Classifications

• • 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
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  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
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  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/65—Mixtures of anionic with cationic compounds
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  • 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
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  • 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
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  • 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 a soil dispersant polymer, 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 hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter and are thus notoriously difficult to remove.
• An additional problem is encountered in the form of lime-soap deposits; the insoluble hardness ion salt (e.g. Ca2 +/Mg2 + ) of fatty acids derived from the degradation of triglyceride soils.
• Low levels of hydrophobic soils, residual stains and lime-soap deposits often remain on the surface of the fabric after washing.
• 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 hydrophobic soils and lime-soap deposits, commonly encountered.
• the bis-AQA surfactants of the present invention provide substantial benefits to die formulator, over cationic surfactants previously known in the art.
• die 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 manufacturing plant.
• 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.
• the availability of bis-AQA surfactants as highly concentrated solutions provides a substantial economic advantage in transportation costs.
• compositions containing a soil dispersant polymer and a bis-AQA surfactant can deliver additional superior cleaning and whiteness performance versus products containing either technology alone.
• Polymeric dispersants enhance overall detergency by crystal growth inhibition, paniculate soil release peptization, anti-redeposition and soil solubilization.
• benefits of the bis-AQA/soil dispersant polymer system are the result of: (1) AQA action on the stain surface to minimise lime-soap formation and to lift off any calcium soaps present, thereby facilitating improved polymer deposition; (2) AQA providing solubilization deep into the soil, while the polymer acts as a "grease removal shuttle", stripping out the AQA-solubilized stain components and dispersing them into the wash liquor.
• 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 a soil dispersant polymer, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:
• R is a linear, branched or substituted Cg- g alkyl, alkenyl, aryl, alkanyl, ether or gluycityl ether moiety
• R ⁇ is a C1-C3 alkyl moiety
• R and R ⁇ can vary independently and are selected from hydrogen, methyl and ethyl
• X is an anion
• a and A' can vary independently and are each C1-C4 alkoxy
• p and q can vary independantly and are integers of from 1 to 30.
• compositions of the present invention comprise a soil dispersant polymer.
• Soil dispersant polymers are present at levels from 0.1 % to 7% , by weight, of the compositions herein. During the wash, these polymers work at the stain/wash liquor interface.
• Suitable dispersants for use herein include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.
• 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 ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U S Patent 3,308,067, issued March 7, 1967
• Acrylic/maleic-based copolymers may also be used as a preferred soil dispersant polymers
• 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, ammomum and substituted ammomum salts Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No.
• EP 193,360 published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate
• Still other useful dispersants include the maleic/acrylic/vinyl alcohol terpolymers.
• Such mate ⁇ als are also disclosed m EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol
• PEG polyethylene glycol
• 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
• Dispersants such as polyaspartate preferably have a molecular weight (avg ) of 10,000
• Most preferred dispersant polymers have characteristic features which include: (1) a reasonably low molecular weight "hydrophobic" polymeric backbone, and (2) pendant "hydrophilic" groups which provide ste ⁇ c stabilization
• a preferred soil dispersant polymer are polyalkoxylated-polyalkylamine polymers (PPP), most preferred are the ethoxylated/propoxylated polyalkylamine or polyalkylimine polymers, such as the ethoxylated polyethyleneamines (PEAs) or the polyethyleneim nes (PEIs) as described in patent application W095/32272.
• bis-AQA Bis-Alkoxylated Quaternary Ammomum
• the second essential component of the present invention comprises an effective amount of a bis-AQA surfactant of the formula:
• R 1 is a linear, branched or substituted alkyl, alkenyl, aryl, alkaryl, ether, glycityl ether moiety containing from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably from 8 tol4 carbon atoms;
• R2 is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl;
• R ⁇ and R 4 can vary independently and are selected from the group consisiting of hydrogen (preferred), meUiyl 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 C1-C4 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 preferably 1 to 4 and q is from 1 to 30, preferably 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.
• the weight ratio of bis-AQA to 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 ingredients.
• 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 die 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 10 to 60 minutes and a wash water temperature of 30°C to 95°C it is preferred to include from 13 ppm to 900 ppm, preferably from 16 ppm to 390 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 0.4% to 2.64% , preferably 0.55% to 1.1 %, 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 me other surfactants (generally anionics or anionic/nonionic mixtures) in the finished compositions. This is to be distinguished from odier 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 1 :70 to 1 :2, preferably from 1 :40 to 1 :6, preferably from 1 :30 to 1 :6, most preferably 1 : 15 to 1:8.
• 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.
• compositions which comprise an anionic surfactant, an optional nonionic surfactant and specialized surfactants such as betaines, sultaines, amine oxides can also be formulated using an effective amount of the bis-AQA surfactants in the manner of this invention.
• Such compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surface cleaners, shampoos, personal cleansing bars, laundry bars, and the like. Since the habits and practices of the users of such compositions show minimal variation, it is satisfactory to include from about 0.25% to about 5% , preferably from about 0.45% to about 2% , by weight, of the bis-AQA surfactants in such compositions.
