proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al. ; (Ill) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201 ,824, Violland et al; (IV) poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01 % to 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene- pentamine.
  • Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal- antiredeposition agents are the cationic compounds disclosed in European Patent
  • Clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111 ,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. See U.S. Patent 4,891 ,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.
  • Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Polymeric dispersing agents can advantageously be utilized at levels from 0.1 % to 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder 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 materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammomum salts.
  • Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from 2.000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from 30: 1 to 1: 1, more preferably from 10: 1 to 2: 1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammomum salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acry lie/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1 ,000 to 50,000, more preferably from 1 ,500 to 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.01 % to 1.2% , by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents" , M.
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona.
  • Tinopal UNPA Tinopal CBS and Tinopal 5BM
  • Ciba-Geigy Artic White CC and Artic White CWD
  • 2-(4-styryl- phenyl)-2H-naptho[1 ,2-d]triazoles 4,4'-bis-(1 ,2,3-triazol-2-yl)-stilbenes
  • 4,4'- bis(styryl)bisphenyls 4,4'- bis(styryl)bisphenyls
  • aminocoumarins aminocoumarins.
  • Preferred poiyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or
  • 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.
  • the number of amine oxide groups present in the poiyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the poiyamine oxides can be obtained in almost any degree of
  • 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" .
  • the PVPVI copolymers typically have a molar ratio of N- vinylimidazole to N-vinylpyrrolidone from 1 : 1 to 0.2: 1 , more preferably from 0.8: 1 to 0.3: 1 , most preferably from 0.6:1 to 0.4: 1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1 ,000 to 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50: 1 , and more preferably from 3:1 to 10: 1.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R 1 is anilino
  • R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4' ,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2- yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R 1 is anilino
  • R 2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N- methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM- GX by Ciba-Geigy Corporation.
  • R 1 is anilino
  • R 2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials e.g.
  • PVNO and/or PVPVI with such selected optical brighteners (e.g., Tinopal 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 detergent composition components when used alone.
  • selected optical brighteners e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient" .
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in 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 emylenedianiinetetraceta.es, N-hydroxyethy lethy lenediaminetriacetates, nitrilotriacetates, ethylenediamine
  • tetraproprionates triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammomum, and substimted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in 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 1 ,2-dihydroxy- 3,5-disulfobenzene.
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate
  • EDDS especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates.
  • MGDA water-soluble methyl glycine diacetic acid
  • these chelating agents will generally comprise from 0 .1 % to 15 % by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0. 1 % to 3 .0% by weight of such compositions Suds Suppressors
  • 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
  • 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 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammomum and alkanolammonium salts.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • hydrocarbons such as paraffin, fatty acid esters (e.g. , fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 ketones (e.g , stearone), etc.
  • suds inhibitors include N-alkylated ammo 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 -40°C and 50°C, and a minimum boiling point not less thanl 10°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 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 12 to 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
  • Silicone 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.
  • silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone 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, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about
  • 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 primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise 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 silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone 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 polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorgan
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) 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 6 -C 16 alkyl alcohols having a C 1 -C 16 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • 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 either overflow the washing machine or negatively affect the washing mechanism of the dishwasher.
  • Suds suppressors, when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry or dishwashing detergents for use in automatic laundry or dishwashing machines.
  • compositions herein will generally comprise from 0% to 10% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to 5% , by weight, of the detergent composition.
  • Silicone suds suppressors are typically utilized in amounts up to 2.0% , by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01 % to 1 % of silicone suds suppressor is used, more preferably from 0.25 % to 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any optional materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1 % to 2% , by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01 % to 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.
  • 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. 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. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from 0.01 % to 2% , by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from 0.0001 % to 90% of a finished perfume composition.
  • Non-limiting examples of perfume ingredients useful herein include: 7-acetyl- 1 ,2,3,4,5,6,7,8-octahydro-1 , 1 ,6,7-tetramethyl naphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1 ,6, 10-trimethyl-2,5,9- cyclododecatrien-1-yl ketone; 7-acetyl-1 ,1 ,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert- butyl-1 ,1-dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta- naphthyl ketone; 6-acetyl-1, 1 ,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1 , 1,2,6- tetramethyl indane
  • Particularly preferred perfume materials are those that provide the largest odor
  • perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(para-tert- butylphenyl)-propionaldehyde; 7-acetyl-1 ,2,3,4,5,6,7,8-octahydro-1,1 ,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; para-tert-buryl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta- naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8- hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benz
  • perfume materials include essential oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
  • Still other perfume chemicals include phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2-(1, 1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol.
