EP0906392A2 - Composition detergente - Google Patents

Composition detergente

Info

Publication number
EP0906392A2
EP0906392A2 EP97924741A EP97924741A EP0906392A2 EP 0906392 A2 EP0906392 A2 EP 0906392A2 EP 97924741 A EP97924741 A EP 97924741A EP 97924741 A EP97924741 A EP 97924741A EP 0906392 A2 EP0906392 A2 EP 0906392A2
Authority
EP
European Patent Office
Prior art keywords
bis
aqa
die
surfactant
compositions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97924741A
Other languages
German (de)
English (en)
Inventor
Kaori Asano
Jeffrey John Scheibel
Kaori Minamikawa
Laura Cron
Peter Robert Foley
Thomas Anthony Cripe
John Downing Curry
Kenneth William Willman
Ian Martin Dodd
Christiaan Arthur Jacques Kamiel Thoen
Michael Alan John Moss
Rinko Katsuda
Frank Andrej Kvietok
Mark Hsiang-Kuen Mao
Susumu Murata
Khizar Mohamed Khan Sarnaik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0906392A2 publication Critical patent/EP0906392A2/fr
Withdrawn legal-status Critical Current

Links

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

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising an aluminosilicate builder, 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 specialty 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.
  • Low levels of hydrophobic soils and residual stains often remain on the surface of the fabric after washing.
  • Detergent builders are employed in the compositions described herein to assist in controlling mineral hardness, especially Ca ⁇ + and/or Mg2+ ions, in wash water or to assist in the removal of particulate soils from surfaces.
  • Builders can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned.
  • These builder materials are typically inorganic and insoluble/partially soluble.
  • a particular problem associated with the use of insoluble/partially soluble, inorganic builders is the formation of insoluble complexes with hardness ions that may deposit on the surface of the washed substrate for example fabric, leaving a layer of encrusted material trapped on or within the surface of the washed substrate i.e. the fabric.
  • bis-alkoxylated quaternary ammonium (bis-AQA) compounds can be used in various detergent compositions to boost detergency performance on a variety of soil and stain types, particularly the hydrophobic soil types, commonly encountered.
  • the bis-AQA surfactants of the present invention provide substantial benefits to the formulator, over cationic surfactants previously known in the art.
  • the bis-AQA surfactants used herein provide marked improvement in cleaning of "everyday" greasy /oily hydrophobic soils regularly encountered.
  • the bis-AQA surfactants are compatible with anionic surfactants commonly used in detergent compositions such as alkyl sulfate and alkyl benzene sulfonate; incompatibility with anionic components of the detergent composition has commonly been the limiting factor in the use of cationic surfactants previously known.
  • 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 bis-AQA surfactants and aluminosilicate builder deliver superior cleaning and whiteness performance versus products containing either technology alone.
  • high levels of inorganic, insoluble or partially soluble builders can be employed in the compositions of the present invention without increasing the level of residual encrusted material remaining on the washed substrate. It is believed that insoluble inorganic builders such as aluminosilicate builders are composed of discreet units, some faces of which will be negatively charged.
  • Bis-AQA which has a positively charged headgroup, may interact with these faces to lift off the residual inorganic particles of builder/soil/stain from fabrics by formation of hydrophilic, charged surfactant bilayers around the inorganic particles resulting in the effective solubization of the inorganic particles in the wash water.
  • the present invention thus provides a detergent composition which delivers effective cleaning of everyday, especially hydrophobic soils by way of a detergent composition comprising aluminosilicate builder and a bis-AQA surfactant.
  • Rl is a linear, branched, substituted Cg-Ci g alkyl, alkenyl, aryl, alkaryl, e ⁇ her or glycityl 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.
  • the first essential component of die composition of die present invention is an aluminosilicate builder.
  • Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels.
  • Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na z [(AlO2) z (SiO2)y]. XH2O wherein z and y are integers of at least 6; the molar ratio of z to y is in the range of from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material can be crystalline or amporphous but are preferably crystalline and inhydrate, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P (or Zeolite MAP), Zeolite X, Zeolite HS and mixtures thereof.
  • Zeolite A has the formula
  • x is from 20 to 30, especially 27.
  • Zeolite X a preferred aluminosilicate has me formula Nag ⁇ [(AK>2)86(SiO2)l06]- 276 H2O.
  • Zeolite MAP as disclosed in EP-B-384,070 is also a preferred aluminosilicate builder herein.
  • die aluminosilicate has a particle size of 0.1 to 10 microns in diameter.
  • the aluminosilicate builder is typically present at a level of from 1 % to 80% by weight, preferably from 10% to 80% by weight, most preferably from 15% to 50%or even 60% weight of the composition.
  • R* is a linear, branched or substituted alkyl, alkenyl, aryl, alkaryl, edier, glycityl ether moiety containing from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably from 8 tol4 carbon atoms;
  • R is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl;
  • R ⁇ and R 4 can vary independently and are selected from die group consisting of hydrogen (preferred), memyl 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 1 to 15, more preferably 1 to 8, even more preferably 1 to 4. Most preferably bom p and q are 1.
  • Bis-AQA compounds wherein me hydrocarbyl substituent R 1 is Cg-Cj2, especially Cg- C ⁇ o > enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials. Accordingly, me Cg-C j 2 bis- AQA surfactants may be preferred by some formulators.
  • 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, eimer 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.
  • me 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 otiier 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 die wash water temperature, me volume of wash water and the type of washing machine. For example, in a top-loading, vertical axis U.S.