• 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.
• This can be an important consideration for formulators of detergent compositions of the type which are conventionally designed for use in top loading automatic washing machines, especially of the type used in North America, as well as under Japanese usage conditions.
• such compositions will comprise an anionic surfactant: nonionic surfactant weight ratio in the range from about 25: 1 to about 1:25, preferably about 20: 1 to about 3:1.
• European-type formulas which typically will comprise anionic: nonionic ratios in the range of about 10: 1 to 1 : 10, preferably about 5: 1 to about 1:1.
• Step 1 of the reaction is preferably conducted in an aqueous medium.
• Reaction temperatures are typically in the range of 140-200°C.
• Reaction pressures are 50-1000 psig.
• a base catalyst preferably sodium hydroxide can be used.
• the mole ratio of reactants are 2: 1 to 1: 1 amine to alkyl sulfate.
• the reaction is preferably conducted using Cg-Ci4 alkyl sulfate, sodium salt.
• the ethoxylation and quaternization steps are carried out using conventional conditions and reactants.
• reaction Scheme 5 results in products which are sufficiently soluble in the aqueous reaction medium that gels may form. While the desired product can be recovered from the gel, an alternate, two-step synthesis Scheme 6, hereinafter, may be more desirable in some commercial circumstances.
• the first step in Scheme 6 is conducted as in Scheme 5.
• the second step (ethoxylation) is preferably conducted using ethylene oxide and an acid such as HC1 which provides the quaternary surfactant.
• chlorohydrin i.e. , chloroethanol, can also be reacted to give the desired bishydroxyethyl derivative.
• the first step is preferably conducted in an aqueous medium.
• 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 HS04-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.
• Scheme 7 can optionally be conducted using ethylene oxide under standard ethoxylation conditions, but without catalyst, to achieve monoethoxylation.
• the mixture is cooled to room temperamre and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform The funnel is shaken well for a few minutes and then me mixture is allowed to separate The lower chloroform layer is drained and the chloroform evaporated off to obtain product.
• the mixture is cooled to room temperature and the liquid contents of the glass lmer are poured into a 250 ml separatory funnel along with 80 ml of chloroform 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.
• 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 me ethoxylation reactions typically yield mixtures of materials witii differing degrees of ethoxylation. Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "E02.5", "E03.5".
• R is Cg-Cjg hydrocarbyl and mixmres thereof, preferably Cg, C ⁇ Q, C12, Cj4 alkyl and mixmres 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 Cg-Cjg hydrocarbyl, preferably Cg-Ci4 alkyl, independently p is 1 to 3 and q is 1 to 3, R2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
• a highly preferred bis-AQA compound for use in under built formulations are of the formula wherein p and/or q are integers in the range of between 10 and 15. This compound is particularly useful in laundry handwash detergent compositions.
• 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.
• C ⁇ - jg betaines and sulfobetaines can also be included in the overall compositions.
• C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain soaps may be used.
• Other conventional useful surfactants are listed in standard texts.
• Nonlimiting examples of nonionic surfactants useful herein 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), Cjo-Ci glyceroi ethers.
• AE alkoxylated alcohol
• PFAA's polyhydroxy fatty acid amides
• APG's alkyl polyglycosides
• Cjo-Ci glyceroi ethers Cjo-Ci glyceroi 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 Cj 1- 5 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the condensation product of C12- 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol ⁇ M 45.9 ( me condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C ] 2-Ci3 linear alcohol with 3 moles of ethylene oxide),
• Neodol ⁇ M 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide) and Neodol ⁇ M 45.5 (t e condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; Kyro ⁇ M goB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA 030 or 050 (the condensation product of C12-C14 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.
• Another class of preferred nonionic surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
• R 1 is H, or C ⁇ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
• R 2 is C5.31 hydrocarbyl
• Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to me chain, or an alkoxylated derivative ereof.
• R* is mediyl
• R 2 is a straight Cu_i5 alkyl or ⁇ 15-17 a lkyl or alkenyl chain such as coconut alkyl or mixtures mereof
• Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
• Typical examples include the Ci2-C ⁇ g and C12- 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 substituted 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:
• R2 ⁇ (C n H 2n O)t(glycosyl) x
• R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixmres 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 meir 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 me 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 to 15 moles, of ethylene oxide per mole of alkyl phenol.
• nonionic surfactants of d is type include Igepal ⁇ M 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. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g. , alkyl phenol ethoxylates).
• the condensation products of ethylene oxide wi a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in me present invention.
• the hydrophobic portion of these compounds will preferably have a molecular weight of from 1500 to 1800 and will exhibit water insolubility.
• the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of me 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.
• 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 ⁇ -C ⁇ . preferably C ⁇ -C ⁇ Q 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.
• 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 me removal of paniculate 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 o er 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 mixmres 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 polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.
• Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6: 1 to 3.2: 1 , including, particularly for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp. under the tradename BRITESIL ® , e.g., BRITESIL H20; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck.
• NaSKS-6 is a crystalline layered aluminium-free ⁇ -Na2Si ⁇ 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 ⁇ 2 ⁇ + ryH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein.
• Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11 , as the ⁇ , ⁇ and ⁇ layer-silicate forms.
• Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.
• crystalline ion exchange materials or hydrates mereof having chain structure and a composition represented by the following general formula in an anhydride form: xM2 ⁇ ySi ⁇ 2.zM'0 wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711 , Sakaguchi et al, June 27, 1995.
• 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, al ough 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 2Na2C ⁇ 3.CaC ⁇ 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.
• Alurninosilicate 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 z (Al ⁇ 2) z (Si ⁇ 2) v ] xH2° 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 alurninosilicate production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976.
• the alurninosilicate has a panicle size of 0.1-10 microns in diameter.
• Suitable organic detergent builders include polycarboxylate compounds, including water- soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
• Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
• Polycarboxylate builders include the ether polycarboxylates, such as 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.
• Omer suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1 , 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid; carboxyme yloxysuccinic acid; the various alkali metal, ammomum and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1 ,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
• Citrates e.g., 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- l-hydroxy-l , l-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.
• detersive surfactants or their short-chain homologs also have a builder action. For unambiguous formula accounting purposes, when they have surfactant capability, these materials are summed up as detersive surfactants.
• Preferred types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-l ,6-hexanedioates and the related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986.
• Succinic acid builders include e C5-C20 alkyl and alkenyl succinic acids and salts mereof.
• 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 ⁇ - 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 Uiat 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 mixmres 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 mixmres thereof.
• Preferred builders of this type in their simplest forms are selected from the group consisting of Na 2 Ca(C ⁇ 3) 2 , K 2 Ca(C0 3 )2, Na 2 Ca 2 (C ⁇ 3) 3 , NaKCa(C0 3 ) 2 , NaKCa2(C ⁇ 3)3, K2Ca2(C ⁇ 3)3, and combinations thereof.
• An especially preferred material for the builder described herein is Na2Ca(C03)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 mineral forms include Nyererite, Fairchildite and Shortite.
• compositions described herein may contain a bleach.
• 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 system contains a hydrogen peroxide source and a bleach catalyst.
• the production of me organic peroxyacid occurs by an in si reaction of me bleach activator with a source of hydrogen peroxide.
• Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
• a preformed peracid is incorporated directly into the composition. Compositions containing mixmres of a hydrogen peroxide source and bleach activator in combination with a preformed peracid are also envisaged
• Preferred peroxygen bleaches are perhydrate bleaches. Although the perhydrate bleach itself has some bleaching capability, a superior bleach exists in the peracid formed as a product of the reaction between the hydrogen peroxide released by the perhydrate and a bleach activator. Preformed peracids are also envisaged as a preferred peroxygen bleaching species.
• suitable perhydrate salts include perborate, percarbonate. perphosphate, persulfate and persilicate salts.
• the preferred perhydrate salts are normally the alkali metal salts.
• the perhydrate salt may be included as the crystalline solid without additional protection.
• the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
• Sodium perborate can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
• Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention.
• Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
• Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise.
• a preferred percarbonate bleach comprises dry particles having an average particle size in me 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 is most preferably incorporated into such compositions in a coated form which provides in-product stability.
• a suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,799, granted to Interox on 9th March 1977.
• the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:200 to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1 :49 to 1 : 19.
• the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S ⁇ 4.n.Na2C ⁇ 3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
• coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.
• a 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 metachJoro 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.
• bleaching agents include photoactivated bleaching agents such as me sulfonated zinc and/or aluminum phmalocyanines. 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.
• Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.
• Bleach activators are preferred components where the compositions of me present invention additionally comprises a peroxygen bleaching agent. Bleach activators when present are typically at levels of from 0.1 % to 60%, more typically from 0.5% to 40% of me 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 me peroxy acid or peracid corresponding to the bleach activator.
• bleach activators 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.
• NOBS nonanoyloxybenzene sulfonate
• TAED tetraacetyl ediylene diamine
• Highly preferred amido-derived bleach activators are those of the formulae:
• R* is an alkyl group containing from 6 to 12 carbon atoms
• R 2 is an alkylene containing from 1 to 6 carbon atoms
• R ⁇ is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms
• L is any suitable leaving group.
• a leaving group is any group that is displaced from the bleach activator as a consequence of me nucleophilic attack on the bleach activator by the perhydrolysis anion.
• a preferred leaving group is phenyl sulfonate.