  • Carriers such as diethylphthalate can be used in the finished perfume compositions.
  • Other Ingredients such as diethylphthalate can be used in the finished perfume compositions.
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C 10 -C 16 alkanolamides can be incorporated into the compositions, typically at 1 %-10% levels.
  • monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing optional surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • water-soluble magnesium and/or calcium salts such as MgCl 2 , MgSO 4 , CaCl 2 CaSO 4 , can be added at levels of, typically, 0.1 %-2%, to provide additional suds and to enhance grease removal performance.
  • Various 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.
  • SIPERNAT D10 DeGussa
  • a proteolytic enzyme solution containing 3 %- 5 % of C 13- 15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • EO 7 ethoxylated alcohol
  • enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g. , 1,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90% . typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5.
  • Liquid dishwashing product formulations preferably have a pH between 6.8 and 9.0.
  • Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • Granules Manufacture Adding the bis-alkoxylated cationics of this invention into a crutcher mix, followed by conventional spray drying, helps remove any residual, potentially malodorous, short-chain amine contaminants.
  • the formulator wishes to prepare an admixable particle containing the alkoxylated cationics for use in, for example, a high density granular detergent, it is preferred that the particle composition not be highly alkaline. Processes for preparing high density (above 650 g/l) granules are described in U.S. Patent 5,366,652. Such particles may be formulated to have an effective pH in-use of 9, or below, to avoid the odor of impurity amines.
  • PEG4000 Polyethylene glycol; average molecular weight 4000
  • SRA-1 Soil release agent methyl cellulose; molecular weight about 13000, degree of substitution 1.8-1.9
  • Granular detergents are as follows in Examples A and B. Dosage - 20 g/30 L
  • AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants AQA-2 through AQA-22 or other AQA surfactants herein.
  • the bis-AQA- 1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • the following illustrates a laboratory procedure and test results, over a variety of soils and stains, using compositions within the scope of the invention. As will be seen from the data, overall cleaning improvements are achieved with a wide variety of soils and stains on various fabrics.
  • the sample preparation basically involves following steps :
  • the individual surfactants are weighed and mixed in the following sequence :
  • This 500 ml mixture of surfactants is good for five washes, 100 mls of this stock solution are used for per wash. This 100 ml solution when added to 49 liters of tap water gives the corresponding wash concentrations for individual surfactants.
  • Silicate 148.32 gms per 900 ml of Distilled water; 50 mls of this solution are used per wash.
  • Granules Each granule component is weighed separately in the same beaker. Order of addition to the washing machine :
  • DKPE is double-knit polyester.
  • DMO dirty motor oil
  • Test Results I show the performance of compositions according to the present invention using CoCoMeEO2 plus a mixture of LAS/AS and Test Results II show the performance using CoCoMeEO10* plus LAS/AS, as compared with CoCoMeEO2/LAS.
  • performance is measured against various soil types, i.e., body soil, builder sensitive soil, bleach sensitive soil, surfactant sensitive soil and socks.
  • EO10 indicates two poly-EO chains with an overall average of 10 EO units in the molecule, typically (but not restricted to) about 5 er chain.