  • 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.
  • tiiis On me basis of usage rates of from 40 g to 210 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g/1) tiiis translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.5 % to 3.5 %, preferably from 0.7 % to 1.5 % .
  • tiiis On me basis of usage rates of from 140 g to 400 g per load for spray-dried granules (i.e. , "fluffy" ; density below 650 g/1), tiiis translates into an in-product concentration (wt.) of die bis- AQA surfactant of from 0.13% to 1.8%, preferably from 0.18% to 0.76%.
  • 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.
  • 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 me 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 die other surfactants (generally anionics or anionic/nonionic mixtures) in me finished compositions. This is to be distinguished from other compositions of the art wherein various cationic surfactants are used with anionic surfactants at or near stoichiometric levels.
  • me weight ratio of bis-AQA: anionic surfactant in laundry compositions is in me 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 me bis-AQA surfactants in such compositions.
  • the weight ratio of me bis-AQA surfactant to omer surfactants present in such compositions is low, i.e., sub-stoichiometric in die 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.
  • compositions which are conventionally designed for use in top loading automatic washing machines, especially of me 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.
  • 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.
  • 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.
  • 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.
  • anionic: nonionic ratios in the range of about 10:1 to 1:10, preferably about 5: 1 to about 1:1.
  • emoxylated cationic surfactants herein are available under the trade name ETHOQUAD from Akzo Nobel Chemicals Company.
  • ETHOQUAD emoxylated cationic surfactants
  • such materials can be synthesized using a variety of different reaction schemes (wherein "EO” represents -CH2CH2O- units), as follows.
  • Step 1 of the reaction is preferably conducted in an aqueous medium.
  • Reaction temperatures are typically in die 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-Cj4 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 mat gels may form. While die desired product can be recovered from me 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 (edioxylation) is preferably conducted using ethylene oxide and an acid such as HC1 which provides me quaternary surfactant.
  • chlorohydrin i.e., chloroemanol
  • the first step is preferably conducted in an aqueous medium.
  • Reaction temperatures are typically in me range of 100-230°C.
  • Reaction pressures are 50-1000 psig.
  • a base preferably sodium hydroxide, can be used to react with the HSO4-generated during me reaction, or an excess of the amine can be employed to also react wim 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.
  • die 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 bis-substituted amines prepared in me foregoing Syntheses can be further ethoxylated in standard fashion. Quaternization wim 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 me bis-AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically yield mixtures of materials with differing degrees of etiioxylation. Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "EO2.5”, "EO3.5".
  • R* is Cg-Cig hydrocarbyl and mixtures tiiereof, preferably Cg, Cio, C12, C14 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • R* is derived from coconut (C12-C14 alkyl) fraction fatty acids, R 2 is methyl and ApR 3 and A'qR 4 are each monoetir ⁇ xy, mis preferred type of compound is referred to herein as "CocoMeEO2" or "bis-AQA- 1" in me above list.
  • bis-AQA surfactants useful herein include compounds of me formula:
  • R 1 is Cg-Cjg hydrocarbyl, preferably Cg-Ci4 alkyl, independently p is 1 to 3 and q is 1 to 3, R 2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • die compositions of the present invention preferably further comprise a non-AQA surfactant.
  • Non-AQA surfactants may include essentially any anionic, nonionic or additional cationic surfactant.
  • Nonlimiting examples of anionic surfactants useful herein typically at levels from 1 % to 55%, by weight, include me conventional Cj i-Ci g alkyl benzene sulfonates ("LAS") and primary ("AS"), branched-chain and random C10-C20 alkyl sulfates, the Cjo-Cig secondary (2,3) alkyl sulfates of me formula CH3(CH2) x (CHOSO3 ⁇ M "f ) CH3 and CH3 (CH2)y(CHOSO3 _ M + ) CH2CH3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, me Cj2-C ⁇ g alpha-sulfonated fatty acid esters, me Cirj-Cig sulfated polyglycosides, die Cjo-Ci g alkyl al
  • C12-C18 betaines and sulfobetaines can also be included in me overall compositions.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, die branched-chain CJQ-CIO soaps may be used.
  • Other conventional useful surfactants are listed in standard texts.
  • Nonionic Surfactants typically at levels from 1 % to 55% , by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), Cj ⁇ -Cig glycerol emers.
  • AE alkoxylated alcohol
  • PFAA's polyhydroxy fatty acid amides
  • APG's alkyl polyglycosides
  • Cj ⁇ -Cig glycerol emers Cj ⁇ -Cig glycerol emers.
  • condensation products of primary and secondary aliphatic alcohols with from 1 to 25 moles of emylene oxide (AE) are suitable for use as me 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 (die condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (die condensation product of C12-C14 primary alcohol wim 6 moles ethylene oxide wim a narrow molecular weight distribution), bom marketed by Union Carbide Corporation; NeodolTM 45.9 ( me condensation product of C14-C15 linear alcohol wim 9 moles of ethylene oxide), NeodolTM 23-3 (die condensation product of C12-C13 linear alcohol wim 3 moles of ethylene oxide), NeodolTM 45.7 ( me condensation product of C14-C 1 5 linear alcohol wim 7 moles of ethylene oxide) and NeodolTM 45.5 ( me condensation product of C14-C 1 5 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; KyroTM £OB (me condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Proc
  • Another class of preferred nonionic surfactants for use herein are die polyhydroxy fatty acid amide surfactants of me formula.