• bleach activators of the above formulae include (6-octanamido- caproyl)oxybenzenesulfonate , (6-nonanamidocaproy l)oxybenzenesulfonate , (6-decanamido- caproy oxybenzenesulfonate, and mixmres 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 mixmres 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 per
• 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 ⁇ 2( u "0)3(l ,4,7- trimethyl-l ,4,7-triazacyclononane)2(PF6)2, Mn I ⁇ 2(u-0) ⁇ (u-OAc)2(l ,4,7-trimethyl-l,4,7- triazacyclononane)2-(Cl ⁇ 4)2, Mn rV 4(u-0)g(l ,4,7-triazacyclononane)4(Cl ⁇ 4)4, MnlH” Mn IV 4(u-0)i(u-OAc)2-(l,4,7-trimethyl-l ,4,7-triazacyclononane)2(CI ⁇ 4)3, Mn ⁇ d ,4,7- trimemyl-l,4,7-triazacyclononane)- (OCH3)3(PF6), and mixmres thereof
• O ⁇ ier metal- based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
• the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5, 153, 161; and 5,227,084.
• compositions and processes herein can be adjusted to provide on me order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundry liquor.
• Cobalt bleach catalysts useful herein are known, and are described, for example, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinore. Mech.. (1983), 2, pages 1-94.
• cobalt pentaamine acetate salts having the formula [Co(NH3)5 ⁇ Ac] T v , wherein "OAc” represents an acetate moiety and “Ty” is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5 ⁇ Ac]Cl2; as well as [Co(NH3)5 ⁇ Ac](OAc)2; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ; [Co(NH 3 ) 5 OAc](S0 4 ); [Co(NH 3 ) 5 OAc](BF 4 )2; and [Co(NH3) 5 OAc](N0 3 ) 2 (herein "PAC").
• the automatic dishwashing compositions and cleaning processes herein can be adjusted to provide on me order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from 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 me cleaning compositions.
• 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 mixmres 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.
• Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
• Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases.
• Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and/ or proteases.
• Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount".
• cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware.
• typical amounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.
• the compositions herein will typically comprise from 0.001 % to 5% , preferably 0.01 %-l % by weight of a commercial enzyme preparation.
• Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
• AU Anson units
• proteases are d e subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
• One suitable 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.
• 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. See also a high pH 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.
• 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 antyloliquefaciens 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; RAPIDASE ® , International Bio-Synthetics, Inc. and TERMAMYL ® , 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.
• These preferred amylases herein share me characteristic of being "stability -enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: 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; or alkaline stability, e.g.
• Stability can be measured using any of me 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 commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability -enhanced amylases vs.
• amylases are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
• preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. antyloliquefaciens, B. sub ⁇ lis, or B.
• Met was substimted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) 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 odier 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. Other 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 man the specific activity of Termamyl® at a temperamre 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. (Such Phadebas® ⁇ -amylase activity assay is described at pages 9-10, WO 95/26397.) Also included herein are ⁇ -amylases which are at least 80% homologous with the amino acid sequences shown in me SEQ ID listings in me references. These enzymes are preferably incorporated into laundry detergent 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 moilusk, 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 me trade name Lipase P "Amano,” or "Amano-P.” Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
• lipotyticum 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.
• the lipase variant may be added in an amount corresponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor.
• the present invention provides me 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 wim 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.
• 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 8909813 A to Novo.
• a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. 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. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
• the enzyme-containing compositions herein may optionally also comprise from 0.001 % to 10% , preferably from 0.005% to 8% , most preferably from 0.01 % to 6%, by weight of an enzyme stabilizing system.
• the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g. , by the formulator or by a manufacturer of detergent-ready enzymes.
• Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixmres thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
• One stabilizing approach is me use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to me enzymes.
• Calcium ions are generally more effective man magnesium ions and are preferred herein if only one type of cation is being used.
• Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 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 me 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.
• Substimted 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 substimted 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.
• chlorine bleach scavengers 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; accordingly, enzyme stability to chlorine in-use is sometimes problematic.
• 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 ethylenedia inetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixmres thereof can likewise be used.
• scavengers such as bisulfate. nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc. , and mixmres thereof can be used if desired.
• me chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g.
• SRA polymeric soil release agents
• SRA's can optionally be employed in the present detergent compositions. If utilized, SRA's will generally comprise from 0.01 % to 10.0% , typically from 0.1 % to 5%, preferably from 0.2% to 3.0% by weight, of the composition.
• 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 die 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. 4,956,447), as well as noncharged monomer units and structures may be linear, branched or even star-shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active properties. Structures and charge distributions may be tailored for application to different fiber or textile types and for varied detergent or detergent additive products.
• Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(rV) alkoxide.
• oligomeric terephthalate esters typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(rV) alkoxide.
• Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without of course forming a densely crosslinked overall structure.
• Suitable SRA's include: a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451 , November 6, 1990 to J.J. Scheibel and E.P.
• 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) ediyl 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 me anionic, especially sulfoaroyl, end- capped terephmalate 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.
• SRA's also include simple copolymeric blocks of ethylene terephthalate or propylene terephthalate wi polye ylene oxide or polypropylene oxide terephmalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as me hydroxye er cellulosic polymers available as METHOCEL from Dow; and the C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December 28, 1976 to Nicol, et al.