  • TAS Sodium tallow alkyl sulfate
  • Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
  • TPKFA C 12 -C 14 topped whole cut fatty acids
  • STPP Anhydrous sodium tripolyphosphate
  • Zeolite A Hydrated Sodium Aluminosilicate of formula
  • Citric acid Anhydrous citric acid
  • Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between
  • MA/AA Copolymer of 1 :4 maleic /acrylic acid
  • Protease Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename
  • Alcalase Proteolytic enzyme of activity 3AU/g sold by
  • Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme
  • Amylase Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename
  • Lipase Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S under the tradename
  • Endolase Endoglunase enzyme of activity 3000 EVU/g sold by NOVO Industries A/S
  • PB4 Sodium perborate tetrahydrate of nominal formula NaBO 2 .3H 2 O.H 2 O 2
  • PB1 Anhydrous sodium perborate bleach of
  • NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
  • NACA-OBS (6 nonanamido caproyl) oxybenzene
  • Mn Catalyst Mn IV 2 (m-O) 3 (1 ,4,7-trimethyl-1 ,4,7- triazacyclononane) 2 -(PF 6 ) 2 as described in
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-
  • PVNO Polyvinylpyridine N-oxide
  • PVPVI Copolymer of polyvinylpyrrolidone
  • Silicone antifoam Polydimethylsiloxane foam controller with
  • siloxane-oxyalkylene copolymer as dispersing
  • said dispersing agent of 10: 1 to 100:1.
  • a and C are phosphorus-containing detergent compositions and B is a zeolite- containing detergent composition.
  • the bis-AQA- 1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • nil bleach-containing detergent formulations are of particular use in washing colored clothing.
  • the bis-AQA- 1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • the bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • the bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • liquid detergent formulations according to the present invention are prepared:
  • the bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • Any of the granular detergent compositions provided herein may be tabletted using known tabletting methods to provide detergent tablets.
  • compositions can contain various particulate detersive ingredients (e.g. , bleaching agents, as disclosed hereinabove) stably suspended therein.
  • Such non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • the AQA surfactants are incorporated in the compositions at the levels and in the manner described hereinabove for the manufacture of other laundry detergent compositions.
  • the liquid phase will generally comprise from 35 % to 99% by weight of the detergent compositions herein. More preferably, the liquid phase will comprise from 50% to 95% by weight of the compositions. Most preferably, the liquid phase will comprise from 45% to 75% by weight of the compositions herein.
  • the liquid phase of the detergent compositions herein essentially contains relatively high concentrations of a certain type anionic surfactant combined with a certain type of nonaqueous, liquid diluent.
  • the anionic surfactant essentially utilized as an essential component of the nonaqueous liquid phase is one selected from the alkali metal salts of alkylbenzene sulfonic acids in which the alkyl group contains from 10 to 16 carbon atoms, in straight chain or branched chain configuration.
  • alkylbenzene sulfonic acids in which the alkyl group contains from 10 to 16 carbon atoms, in straight chain or branched chain configuration.
  • LAS sodium and potassium linear straight chain alkylbenzene sulfonates
  • the average number of carbon atoms in the alkyl group is from 11 to 14.
  • Sodium C 11 -C 14 LAS is especially preferred.
  • the alkylbenzene sulfonate anionic surfactant will be dissolved in the nonaqueous liquid diluent which makes up the second essential component of the nonaqueous phase.
  • me alkylbenzene sulfonate anionic surfactant is generally present to the extent of from 30% to 65% by weight of the liquid phase. More preferably, the alkylbenzene sulfonate anionic surfactant will comprise from 35% to 50% by weight of the nonaqueous liquid phase of the compositions herein. Utilization of this anionic surfactant in these concentrations corresponds to an anionic surfactant concentration in the total composition of from 15% to 60% by weight, more preferably from 20% to 40% by weight, of the composition.
  • the hereinbefore described alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent which contains two essential components. These two components are a liquid alcohol alkoxylate material and a nonaqueous, low-polarity organic solvent,
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C 12 - C 13 alcohol having 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C 9 - C 11 primary alcohol having 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 C 9 - C 11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C 12 -C 15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • the alcohol alkoxylate component which is essentially utilized as part of the liquid diluent in the nonaqueous compositions herein will generally be present to the extent of from 1 % to 60% of the liquid phase composition. More preferably, the alcohol alkoxylate component will comprise 5% to 40% of the liquid phase. Most preferably, the essentially utilized alcohol alkoxylate component will comprise from 5% to 30% of the detergent composition 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 1 % to 60% by weight, more preferably from 2% to 40% by weight, and most preferably from 5% to 25% by weight, of the composition. ii) Nonaqueous Low-Polarity Organic Solvent
  • a second essential component of the liquid diluent which forms part of the liquid phase of the detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s).