  • R* is H, or C ⁇ _4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture mereof
  • R 2 is C5.31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R* is methyl
  • R 2 is a straight C ⁇ ⁇ _ ⁇ ⁇ alkyl or Cj5_i7 alkyl or alkenyl chain such as coconut alkyl or mixtures tfiereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive animation reaction.
  • Typical examples include die C ⁇ -Cjg and C12-C14 N-mefhylglucamides. 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 diose 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 me glucosyl moieties (optionally me hydrophobic group is attached at me 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 die one position of die additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on me preceding saccharide units.
  • the preferred alkylpolyglycosides have the formula:
  • R 2 is selected from die group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
  • the glycosyl is preferably derived from glucose.
  • me alcohol or alkylpolyethoxy alcohol is formed first and men reacted wim glucose, or a source of glucose, to form the glucoside (attachment at die 1 -position).
  • the additional glycosyl units can tiien be attached between their 1 -position and die preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately die 2-position.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of die surfactant systems of die present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include me condensation products of alkyl phenols having an alkyl group containing from 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in eitiier a straight-chain or branched-chain configuration with die alkylene oxide.
  • me ethylene oxide is present in an amount equal to from 2 to 25 moles, more preferably from 3 tol5 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by die GAF Corporation; and TritonTM X ⁇ 5, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxy lates (e.g., alkyl phenol ethoxylates).
  • the condensation products of emylene oxide wim a hydrophobic base formed by die condensation of propylene oxide witii propylene glycol are also suitable for use as me 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 polyoxyetiiylene moieties to this hydrophobic portion tends to increase die water solubility of die molecule as a whole, and die liquid character of die product is retained up to die point where me polyoxyethylene content is 50% of die total weight of die condensation product, which corresponds to condensation witii up to 40 moles of ethylene oxide.
  • Examples of compounds of diis type include certain of die commercially-available PluronicTM surfactants, marketed by BASF.
  • die condensation products of etiiylene oxide wim die product resulting from die reaction of propylene oxide and etiiylenediamine are die condensation products of etiiylene oxide wim die product resulting from die reaction of propylene oxide and etiiylenediamine.
  • the hydrophobic moiety of tiiese products consists of me reaction product of etiiylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to die extent tiiat 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 die 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 die 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, hydroxyediyl or hydroxypropyl groups.
  • Otiier suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • compositions described herein may comprise an additional builder.
  • An additional builder may be present at a level of at least 1 % .
  • Liquid formulations typically comprise 5% to 50%, more typically 5% to 35% of builder, a proportion of which may be comprised by additonal builder.
  • Granular formulations typically comprise from 10% to 80%, more typically 15% to 50% builder by weight of die detergent composition, a proportion of which may be comprised by additonal builder. Lower or higher levels of builders are not excluded.
  • Mixed builder systems comprising two or more builders are envisaged herein.
  • Mixed builder systems are optionally complemented by chelants, pH-buffers or fillers, though tiiese 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 me range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1.0.
  • Suitable additional 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 tiiree-dimensional- structure as well as amorphous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals otiier than sodium carbonate or sesquicarbonate; 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 tiiree-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 die engineering of stable surfactant and/or builder-containing detergent compositions.
  • 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 die 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 die 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.
  • Otiier layered silicates such as those having the general formula NaMSi x ⁇ 2 ⁇ + ⁇ VH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein.
  • Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the ⁇ , ⁇ and ⁇ layer-silicate forms.
  • Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.
  • crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM2 ⁇ ySi ⁇ 2.zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711 , 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, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and otiier carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3-CaCO3 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.
  • Suitable organic detergent builders include polycarboxylate compounds, including water- soluble nonsurfactant dicarboxylates and tricarboxylates.
  • Mort 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.
  • Otiier suitable builders are die etiier hydroxypolycarboxylates, copolymers of maleic anhydride wim etiiylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid; carboxymethyloxysuccimc acid; the various alkali metal, ammomum and substituted ammonium salts of polyacetic acids such as etiiylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, poly maleic 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- 1 -hydroxy- 1,1-diphosphonate and other known phosphonates, e.g., those of U.S.
  • 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable antiscaling properties.
  • 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 die related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986.
  • Succinic acid builders include die C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • 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 ⁇ -Cjg monocarboxylic acids, can also be incorporated into die 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 tiian carbonate may be added provided that the overall charge is balanced or neutral.
  • a water-soluble cation selected from me group consisting of hydrogen, water- soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred.
  • noncarbonate anions include tiiose selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures tiiereof.
  • Preferred builders of this type in their simplest forms are selected from die group consisting of Na2Ca(CO3)2, K2Ca(CO 3 )2, Na2Ca2(CO3)3, NaKCa(CO 3 )2, NaKCa2(CO3)3, K2Ca2(CO3)3, and combinations thereof.
  • An especially preferred material for the builder described herein is Na2Ca(CO3)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, Butschliite, Cancrinite, Carbocemaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregory ite, Jouravskite, KamphaugiteY, Kettnerite, Khanneshite, LepersonniteGd, Liottite, MckelveyiteY, Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite, and Zemkorite.
  • Preferred mineral forms include Nyererite,
  • the detergent compositions herein may optionally comprise a bleaching agent.