• Suitable SRA's characterised by poly (vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C -C 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 toge er with 90-80% by weight of polyoxyethylene terepltthalate, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
• Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.
• Another preferred SRA is an oligomer having empirical formula
• CAP2(EG/PG)5(T)5(SIP) ⁇ which comprises terephthaloyl (T), sulfoisophthaloyl (SIP). oxyethyJeneoxy and oxy-l ,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-l ,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.
• 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 mixmres 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-hydroxyemoxy)-ethanesulfonate, DMT, Na- dimethyl 5- sulfoisophthalate, EG and PG.
• oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxy sulfonates, 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 e oxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixmres mereof.
• Preferred of such esters Preferred of such esters
• CAP, EG/PG, PEG, T and SIP are as defined hereinabove
• DEG represents di(oxyemylene)oxy units
• SEG represents units derived from me sulfoethyl ether of glycerin and related moiety units
• B represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone
• x is from about 1 to about 12
• y' is from about 0.5 to about 25
• y" is from 0 to about 12
• y' " is from 0 to about 10
• z is from about 1.5 to about 25
• z' is from 0 to about 12
• q is from about 0.05 to about 12
• m is from about 0.01 to about 10
• SEG and CAP monomers for the above esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate (“SEG”), Na-2- ⁇ 2-(2-hydroxyemoxy) 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 me product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2- hydroxyethoxy)ethoxy ⁇ ethanesulfonate and/or sodium 2-[2- ⁇ 2-(2-hydroxyethoxy)- ethoxy ⁇ ed ⁇ oxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(TV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ S[CH 2 CH2 ⁇ ]3.5)- and B is a unit from glycerin 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 tereph ⁇ ialates 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 ra er man by opening of the anhydride linkage.
• Either nonionic or anionic SRA's may be used as starting materials as long as ey have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.; (Ill) anionic terephmalate-based SRA's of the urethane-1 inked variety, see U.S. 4,201 ,824, Violland et al; (IV) poly(vinyl caprolactam) and related co-polymers wim monomers such as vinyl pyrrolidone and/or dimemylaminoethyl 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 ese 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 emoxylated 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 me cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
• Other clay soil removal/antiredeposition agents which can be used include me ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; me zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and me amine oxides disclosed in U.S.
• Patent 4,548,744, Connor issued October 22, 1985.
• Other clay soil removal and/or a i redeposition agents known in the art can also be utilized in die 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 me carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
• optical brighteners or o er 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, meminecyanines, dibenzod ⁇ iophene-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.
• Omer brighteners disclosed in mis reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, the 2-(4-styryl- phenyl)-2H-naptho[l ,2-d]triazoles; 4,4'-bis-(l,2,3-triazol-2-yl)-stilbenes; 4,4'- bis(styryl)bisphenyls; and the aminocoumarins.
• d ese brighteners include 4-med ⁇ yl-7-diethyl- amino coumarin; l ,2-bis(benzimidazol-2-yl)emylene; 1,3- diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)miophene; 2-styryl-naptho[l ,2-d]oxazole; and 2-(stilben-4-yl)-2H-naphtho[l ,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.
• compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to anomer during die cleaning process.
• dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese ph alocyanine, peroxidases, and mixmres thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5% , and more preferably from 0.05% to 2% .
• Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives mereof.
• the N-0 group can be represented by the following general structures:
• R ⁇ , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups.
• the amine oxide unit of me polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
• Any polymer backbone can be used as long as me 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 mixmres thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and me other monomer type is an N-oxide.
• the amine N-oxide polymers typically have a rauo of amine to me amine N-oxide of 10: 1 to 1 : 1 ,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
• the polyamine oxides can be obtained in almost any degree of polymerization. Typically, me average molecular weight is wimin the range of 500 to 1 ,000,000; more preferred 1,000 to 500,000; most preferred 5.000 to 100,000. This preferred class of materials can be referred to as "PVNO".
• poly(4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1 :4.
• PVPVT N-vinylpyrrolidone and N-vinylimidazole polymers
• die PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al. , Chemical Analysis, Vol 113.
• 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.
• the detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01 % to 1 % by weight of such optical brighteners.
• hydrophilic optical brighteners useful in the present invention are those having the structural formula:
• Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
• R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyemyl-N-memylamino, morphilino, chloro and amino
• M is a salt-forming cation such as sodium or potassium.
• R ⁇ is anilino
• R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
• ie 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.
• Rj is anilino
• R2 is N-2-hydroxyemyl-N-2-methylamino
• M is a cation such as sodium
• the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyemyl-N- memylamino)-s-triazme-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 is anilino
• R2 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 die 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 die selected polymeric dye transfer inhibiting agents hereinbefore described.
• the combination of such selected polymeric materials (e.g. , PVNO and/or PVPVI) wim 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 man does either of these two detergent composition components when used alone. Widiout being bound by theory, it is believed that such brighteners work this way because ey have high affinity for fabrics in die wash solution and dierefore deposit relatively quick on diese fabrics.
• exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) d e initial brightener concentration in the wash liquor. Brighteners wim relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in me 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 me group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aro ⁇ matic chelating agents and mixmres 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 eir exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
• Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyemylemylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diemylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substimted ammonium salts merein and mixmres 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 me compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al.
• Preferred compounds of diis type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy- 3 ,5-disulfobenzene.
• a preferred biodegradable chelator for use herein is e ylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
• EDDS e ylenediamine disuccinate
• compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful wi , for example, insoluble builders such as zeolites, layered silicates.
• MGDA water-soluble methyl glycine diacetic acid
• mese 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 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 Odimer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
• One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
• the monocarboxylic fatty acids and salts mereof 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.
• non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ⁇ -C4Q ketones (e.g., stearone), etc.
• suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or diree 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 haloparaffm 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 dianl 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 die use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein me polyorganosiloxane is chemisorbed or fused onto ie silica.
• Silicone suds suppressors are well known in die 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.
• An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
• polydimediylsiloxane fluid having a viscosity of from about 20 cs. to about
• the solvent for a continuous phase is made up of certain polyed ylene glycols or polyethylene-polypropylene glycol copolymers or mixmres mereof (preferred), or polypropylene glycol.
• the primary silicone suds suppressor is branched/cross linked 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 temperamre of more than about 2 weight % ; and widiout polypropylene glycol.
• a primary antifoam agent which is a mixture of (a)
• the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less man about 1 ,000, preferably between about 100 and 800.
• the polyethylene glycol and polyed ylene/polypropylene copolymers herein have a solubility in water at room temperamre of more than about 2 weight % , preferably more man about 5 weight % .
• the preferred solvent herein is polye iylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyediylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
• Preferred is a weight ratio of between about 1 : 1 and 1 : 10, most preferably between 1:3 and 1 :6, of polyediylene glycol :copolymer of polyediylene- polypropylene glycol.
• the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
• Omer suds suppressors useful herein comprise the secondary alcohols (e.g. , 2-alkyi alkanols) and mixmres 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 C6-Ci6 alkyl alcohols having a Cj-Cjg chain.
• a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
• Mixmres of secondary alcohols are available under die trademark ISALCHEM 123 from Enichem.
• Mixed suds suppressors typically comprise mixmres of alcohol + silicone at a weight ratio of 1 :5 to 5:
• Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
• Suds suppressing amount is meant that die formulator of the composition can select an amount of diis suds controlling agent that will sufficiently control die 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.
• from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
• 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 ⁇ inimized and effectiveness of lower amounts for effectively controlling sudsing.
• from 0.01 % to 1 % of silicone suds suppressor is used, more preferably from 0.25% to 0.5 % .
• 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.
• Alkoxylated Polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq. , incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2 ⁇ ) m (CH2) n CH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to d e polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of 2000 to 50,000. Such alkoxylated polycarboxylates can comprise from 0.05% to 10% , by weight, of ie compositions herein.
• 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 mixmres 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 mixmres 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-l,l, 6, 7-tetramethyl naphthalene; ionone methyl; ionone gamma memyl; memyl cedrylone; methyl dihydrojasmonate; methyl l,6, 10-trimemyl-2,5,9- cyclododecatrien-1-yl ketone; 7-acetyl-l ,l ,3,4,4,6-hexamethyl tetralin: 4-acetyl-6-tert- buty 1-1 , 1 -dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta- naphthyl ketone; 6-acetyl-l , l ,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyI-l , l,2,6
• perfume materials are those that provide the largest odor improvements in finished product compositions containing cellulases.
• These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-medryl-3-(para-tert- butylpheny -propionaldehyde; 7-acetyl-l,2,3,4,5,6,7,8-octahydro-l ,l ,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-l ,l ,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; memyl beta- naphdiyl ketone; 2-med ⁇ yl-2-(para-iso-propylphenyl)-propionaldehyde; 1 ,3,4,6,7,8- hexa
• Odier 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 omer perfume chemicals include phenyl ethyl alcohol, terpineol, linalool. linalyl acetate, geraniol, nerol, 2-(l,l-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol.
• Carriers such as died ylphd alate can be used in me finished perfume compositions.
• Other Ingredients such as died ylphd alate can be used in me finished perfume compositions.
• omer ingredients useful in detergent compositions can be included in me compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
• suds boosters such as me CJO-CIO alkanolamides can be incorporated into die compositions, typically at 1 %-10% levels.
• the C10-C14 monoedianol and diedianol 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 MgCl2, MgS ⁇ 4, CaCl2 CaS ⁇ 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 die present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, dien coating said substrate widi a hydrophobic coating.
• me detersive ingredient is admixed with a surfactant before being absorbed into die porous substrate.
• the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
• a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed widi a proteolytic enzyme solution containing 3%- 5% of C13.15 ethoxylated alcohol (EO 7) nonionic surfactant.