  • solvent is used herein to connote the non-surface active carrier or diluent portion of the liquid phase of the composition. 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 material dispersed within the “solvent"-containing liquid phase. Thus the term “solvent” is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
  • the nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity.
  • low-polarity liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • relatively polar solvents such as ethanol should not be utilized.
  • Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include non-vicinal C 4 -C 8 alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides.
  • a preferred type of nonaqueous, low-polarity solvent for use in the compositions herein comprises the non-vicinal C 4 -C 8 branched or straight chain alkylene glycols.
  • Materials of this type include hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1 ,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is the most preferred.
  • nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra- C 2 -C 3 alkylene glycol mono C 2 -C 6 alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred.
  • Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
  • nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs). Such materials are those having molecular weights of at least 150. PEGs of molecular weight ranging from 200 to 600 are most preferred.
  • PEGs of molecular weight ranging from 200 to 600 are most preferred.
  • Yet another preferred type of non-polar, nonaqueous solvent comprises lower molecular weight methyl esters. Such materials are those of the general formula: R 1 -C(O)-OCH 3 wherein R 1 ranges from 1 to 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the nonaqueous, low-polarity 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 will generally be utilized in an amount of from 1 % to 70% by weight of the liquid phase.
  • the nonaqueous, low-polarity organic solvent will comprise from 10% to 60% by weight of the liquid phase, most preferably from 20% to 50% by weight, of the liquid phase of the composition. Utilization of this organic solvent in these concentrations in the liquid phase corresponds to a solvent concentration in the total composition of from 1 % to 50% by weight, more preferably from 5% to 40% by weight, and most preferably from 10% to 30% by weight, of the composition.
  • the ratio of alcohol alkoxylate to organic solvent within the liquid diluent can be used to vary the rheological properties of the detergent compositions eventually formed.
  • the weight ratio of alcohol alkoxylate to organic solvent will range from 50: 1 to 1:50. More preferably, this ratio will range from 3: 1 to 1 :3.
  • the amount of total liquid diluent in the nonaqueous liquid phase herein will be determined by the type and amounts of other composition components and by me desired composition properties.
  • the liquid diluent will comprise from 35% to 70% of the nonaqueous liquid phase of the compositions herein. More preferably, the liquid diluent will comprise from 50% to 65% of the nonaqueous liquid phase. This corresponds to a nonaqueous liquid diluent concentration in the total composition of from 15% to 70% by weight, more preferably from 20% to 50% by weight, of the composition.
  • nonaqueous liquid detergent compositions herein can be prepared by combining the essential and optional components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein.
  • essential and certain preferred optional components will be combined in a particular order and under certain conditions.
  • a second process step the heated admixture formed as hereinbefore described is maintained under shear agitation at a temperature from 40°C to 100°C for a period of from 2 minutes to 20 hours.
  • a vacuum can be applied to the admixture at this point.
  • This second process step serves to completely dissolve the anionic surfactant in the nonaqueous liquid phase.
  • this liquid phase combination of materials is cooled to a temperature of from 0°C to 35 °C.
  • This cooling step serves to form a structured, surfactant-containing liquid base into which the particulate material of the detergent compositions herein can be added and dispersed.
  • Particulate material is added in a fourth process step by combining the particulate material with the liquid base which is maintained under conditions of shear agitation.
  • any optional surfactants in solid particulate form can be added in the form of particles ranging in size from 0.2 to 1,000 microns.
  • particles of substantially all of an organic builder, e.g. , citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate can be added while continuing to maintain this admixture of composition components under shear agitation.
  • Other solid form optional ingredients can then be added to the composition at this point. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
  • the particles of the highly preferred peroxygen bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation.
  • the peroxygen bleaching agent material By adding the peroxygen bleaching agent material last, or after all or most of the otfier components, and especially after alkalinity source particles, have been added, desirable stability benefits for the peroxygen bleach can be realized. If enzyme prills are incorporated, they are preferably added to the nonaqueous liquid matrix last.
  • agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics.
  • one or more of the solid components may be added to the agitated mixture as a slurry of particles premixed with a minor portion of one or more of the liquid components.
  • a premix of a small fraction of the alcohol alkoxylate and/or nonaqueous, low-polarity solvent with particles of the organic builder material and/or the particles of the inorganic alkalinity source and/or particles of a bleach activator may be separately formed and added as a slurry to the agitated mixture of composition components.