  • bleaching agents will typically be at levels of from 1 % to 30%, more typically from 5% to 20%, of tiie detergent composition, especially for fabric laundering.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or otiier cleaning purposes that are now known or become known. These include oxygen bleaches as well as otiier bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • Anotiier category of bleaching agent that can be used widiout restriction encompasses percarboxylic acid bleaching agents and salts tiiereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, die magnesium salt of meta- chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781 , Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in die range from 500 micrometers to 1,000 micrometers, not more tiian 10% by weight of said particles being smaller than 200 micrometers and not more man 10% by weight of said particles being larger than 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as die sulfonated zinc and/or aluminum phthalo- cyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • Mixtures of bleaching agents can also be used.
  • Bleach activators are preferred components of a composition where an oxygen bleach is present. If present, the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • peroxygen bleaching agents and bleach activators results in tiie in situ production in aqueous solution (i.e. , during the washing process) of the peroxy acid corresponding to die bleach activator.
  • 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 etiiylene diamine
  • amido-derived bleach activators are tiiose 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 the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of die above formulae include (6-octanamido- caproyOoxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido- caproyl)oxybenzenesulfonate, and mixtures tiiereof as described in U.S. Patent 4,634,551, inco ⁇ orated 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 die benzoxazin-type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • R ⁇ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms.
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimeti ⁇ ylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5- trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, inco ⁇ orated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam,
  • Bleach catalysts are optional components of die 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-O)3(l,4,7- trimethyl-1 ,4,7-triazacyclononane)2(PF6)2, Mn ⁇ 2( u_ 0) ⁇ (u-OAc)2(l ,4,7-trimethyl-l ,4,7- triazacyclononane)2-(ClO4)2, MnHI" Mn rV 4(u-O) ⁇ (u-OAc)2-(l,4,7-trimethyl-l ,4,7-triazacyclononane)2(Cl ⁇ 4)3, Mn IV (l ,4,7- trimethyl-l, 4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof.
  • 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 wim 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.
  • die compositions and processes herein can be adjusted to provide on die 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.
  • cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] T y , wherein "OAc” represents an acetate moiety and “Ty” is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH3)5OAc](OAc)2;
  • the automatic dishwashing compositions and cleaning processes herein can be adjusted to pr vide on die order of at least one part per hundred million of the active bleach catalyst sp . ⁇ es 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 die bleach catalyst species in the wash liquor.
  • typical automatic dishwashing compositions herein will comprise from 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.
  • Enzymes can be included in the present detergent compositions for a variety of pu ⁇ oses, 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, Upases, cellulases, peroxidases, and mixtures tiiereof 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 pu ⁇ oses 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 the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
  • One suitable protease is obtained from a strain of
  • ESPERASE ® 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".
  • Otiier suitable proteases include ALCALASE ® and SAVINASE ® from Novo and MAXATASE ® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. 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.
  • Other preferred proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased adso ⁇ tion 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 witii one or more amino acid residue positions equivalent to tiiose selected from the group consisting of +99, + 101, + 103, + 104, +107, + 123, +27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in die patent applications of A.
  • Amylases suitable herein, especially for, but not limited to automatic dishwashing pu ⁇ oses 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 die 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 the 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., at a pH from 8 to 11, measured versus die above-identified reference-point amylase.
  • Stability can be measured using any of die 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 die Bacillus amylases, especially die Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability -enhanced amylases vs. die above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such preferred amylases include (a) an amylase according to die hereinbefore inco ⁇ orated 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. amyloliquefaciens, B. subtilis, or B.
  • (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T witii 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 die immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo.
  • Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • amylase enzymes include those described in WO 95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056.
  • Specific amylase enzymes for use in die detergent compositions of die present invention include ⁇ -amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in tiie range of 8 to 10, measured by die Phadebas® ⁇ -amylase activity assay.
  • ⁇ -amylases which are at least 80% homologous witii the amino acid sequences shown in tiie SEQ ID listings in the references. These enzymes are preferably inco ⁇ orated 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 die genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS- 2.247.832.
  • CAREZYME® and CELLUZYME* are especially useful. See also WO 9117243 to Novo.
  • Suitable lipase enzymes for detergent usage include tiiose produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” or "Amano-P.” Otiier suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., 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 tiie benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions containing die bis-AQA surfactants in the manner disclosed herein, especially when the D96L is used at levels in die range of 50 LU to 8500 LU per liter of wash solution.
  • Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during die wash to otiier substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
  • a range of enzyme materials and means for tiieir inco ⁇ oration 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 tiieir inco ⁇ oration 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.
  • 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 otiier formulation actives, or be added separately, e.g., by die formulator or by a manufacturer of detergent-ready enzymes.
  • Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
  • One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to die enzymes.
  • Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from 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 die multiplicity, type and levels of enzymes inco ⁇ orated.
  • 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 die grease-cutting action of certain types of surfactant.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3 % by weight of boric acid or otiier borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
  • Stabilizing systems of certain cleaning compositions may further comprise from 0 to 10%, preferably from 0.01 % to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating die enzymes, especially under alkaline conditions.
  • chlorine bleach scavengers While chlorine levels in water may be small, typically in die 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. Since percarbonate has the ability to react with chlorine bleach the use of additional stabilizers against chlorine, may, most generally, not be essential, though improved results may be obtainable from their use.
  • Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammomum cations witii sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (ME A), and mixtures tiiereof can likewise be used.
  • EDTA ethylenediaminetetracetic acid
  • ME A monoethanolamine
  • mixtures tiiereof can likewise be used.
  • special enzyme inhibition systems can be incorporated such that different enzymes have maximum compatibility.
  • 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 mixtures thereof can be used if desired.
  • ammonium salts can be simply admixed with die detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in US 4,652,392, Baginski et al.