• EO 7 ethoxylated alcohol
• d e enzyme/surfactant solution is 2.5 X die weight of silica.
• silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
• the resulting silicone oil dispersion is emulsified or odierwise 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 od er 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 die use of buffers, alkalis, acids, etc. , and are well known to those skilled in die art.
• die formulator wishes to prepare an admixable particle containing the alkoxylated cationics for use in, for example, a high density granular detergent, it is preferred diat die 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 die odor of impurity amines.
• Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide
• CocoE02 Rl .N + (CH 3 )(C 2 H4 ⁇ H)2 with Ri C 12 - C 14 Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
• 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
• Silicate Amorphous Sodium Silicate SiC>2:Na2 ⁇ ; 2.0 ratio
• MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight 70,000.
• PA30 Polyacrylic acid of average molecular weight approximately 8,000.
• 480N Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500
• NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
• Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
• Brightener 2 Disodium 4,4'-bis(4-amlino-6-morpholino-1.3.5- triazin-2-y l)amino) stilbene-2 : 2 ' -disulfonate .
• Zeolite A 10.0 24.0 4.0
• the bis-AQA- 1 (CocoMeE02) 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 clodiing.
• Zeolite A 15.0 15.0 2.5 Sodium sulfate 0.0 5.0 1.0 LAS 2.0 2.0 -
• CocoMeE02* 1.0 1.0 1.5
• the bis-AQA- 1 (CocoMeE02) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 d rough bis-AQA-22 or other bis-AQA surfactants herein.
• CocoMeE02* 1.0 1.0 1.0
• the bis-AQA- 1 (CocoMeE02) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or odier bis-AQA surfactants herein.
• Zeolite A 15.0 15.0 15.0
• CocoMeE02* 1.0 1.5 1.5 DTPMP 0.4 0.4 0.4
• the bis-AQA- 1 (CocoMeE02) surfactant of die 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 (CocoMeE02) 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.
• die granular detergent compositions provided herein may be tabletted using known tabletting mediods to provide detergent tablets.
• Sokolan CP-5 2 0.40 1.00 0-2.5 bis-AQA- 1 3 2.0 0.5 0.15-3.0
• Lipase enzyme 0.10 0-0.6
• ⁇ Balance comprises water (2% to 8% , including water of hydration), sodium sulfate, calcium carbonate, and odier minor ingredients.
• the following hand wash detergent formulations are prepared by mixing me ingredients together in die 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 diose with from 10 to 15 e oxy groups; for example AQA-10, AQA-16.
• Example further illustrates the invention herein widi respect to a shampoo.
• NaDCC Bleach 2 2 bis-AQA-1* 0.5 1.0
• the bis-AQA- 1 surfactant can be replaced by bis-AQA-2 dirough bis-AQA-22.
• EXAMPLE X The following Examples further illustrate die invention herein wi respect to a liquid-gel automatic dishwashing or odier detergent widi increased levels of stain removal benefits.
• Na2CO3/K2C03 25 25 25 15 15 15 bis-AQA-1* 0.5 0.7 0.5 0.5 0.4 0.6 0.7
• the bis-AQA- 1 (CocoMeE02) surfactant of die Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or odier bis-AQA surfactants herein.
• Various gelling agents such as CMC and clays, can be used in ie compositions to provide varying degrees of viscosity or rigidity, according to die desires of die formulator.
• EXAMPLE XI The following illustrates mixtures of bis-AQA surfactants which can be substimted for the bis-AQA surfactants listed in any of die foregoing Examples.
• such mixmres 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 mixmres differ by at least 1.5, preferably 2.5- 20, total EO units.
• Ratio ranges (wt.) for such mixmres are typically 10: 1-1 : 10.
• Non ⁇ limiting examples of such mixmres are as follows.
• mixmres of die bis-AQA surfactants herein with die corresponding cationic surfactants which contain only a single ethoxylated chain can also be used.
• compositions advantageously provide improved detergency performance (especially in a fabric laundering context) over a broader range of water hardness than do die cationic surfactants herein used individually.
• diat shorter EO cationics e.g., E02
• higher EO cationics e.g., E015
• diat 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.
• EXAMPLE X ⁇ This Example illustrates perfume formulations (A-C) made in accordance widi 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.
• perfume compositions are admixed or sprayed-onto (typically at levels up to about 2% by weight of die total detergent composition) any of die bis-AQA surfactant-containing cleaning (including bleaching) compositions disclosed herein.