  • compositions of this invention can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics.
  • an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering/bleaching solutions.
  • the aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.
  • An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from 500 to 7,000 ppm of composition in aqueous solution. More preferably, from 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.
  • a non-limiting example of a bleach-containing nonaqueous liquid laundry detergent is prepared having the composition as set forth in Table I.
  • bis-AQA-1 may be replaced by bis-AQA surfactants 2-22 or other bis- AQA surfactants herein.
  • the composition is prepared by mixing the bis-AQA and LAS, then the hexylene glycol and alcohol ethoxylate, together at 54°C (130°F) for 1/2 hour. This mixture is then cooled to 29°C (85°F) whereupon the remaining components are added. The resulting composition is then stirred at 29°C (85°F) for another 1/2 hour.
  • the resulting composition is a stable anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations.
  • the following Examples A and B further illustrate the invention herein with respect to a laundry bar.
  • bis-AQA-1 may be replaced by an equivalent amount of bis-AQA surfactants bis-AQA2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • the following hand wash detergent formulations are prepared by mixing the ingredients together in the percentage weight amounts as indicated below.
  • AQA-9* May be replaced by any AQA surfactant described herein.
  • Preferred AQA surfactants for use in this example are those with from 10 to 15 ethoxy groups; for example AQA-10, AQA-16.
  • Modern, high performance hand dishwashing compositions can contain ingredients which are designed to provide specific in-use product attributes such as grease cutting ability, high sudsing, mildness and skin feel benefits.
  • ingredients for use with the bis-AQA surfactants herein include, for example, amine oxide surfactants, betaine and/or sultaine surfactants, alkyl sulfate and alkyl ethoxy sulfate surfactants, liquid carriers, especially water and water/propylene glycol mixtures, natural oils such lemon oil.
  • preferred liquid and/or gel hand dishwashing compositions may also contain calcium ions, magnesium ions, or mixtures of calcium/magnesium ions, which afford additional grease cutting performance advantages especially when used in combination with detersive mixtures comprising the bis-AQA surfactant herein in combination with, for example, amine oxide, alkyl sulfates and alkyl ethoxy sulfates.
  • Magnesium or calcium or mixed Mg/Ca ion sources typically comprise from 0.01 % to 4% , preferably from 0.02% to 2% , by weight, of such compositions.
  • Various water-soluble sources of these ions include, for example, sulfate, chloride and acetate salts.
  • compositions may also contain nonionic surfactants, especially those of the polyhydroxy fatty acid amide and alkyl polyglucaside classes.
  • nonionic surfactants especially those of the polyhydroxy fatty acid amide and alkyl polyglucaside classes.
  • Preferred are the C 12 -C 14 (coconut alkyl) members of these classes.
  • An especially preferred nonionic surfactant for use in hand dishwashing liquids is C 12 -C 14 N-methylglucamide.
  • Preferred amine oxides include C 12 -C 14 dimemylamine oxide.
  • the alkyl sulfates and alkyl ethoxy sulfates are as described hereinabove. Usage levels for such surfactants in dishwashing liquids is typically in the range from 3% to 50% of the finished composition.
  • dishwashing liquid compositions has been described in more detail in various patent publications including U.S. 5,378,409, U.S. 5,376,310 and U.S. 5,417,893, incorporated herein by reference.
  • Modern automatic dishwashing detergents can contain bleaching agents such as hypochlorite sources; perborate, percarbonate or persulfate bleaches; enzymes such as proteases, lipases and amylases, or mixtures thereof; rinse-aids, especially nonionic surfactants; builders, including zeolite and phosphate builders; low-sudsing detersive surfactants, especially ethylene oxide/propylene oxide condensates.
  • Such compositions are typically in the form of granules or gels. If used in gel form, various gelling agents known in the literature can be employed.
  • Example further illustrates the invention herein with respect to a hand dishwashing liquid.
  • the bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • compositions can be used in the compositions to provide varying degrees of viscosity or rigidity, according to the desires of the formulator.
  • mixtures of bis-AQA surfactants which can be substimted for the bis-AQA surfactants listed in any of the foregoing Examples.