  • SRA polymeric soil release agents
  • SRA's can optionally be employed in die 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 wweeiigehhtt., ooff ti thiee ccoommppoossiittiioonn.
  • Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with SRA to be more easily cleaned in later washing procedures.
  • SRA's can include a variety of charged, e.g., anionic or even cationic (see U.S.
  • 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 titaniu ⁇ wTV) alkoxide.
  • esters may be made using additional monomers capable of being inco ⁇ orated into die 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 terephtiialoyl 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) ethoxy lating allyl alcohol, (b) reacting the product of (a) witii dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification/ oligomerization procedure and (c) reacting the product of (b) witii sodium metabisulfite in water; the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • Gosselink et al for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from etiiylene 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 terephthalate esters of U.S.
  • Gosselink et al 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400.
  • SRA's also include simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, 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 the hydroxyether cellulosic polymers available as METHOCEL from Dow; and die 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 ⁇ -Cg 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. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany.
  • SRA's are polyesters with repeat units containing 10-15% by weight of ethylene terephthalate togetiier with 90-80% by weight of polyoxyethylene terephthalate, derived from a polyoxyetiiylene glycol of average molecular weight 300-5,000.
  • Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.
  • Anotiier preferred SRA is an oligomer having empirical formula (CAP)2(EG/PG)5(T)5(SIP) ⁇ which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-l,2-propylene (EG/PG) units and which is preferably terminated wim end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyetfiyleneoxy 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.
  • CAP wim end-caps
  • Said SRA preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabiliser, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene- sulfonates or mixtures tiiereof, 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-hydroxyeti ⁇ oxy)-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 tiiereof; (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 ethoxy lated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures tiiereof.
  • a backbone comprising (a) at least
  • SEG and CAP monomers for the above esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate (“SEG”), Na-2- ⁇ 2-(2-hydroxyethoxy) ethoxy ⁇ etiianesulfonate (“SE3”) and its homologs and mixtures tiiereof and the products of ethoxy lating and sulfonating ally! alcohol.
  • Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2- hydroxyethoxy)ethoxy ⁇ ethanesulfonate and/or sodium 2-[2- ⁇ 2-(2-hydroxyethoxy)- ethoxy ⁇ ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(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+ -0 3 S[CH2CH2 ⁇ ]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 terephthalates using diisocyanate coupling agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al; (IT) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. Witii a proper selection of catalyst, the trimellitic anhydride forms linkages to die terminals of the polymer through an ester of tiie isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.; (Ill) anionic terephtiialate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including botii nonionic and cationic polymers, see U.S.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble etiioxylates amines; liquid detergent compositions typically contain 0.01 % to 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene- pentamine.
  • Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal- antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Otiier clay soil removal/antiredeposition agents which can be used include die ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and die amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
  • Other clay soil removal and/or anti redeposition agents known in die art can also be utilized in tiie compositions herein. See U.S. Patent 4,89
  • CMC carboxy metiiyl cellulose
  • Polymeric dispersing agents can advantageously be utilized at levels from 0.1 % to 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyetiiylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in tiieir 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 etiier, 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 die water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in die 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, die alkali metal, ammomum and substituted ammomum salts.
  • Soluble polymers of tiiis type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of die dispersing/anti-redeposition agent.
  • Such materials include die 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 ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still otiier useful dispersing agents include the maleic/acrylic/vinyl alcohol te ⁇ olymers.
  • Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 te ⁇ olymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.
  • optical brighteners or otiier brightening or whitening agents known in the art can be inco ⁇ orated at levels typically from 0.01 % to 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in die present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • 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. Otiier brighteners disclosed in this 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.
  • tiiese brighteners include 4-meti ⁇ yl-7-diethyl- amino coumarin; l,2-bis(benzimidazol-2-yl)ethylene; 1,3- diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)ti ⁇ iophene; 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 die present invention may also include one or more materials effective for inhibiting die transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures 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 tiiereof.
  • the N-0 group can be represented by the following general structures:
  • Ri , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations tiiereof; x, y and z are 0 or 1; and die nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of tiie polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as die amine oxide polymer formed is water- soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures tiiereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and die otiier monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to die amine N-oxide of 10: 1 to 1 : 1 ,000,000.
  • the number of amine oxide groups present in die 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.
  • tiie average molecular weight is witiiin the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
  • This preferred class of materials can be referred to as "PVNO".
  • the most preferred polyamine N-oxide useful in die detergent compositions herein is poIy(4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.
  • PVPVI N-vinylpyrrolidone and N-vinylimidazole polymers
  • tiie 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 fro:;. ).8:1 to 0.3: 1 , most preferably from 0.6: 1 to 0.4: 1. These copolymers can be eithe: inear 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, inco ⁇ orated herein by reference.
  • Compositions containing PVP can also contain polyetiiylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000.
  • PEG polyetiiylene 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, die compositions herein will preferably comprise from 0.01 % to 1 % by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in die present invention are those having the structural formula:
  • Rj is selected from anilino, N-2-bis-hydroxyeti ⁇ yl and NH-2-hydroxyeti ⁇ yl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-meti ⁇ ylamino, mo ⁇ hilino, 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
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2- yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy
  • Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in die detergent compositions herein.
  • die brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N- methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM- GX by Ciba-Geigy Co ⁇ oration.