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• 1997
  • 1997-05-15 ZA ZA974226A patent/ZA974226B/xx unknown
  • 1997-05-16 WO PCT/US1997/008373 patent/WO1997044433A1/en not_active Application Discontinuation
  • 1997-05-16 CA CA002255005A patent/CA2255005A1/en not_active Abandoned
  • 1997-05-16 EP EP97926568A patent/EP0907705A1/de not_active Withdrawn
  • 1997-05-16 CA CA002255003A patent/CA2255003A1/en not_active Abandoned
  • 1997-05-16 BR BR9710678A patent/BR9710678A/pt not_active Application Discontinuation
  • 1997-05-16 AR ARP970102066A patent/AR007169A1/es unknown
  • 1997-05-16 JP JP9542597A patent/JP2000504061A/ja active Pending
  • 1997-05-16 CN CN97196466A patent/CN1230213A/zh active Pending
  • 1997-05-16 CN CNB971964947A patent/CN1168812C/zh not_active Expired - Fee Related
  • 1997-05-16 JP JP9542572A patent/JPH11511795A/ja active Pending
  • 1997-05-16 WO PCT/US1997/008444 patent/WO1997043388A2/en not_active Application Discontinuation
  • 1997-05-16 JP JP9542596A patent/JPH11511799A/ja active Pending
  • 1997-05-16 EP EP97927653A patent/EP0906405A1/de not_active Withdrawn
  • 1997-05-16 BR BR9710675A patent/BR9710675A/pt not_active Application Discontinuation
  • 1997-05-16 CN CN97196468A patent/CN1225677A/zh active Pending
  • 1997-05-16 WO PCT/US1997/008316 patent/WO1997044418A1/en not_active Application Discontinuation
  • 1997-05-16 WO PCT/US1997/008314 patent/WO1997044425A2/en not_active Application Discontinuation
  • 1997-05-16 JP JP9542571A patent/JPH11511794A/ja active Pending
  • 1997-05-16 AR ARP970102077A patent/AR014606A1/es unknown
  • 1997-05-16 JP JP9541173A patent/JPH11512782A/ja active Pending
  • 1997-05-16 BR BR9709587-7A patent/BR9709587A/pt not_active Application Discontinuation
  • 1997-05-16 JP JP9541172A patent/JPH11510554A/ja active Pending
  • 1997-05-16 EP EP97924741A patent/EP0906392A2/de not_active Withdrawn
  • 1997-05-16 CN CN97196481A patent/CN1225673A/zh active Pending
  • 1997-05-16 CA CA002255006A patent/CA2255006A1/en not_active Abandoned
  • 1997-05-16 CN CN97196467A patent/CN1232489A/zh active Pending
  • 1997-05-16 WO PCT/US1997/008315 patent/WO1997044431A1/en not_active Application Discontinuation
  • 1997-05-16 EP EP97924743A patent/EP0918833A1/de not_active Withdrawn
  • 1997-05-16 WO PCT/US1997/008445 patent/WO1997043394A2/en active Application Filing
  • 1997-05-16 CA CA002254948A patent/CA2254948A1/en not_active Abandoned
  • 1997-05-16 WO PCT/US1997/008317 patent/WO1997044419A2/en not_active Application Discontinuation
  • 1997-05-16 BR BR9710676A patent/BR9710676A/pt not_active Application Discontinuation
  • 1997-05-16 CA CA002254961A patent/CA2254961A1/en not_active Abandoned
  • 1997-05-16 CA CA002254818A patent/CA2254818A1/en not_active Abandoned
  • 1997-05-16 CN CN97196475A patent/CN1225678A/zh active Pending
  • 1997-05-16 EP EP97924766A patent/EP0912686A2/de not_active Withdrawn
  • 1997-05-16 WO PCT/US1997/008372 patent/WO1997044432A1/en not_active Application Discontinuation
  • 1997-05-16 BR BR9710667A patent/BR9710667A/pt not_active Application Discontinuation
  • 1997-05-16 CA CA002254947A patent/CA2254947A1/en not_active Abandoned
  • 1997-05-16 JP JP9542574A patent/JPH11511797A/ja active Pending
  • 1997-05-16 EP EP97925602A patent/EP0912669A2/de not_active Withdrawn
  • 1997-05-16 EP EP97924742A patent/EP0906403A1/de not_active Withdrawn
  • 1997-05-16 CA CA002254820A patent/CA2254820A1/en not_active Abandoned
  • 1997-05-16 JP JP9542573A patent/JPH11511796A/ja active Pending
  • 1997-05-16 BR BR9710444A patent/BR9710444A/pt not_active Application Discontinuation
  • 1997-05-16 BR BR9709321A patent/BR9709321A/pt not_active Application Discontinuation
  • 1997-05-16 BR BR9710445A patent/BR9710445A/pt not_active Application Discontinuation
• 1998
  • 1998-11-17 MX MX9809675A patent/MX9809675A/es unknown
  • 1998-11-17 MX MX9809679A patent/MX9809679A/es unknown
  • 1998-11-17 MX MX9809681A patent/MX9809681A/es unknown
  • 1998-11-17 MX MX9809624A patent/MX9809624A/es unknown
  • 1998-11-17 MX MX9809683A patent/MX9809683A/es unknown
  • 1998-11-17 MX MX9809684A patent/MX9809684A/es unknown
  • 1998-11-17 MX MX9809674A patent/MX9809674A/es unknown
  • 1998-11-17 MX MX9809628A patent/MX9809628A/es unknown

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