  • such mixtures can be used to provide a spectrum of performance benefits and/or to provide cleaning compositions which are useful over a wide variety of usage conditions.
  • the bis-AQA surfactants in such mixtures differ by at least 1.5, preferably 2.5- 20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10: 1-1 : 10.
  • Non- limiting examples of such mixtures are as follows.
  • compositions advantageously provide improved detergency performance (especially in a fabric laundering context) over a broader range of water hardness than do the cationic surfactants herein used individually.
  • shorter EO cationics e.g., EO2
  • higher EO cationics e.g., EO15
  • builders can optimize the performance "window" of anionic surfactants. Until now, however, broadening the window to encompass essentially all conditions of water hardness has been impossible to achieve.
  • This Example illustrates perfume formulations (A-C) made in accordance with the invention for incorporation into any of the foregoing Examples of bis-AQA-containing detergent compositions.
  • the various ingredients and levels are set forth below.

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Abstract

L'invention concerne une composition détersive constituée d'une enzyme, d'un tensioactif non composé d'ammonium quaternaire alcoxylé et d'un tensioactif cationique d'ammonium quaternaire bis-alcoxylé (bis-AQA).
PCT/US1997/008444 1996-05-17 1997-05-16 Composition detersive WO1997043388A2 (fr)

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JP9541172A JPH11510554A (ja) 1996-05-17 1997-05-16 洗剤組成物
EP97924766A EP0912686A2 (fr) 1996-05-17 1997-05-16 Composition detersive
BR9710678A BR9710678A (pt) 1996-05-17 1997-05-16 Composi-Æo detergente

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US60/017,883 1996-05-17

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PCT/US1997/008317 WO1997044419A2 (fr) 1996-05-17 1997-05-16 Composition detergente
PCT/US1997/008373 WO1997044433A1 (fr) 1996-05-17 1997-05-16 Composition de detergent
PCT/US1997/008316 WO1997044418A1 (fr) 1996-05-17 1997-05-16 Composition detergente
PCT/US1997/008444 WO1997043388A2 (fr) 1996-05-17 1997-05-16 Composition detersive
PCT/US1997/008372 WO1997044432A1 (fr) 1996-05-17 1997-05-16 Composition de detergent
PCT/US1997/008314 WO1997044425A2 (fr) 1996-05-17 1997-05-16 Composition detergente
PCT/US1997/008315 WO1997044431A1 (fr) 1996-05-17 1997-05-16 Composition detergente

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PCT/US1997/008373 WO1997044433A1 (fr) 1996-05-17 1997-05-16 Composition de detergent
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PCT/US1997/008315 WO1997044431A1 (fr) 1996-05-17 1997-05-16 Composition detergente

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BR (8) BR9710676A (fr)
CA (8) CA2254961A1 (fr)
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WO (8) WO1997043394A2 (fr)
ZA (1) ZA974226B (fr)

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WO1999063038A1 (fr) * 1998-06-03 1999-12-09 Henkel Kommanditgesellschaft Auf Aktien Detergents contenant une amylase et des derives d'acetonitrile
WO2000060040A1 (fr) * 1999-04-01 2000-10-12 The Procter & Gamble Company Compositions detergentes
US6136769A (en) * 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
WO2000077137A1 (fr) * 1999-06-14 2000-12-21 Colgate-Palmolive Company Composition detergente liquide de blanchisserie contenant un agent tensioactif quaternaire ethoxyle
WO2001027230A1 (fr) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Detergents
DE19948669A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmitteltabletten
DE19948668A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmitteltabletten
WO2001034742A1 (fr) * 1999-11-10 2001-05-17 Unilever Plc Compositions de poudre pour machine a laver la vaisselle contenant des composes tensioactifs cationiques solubles dans l'eau
WO2001034745A1 (fr) * 1999-11-10 2001-05-17 Unilever Plc Compositions pour lave-vaisselle contenant des tensioactifs cationiques hydrosolubles
WO2001088073A1 (fr) * 2000-05-16 2001-11-22 Clariant International Ltd Liquides de nettoyage pour usage delicat
WO2002018527A1 (fr) * 2000-09-01 2002-03-07 Unilever Plc Composition d'entretien pour tissus
WO2002022770A1 (fr) * 2000-09-13 2002-03-21 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de nettoyage a sechage rapide, notamment liquide de vaisselle a la main
WO2002061026A1 (fr) * 2001-02-01 2002-08-08 Ecolab Inc. Compositions solides stables aux enzymes et procedes d'utilisation desdites compositions
EP1323817A1 (fr) * 2001-12-24 2003-07-02 Cognis Iberia, S.L. Compositions cationiques de nettoyage de surfaces dures
WO2003102119A1 (fr) * 2002-05-31 2003-12-11 Akzo Nobel N.V. Compositions de premelange de nettoyage et de degraissage a faible teneur en composes organiques volatils (voc)
EP1418226A1 (fr) * 2002-11-07 2004-05-12 Unilever N.V. Composition détergente
WO2004065535A1 (fr) * 2003-01-14 2004-08-05 Ecolab Inc. Composition detergente liquide et ses methodes d'utilisation
WO2006037438A1 (fr) * 2004-10-04 2006-04-13 Unilever N.V. Composition detergente liquide
WO2014012869A1 (fr) * 2012-07-19 2014-01-23 Henkel Ag & Co. Kgaa Détergent liquide stable à capacité antiredéposition
EP3301160A1 (fr) * 2016-10-03 2018-04-04 The Procter & Gamble Company Composition de détergent pour lessive à bas ph
US20210277329A1 (en) * 2018-07-05 2021-09-09 Evonik Operations Gmbh Active compositions for highly viscous laundry and cleaning formulations
EP4053328A1 (fr) * 2021-03-02 2022-09-07 CHT Germany GmbH Traitement combiné de blanchiment pour textiles
WO2023087194A1 (fr) * 2021-11-18 2023-05-25 Ecolab Usa Inc. Détergent pour le lavage à la main de casseroles et de poêles ayant une fonction d'élimination des taches
NL2032249B1 (nl) * 2022-06-22 2024-01-08 Hg Int B V Samenstelling voor het verwijderen van kalkaanslag van gekleurd sanitair

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ES2391263T3 (es) 2002-12-04 2012-11-22 Clariant Finance (Bvi) Limited Procedimiento para preparar una composición de amonio cuaternario
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JP5642533B2 (ja) * 2010-12-24 2014-12-17 ライオン株式会社 自動食器洗い乾燥機用洗浄剤組成物
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JP6184830B2 (ja) * 2013-06-14 2017-08-23 花王株式会社 漂白洗浄剤組成物
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US6136769A (en) * 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
WO1999063038A1 (fr) * 1998-06-03 1999-12-09 Henkel Kommanditgesellschaft Auf Aktien Detergents contenant une amylase et des derives d'acetonitrile
WO2000060040A1 (fr) * 1999-04-01 2000-10-12 The Procter & Gamble Company Compositions detergentes
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WO2001027230A1 (fr) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Detergents
DE19948669A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmitteltabletten
DE19948668A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmitteltabletten
WO2001034745A1 (fr) * 1999-11-10 2001-05-17 Unilever Plc Compositions pour lave-vaisselle contenant des tensioactifs cationiques hydrosolubles
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US6345633B1 (en) 1999-11-10 2002-02-12 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Automatic dishwashing compositions containing water soluble cationic surfactants