  • R ⁇ is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • die brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) witii such selected optical brighteners e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX
  • Tinopal UNPA-GX Tinopal 5BM-GX
  • Tinopal AMS-GX Tinopal AMS-GX
  • exhaustion coefficient is in general as die ratio of a) die brightener material deposited on fabric to b) die initial brightener concentration in tiie wash liquor. Brighteners witii relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aro- matic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by tiieory, it is believed that the benefit of these materials is due in part to tiieir 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-hydroxyethylediy lenediaminetriacetates , nitrilotriacetates , etiiylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and etiianoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ediylenediaminetetrakis (methylenephosphonates) as DEQUEST.
  • ediylenediaminetetrakis methylenephosphonates
  • tiiese amino phosphonates to not contain alkyl or alkenyl groups witii more than 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in tiie compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of tiiis type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy- 3,5-disulfobenzene.
  • EDDS etiiylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates.
  • MGDA water-soluble methyl glycine diacetic acid
  • tiiese 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 Compounds for reducing or suppressing the formation of suds can be inco ⁇ orated into die compositions of die present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • suds suppressors are well known to those skilled in die art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts tiiereof 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 ⁇ g-C40 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 witii two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in die range of -40 °C and 50°C, and a minimum boiling point not less thanllO°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.
  • paraffin as used in tiiis suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto die 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.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about
  • the solvent for a continuous phase is made up of certain polyetiiylene glycols or polyethylene-polypropylene glycol copolymers or mixtures tiiereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosi
  • 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 tiian about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyediylene/polypropylene copolymers herein have a solubility in water at room temperature of more tiian about 2 weight % , preferably more than about 5 weight % .
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less tiian about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
  • Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol: copolymer of polyethylene- polypropylene glycol.
  • the prefe ⁇ ed 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.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as tiie silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the C6-C16 alkyl alcohols having a C ⁇ -Cj6 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5: 1.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of tiiis suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry or dishwashing detergents for use in automatic laundry or dishwashing machines.
  • compositions herein will generally comprise from 0% to 10% of suds suppressor.
  • monocarboxylic fatty acids, and salts dierein When utilized as suds suppressors, monocarboxylic fatty acids, and salts dierein, will be present typically in amounts up to 5% , by weight, of the detergent composition. Preferably, 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 witii keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01 % to 1 % of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
  • tiiese weight percentage values include any silica tiiat may be utilized in combination witii polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1 % to 2%, by weight, of die 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 die finished compositions.
  • Alkoxylated polycarboxylates such as tiiose 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., inco ⁇ orated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 aery late 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 die 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 die compositions herein.
  • tiirough-tiie-wash fabric softeners especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as otiier softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently witii fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981
  • 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 and esters. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from 0.01 % to 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from 0.0001 % to 90% of a finished perfume composition.
  • the detergent compositions described herein may contain perfume ingredients.
  • perfume ingredients useful herein include: 7-acetyl-l, 2,3,4,5,6,7,8- octahydro-l,l,6,7-tetramethyl naphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl l,6,10-trimethyl-2,5,9-cyclododecatrien-l-yl ketone; 7-acetyl-l, 1, 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- 1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-l,l
  • perfume materials are tiiose that provide die largest odor improvements in finished product compositions containing cellulases.
  • These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-meti ⁇ yl-3-(para-tert- butylphenyl)-propionaldehyde; 7-acetyl-l ,2,3,4,5 ,6,7,8-octahydro-l , 1 ,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-l, 1,3 ,4 ,4, 6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-naptiiol methyl ether; methyl beta- naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,
  • perfume materials include essential oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
  • Still other perfume chemicals include phenyl etiiyl alcohol, te ⁇ ineol, linalool, linalyl acetate, geraniol, nerol, 2-(l,l-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol.
  • Carriers such as diethylphthalate can be used in the finished perfume compositions.
  • a wide variety of otiier ingredients useful in detergent compositions can be included in die 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 the C ⁇ o-Cj6 alkanolamides can be inco ⁇ orated into die compositions, typically at 1%-10% levels.
  • the C10-C 1 4 monoethanol and dietiianol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters witii high sudsing adjunct surfactants such as die amine oxides, betaines and sultaines noted above is also advantageous.
  • water-soluble magnesium and/or calcium salts such as MgCl2, MgSO4, CaCl2 CaSO4, can be added at levels of, typically, 0.1 % -2%, to provide additional suds and to enhance grease removal performance.
  • Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • die detersive ingredient is admixed witii a surfactant before being absorbed into die porous substrate.
  • die detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%- 5% of Ci 3_i5 etiioxylated alcohol (EO 7) nonionic surfactant.
  • EO 7 Ci 3_i5 etiioxylated alcohol
  • tiie enzyme/surfactant solution is 2.5 X tiie weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil dispersion is emulsified or otherwise added to die final detergent matrix.
  • ingredients such as die 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 otiier 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 tiiose 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, die 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 the art.
  • the formulator wishes to prepare an admixable particle containing die alkoxylated cationics for use in, for example, a high density granular detergent, it is preferred tiiat the particle composition not be highly alkaline. Processes for preparing high density (above 650 g/1) 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.
  • PEG4000 Polyetiiylene glycol; average molecular weight 4000
  • SRA-1 Soil release agent methyl cellulose; molecular weight about 13000, degree of substitution 1.8-1.9
  • Granular detergents are as follows in Examples A and B.
  • the AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants AQA-2 through AQA-22 or other AQA surfactants herein.
  • the bis-AQA- 1 (CocoMeE02) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or otiier bis-AQA surfactants herein.