WO2001034742A1 (fr) * 1999-11-10 2001-05-17 Unilever Plc Compositions de poudre pour machine a laver la vaisselle contenant des composes tensioactifs cationiques solubles dans l'eau
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EP1323817A1 (fr) * 2001-12-24 2003-07-02 Cognis Iberia, S.L. Compositions cationiques de nettoyage de surfaces dures
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EP1418226A1 (fr) * 2002-11-07 2004-05-12 Unilever N.V. Composition détergente
WO2004065535A1 (fr) * 2003-01-14 2004-08-05 Ecolab Inc. Composition detergente liquide et ses methodes d'utilisation
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AU2004206217B2 (en) * 2003-01-14 2009-01-08 Ecolab Inc. Liquid detergent composition and methods for using it
WO2006037438A1 (fr) * 2004-10-04 2006-04-13 Unilever N.V. Composition detergente liquide
WO2014012869A1 (fr) * 2012-07-19 2014-01-23 Henkel Ag & Co. Kgaa Détergent liquide stable à capacité antiredéposition
EP3301160A1 (fr) * 2016-10-03 2018-04-04 The Procter & Gamble Company Composition de détergent pour lessive à bas ph
US20210277329A1 (en) * 2018-07-05 2021-09-09 Evonik Operations Gmbh Active compositions for highly viscous laundry and cleaning formulations
US11692153B2 (en) * 2018-07-05 2023-07-04 Evonik Operations Gmbh Long-chain alkyl esterquats for highly viscous laundry and cleaning formulations
EP4053328A1 (fr) * 2021-03-02 2022-09-07 CHT Germany GmbH Traitement combiné de blanchiment pour textiles
WO2022184584A1 (fr) * 2021-03-02 2022-09-09 CHT Germany GmbH Traitement de blanchiment combiné pour textiles
WO2023087194A1 (fr) * 2021-11-18 2023-05-25 Ecolab Usa Inc. Détergent pour le lavage à la main de casseroles et de poêles ayant une fonction d'élimination des taches
NL2032249B1 (nl) * 2022-06-22 2024-01-08 Hg Int B V Samenstelling voor het verwijderen van kalkaanslag van gekleurd sanitair

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CA2254947A1 (fr) 1997-11-27
BR9710444A (pt) 1999-08-17
EP0918833A1 (fr) 1999-06-02
CN1232489A (zh) 1999-10-20
JPH11510554A (ja) 1999-09-14
JPH11511797A (ja) 1999-10-12
CN1168812C (zh) 2004-09-29
BR9710667A (pt) 1999-08-17
BR9710676A (pt) 1999-08-17
CN1225675A (zh) 1999-08-11
WO1997044418A1 (fr) 1997-11-27
MX9809681A (es) 1999-03-01
CN1225678A (zh) 1999-08-11
AR014606A1 (es) 2001-03-28
MX9809624A (en) 1999-03-01
EP0906392A2 (fr) 1999-04-07
CA2254948A1 (fr) 1997-11-27
CN1230213A (zh) 1999-09-29
CA2254961A1 (fr) 1997-11-27
JPH11511796A (ja) 1999-10-12
MX9809675A (en) 1999-03-01
BR9710445A (pt) 1999-08-17
BR9710678A (pt) 1999-08-17
BR9709587A (pt) 2000-04-25
WO1997044425A3 (fr) 1997-12-24
CA2254818A1 (fr) 1997-11-27
EP0912686A2 (fr) 1999-05-06
CA2255003A1 (fr) 1997-11-27
CA2255006A1 (fr) 1997-11-20
WO1997043388A3 (fr) 1998-02-12
WO1997044432A1 (fr) 1997-11-27
BR9709321A (pt) 1999-08-10
MX9809684A (en) 1999-03-01
CN1225677A (zh) 1999-08-11
ZA974226B (en) 1998-12-28
JPH11511799A (ja) 1999-10-12
WO1997044431A1 (fr) 1997-11-27
JP2000504061A (ja) 2000-04-04
MX9809679A (en) 1999-03-01
WO1997044425A2 (fr) 1997-11-27
CA2254820A1 (fr) 1997-11-27
CA2255005A1 (fr) 1997-11-20
WO1997043394A3 (fr) 1997-12-24
MX9809683A (en) 1999-03-01
WO1997043394A2 (fr) 1997-11-20
WO1997044419A3 (fr) 1997-12-31
JPH11511795A (ja) 1999-10-12
EP0906405A1 (fr) 1999-04-07
EP0906403A1 (fr) 1999-04-07
EP0912669A2 (fr) 1999-05-06
BR9710675A (pt) 1999-08-17
JPH11512782A (ja) 1999-11-02
AR007169A1 (es) 1999-10-13
JPH11511794A (ja) 1999-10-12
MX9809628A (en) 1999-02-01
EP0907705A1 (fr) 1999-04-14
MX9809674A (en) 1999-03-01
CN1225673A (zh) 1999-08-11
WO1997044419A2 (fr) 1997-11-27
WO1997044433A1 (fr) 1997-11-27

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