  • the sample preparation basically involves following steps :
  • Step I The individual surfactants are weighed and mixed in die following sequence :
  • Silicate 148.32 gms per 900 ml of Distilled water; 50 mis of this solution are used per wash.
  • Copolymer 92.88 gms per 900 ml of Distilled water; 50 mis of this solution are used per wash.
  • Granules Each granule component is weighed separately in die same beaker.
  • Hardness No extra hardness are added on top of tap water hardness.
  • Load 2.4 kg of load of following composition are typically used,
  • DKPE T shirt (1) P/C Short pants (2) Cotton short pants (1)
  • DKPE is double-knit polyester.
  • DMO is dirty motor oil.
  • Test Results I show die performance of compositions according to the present invention using CoCoMeE02 plus a mixture of LAS/ AS and Test Results II show the performance using CoCoMeEOlO* plus LAS/ AS, as compared with CoCoMeE02/LAS.
  • performance is measured against various soil types, i.e., body soil, builder sensitive soil, bleach sensitive soil, surfactant sensitive soil and socks.
  • soil types i.e., body soil, builder sensitive soil, bleach sensitive soil, surfactant sensitive soil and socks.
  • EOlO indicates two poly-EO chains with an overall average of 10 EO units in tiie molecule, typically (but not restricted to) about 5 per chain.
  • Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3 A C 12- 15 branched primary alcohol condensed witii an average of 3 moles of ethylene oxide
  • CocoE02 R 1 .N+(CH3)(C 2 H 4 OH)2 with Ri C 12 - C14 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
  • MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight 70,000.
  • Brightener 1 Disodium 4,4 * -bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino-1.3.5- triazin-2-y l)amino) stilbene-2 : 2 ' -disulfonate .
  • SRA 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephthaloyl backbone
  • SRA 2 Diethoxylated poly (1, 2 propylene terephtiialate) short block polymer
  • Silicone antifoam Polydimethylsiloxane foam controller wim siloxane-oxyalkylene copolymer as dispersing agent witii a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
  • Zeolite A 10.0 24.0 4.0
  • 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.
  • nil bleach-containing detergent formulations are of particular use in washing colored clothing.
  • CocoMeEO2* 1.0 1.0 1.5
  • the bis-AQA-1 (CocoMeEO2) surfactant of the Example may be re equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or ⁇ surfactants herein.
  • CocoMeEO2* 1.0 1.0 1.0
  • the bis-AQA-1 (CocoMeEO2) 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.
  • Zeolite A 15.0 15.0 15.0
  • the bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 tiirough bis-AQA-22 or other bis-AQA surfactants herein.
  • tiie granular detergent compositions provided herein may be tabletted using known tabletting methods to provide detergent tablets.
  • compositions can contain various particulate detersive ingredients (e.g., bleaching agents, as disclosed hereinabove) stably suspended therein.
  • non-aqueous compositions tiius comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • the AQA surfactants are incorporated in the compositions at the levels and in the manner described hereinabove for the manufacture of otiier laundry detergent compositions.
  • the liquid phase will generally comprise from 35% to 99% by weight of the detergent compositions herein. More preferably, the liquid phase will comprise from 50% to 95% by weight of the compositions. Most preferably, the liquid phase will comprise from 45% to 75% by weight of the compositions herein.
  • the liquid phase of die detergent compositions herein essentially contains relatively high concentrations of a certain type anionic surfactant combined witii a certain type of nonaqueous, liquid diluent.
  • the anionic surfactant essentially utilized as an essential component of the nonaqueous liquid phase is one selected from die alkali metal salts of alkylbenzene sulfonic acids in which the alkyl group contains from 10 to 16 carbon atoms, in straight chain or branched chain configuration. (See U.S. Patents 2,220,099 and 2,477,383, inco ⁇ orated herein by reference.) Especially preferred are die sodium and potassium linear straight chain alkylbenzene sulfonates (LAS) in which the average number of carbon atoms in the alkyl group is from 11 to 14. Sodium C11-C14 LAS is especially preferred.
  • LAS die sodium and potassium linear straight chain alkylbenzene sulfonates
  • the alkylbenzene sulfonate anionic surfactant will be dissolved in the nonaqueous liquid diluent which makes up the second essential component of the nonaqueous phase.
  • die alkylbenzene sulfonate anionic surfactant is generally present to the extent of from 30% to 65% by weight of the liquid phase. More preferably, the alkylbenzene sulfonate anionic surfactant will comprise from 35% to 50% by weight of the nonaqueous liquid phase of die compositions herein. Utilization of this anionic surfactant in tiiese concentrations corresponds to an anionic surfactant concentration in die total composition of from 15% to 60% by weight, more preferably from 20% to 40% by weight, of the composition.
  • the hereinbefore described alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent which contains two essential components. These two components are a liquid alcohol alkoxy late material and a nonaqueous, low-polarity organic solvent. i) Alcohol Alkoxylates
  • die liquid diluent used to form tiie compositions herein comprises an alkoxylated fatty alcohol material. Such materials are themselves also nonionic surfactants. Such materials correspond to die general formula:
  • R 1 (CmH 2 mO) n OH wherein R* is a Cg - Ci6 alkyl group, m is from 2 to 4, and n ranges from 2 to 12.
  • Rl is an alkyl group, which may be primary or secondary, that contains from 9 to 15 carbon atoms, more preferably from 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be edioxylated materials that contain from 2 to 12 ethylene oxide moieties per molecule, more preferably from 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol component of die liquid diluent will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17. More preferably, the HLB of this material will range from 6 to 15, most preferably from 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • fatty alcohol alkoxylates useful as one of the essential components of the nonaqueous liquid diluent in tiie compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain 7 moles of emylene oxide. Such materials have been commercially marketed under die trade names Neodol 25-7 and Neodol
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12 - C13 alcohol having 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9 - Cn primary alcohol having 10 moles of ethylene oxide. Alcohol ethoxy lates of this type have also been marketed by Shell
  • Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol witii an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol etiioxylates that have been commercially marketed by Union Carbide Co ⁇ oration.
  • the former is a mixed ethoxylation product of Cn to C15 linear secondary alkanol with 7 moles of ethylene oxide and die latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Alcohol etiioxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and die number of ethylene oxide groups per mole being 11. Such products have also been commercially marketed by Shell Chemical Company.
  • the alcohol alkoxylate component which is essentially utilized as part of die liquid diluent in the nonaqueous compositions herein will generally be present to tiie extent of from 1 % to 60% of the liquid phase composition. More preferably, me alcohol alkoxylate component will comprise 5% to 40% of the liquid phase.
  • the essentially utilized alcohol alkoxylate component will comprise from 5% to 30% of the detergent composition liquid phase.
  • Utilization of alcohol alkoxylate in tiiese concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of froml% to 60% by weight, more preferably from 2% to 40% by weight, and most preferably from 5% to 25% by weight, of the composition.
  • a second essential component of the liquid diluent which forms part of die liquid phase of die detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s).
  • solvent is used herein to connote tiie non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the “solvent "-containing liquid phase, otiier components will be present as particulate material dispersed within the "solvent "-containing liquid phase. Thus the term “solvent” is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
  • nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity.
  • low-polarity liquids are tiiose which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • relatively polar solvents such as ethanol should not be utilized.
  • Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include non-vicinal C4-C8 alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyemylene glycols, lower molecular weight methyl esters and amides.
  • a preferred type of nonaqueous, low-polarity solvent for use in the compositions herein comprises the non-vicinal C4-C8 branched or straight chain alkylene glycols.
  • Materials of this type include hexylene glycol (4-methyl-2,4- ⁇ entanediol), 1 ,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is die most preferred.
  • Another preferred type of nonaqueous, low-polarity solvent for use herein comprises die mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6 alkyl etiiers.
  • Such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl etiier, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl etiier and dipropylene glycol monobutyl ether are especially preferred.
  • Compounds of die type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
  • Anotiier preferred type of nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyetiiylene glycols (PEGs). Such materials are those having molecular weights of at least 150. PEGs of molecular weight ranging from 200 to 600 are most preferred.
  • non-polar, nonaqueous solvent comprises lower molecular weight metiiyl esters.
  • Such materials are those of the general formula: R*-C(0)-OCH3 wherein R* ranges from 1 to 18.
  • suitable lower molecular weight metiiyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the nonaqueous, low-polarity organic solven s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein.
  • a solvent component will generally be utilized in an amount of from 1 % to 70% by weight of the liquid phase.
  • tiie nonaqueous, low-polarity organic solvent will comprise from 10% to 60% by weight of the liquid phase, most preferably from 20% to 50% by weight, of the liquid phase of die composition. Utilization of this organic solvent in these concentrations in the liquid phase corresponds to a solvent concentration in die total composition of from 1 % to 50% by weight, more preferably from 5% to 40% by weight, and most preferably from 10% to 30% by weight, of the composition.
  • the ratio of alcohol alkoxylate to organic solvent within the liquid diluent can be used to vary die rheological properties of the detergent compositions eventually formed.
  • the weight ratio of alcohol alkoxylate to organic solvent will range from 50: 1 to 1:50. More preferably, this ratio will range from 3: 1 to 1 :3.
  • liquid diluent concentration in die nonaqueous liquid phase will be determined by the type and amounts of otiier composition components and by the desired composition properties.
  • the liquid diluent will comprise from 35% to 70% of the nonaqueous liquid phase of die compositions herein. More preferably, die liquid diluent will comprise from 50% to 65% of the nonaqueous liquid phase. This corresponds to a nonaqueous liquid diluent concentration in the total composition of from 15% to 70% by weight, more preferably from 20% to 50% by weight, of the composition.
  • the nonaqueous detergent compositions herein also essentially comprise from 1 % to 65% by weight, more preferably from 5% to 50% by weight, of a solid phase of particulate material which is dispersed and suspended within the liquid phase.
  • particulate material will range in size from 0.1 to 1500 microns. More preferably such material will range in size from 5 to 200 microns.
  • the particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in tiie nonaqueous liquid phase of tiie composition.
  • the types of particulate materials which can be utilized are described in detail as follows:
  • the nonaqueous liquid detergent compositions herein can be prepared by combining tiie essential and optional components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein.
  • essential and certain preferred optional components will be combined in a particular order and under certain conditions.
  • an admixture of the alkylbenzene sulfonate anionic surfactant and die two essential components of the nonaqueous diluent is formed by heating a combination of these materials to a temperature from 30 °C to 100°C.
  • a second process step the heated admixture formed as hereinbefore described is maintained under shear agitation at a temperature from 40°C to 100°C for a period of from 2 minutes to 20 hours.
  • a vacuum can be applied to die admixture at this point.
  • This second process step serves to completely dissolve die anionic surfactant in tiie nonaqueous liquid phase.
  • this liquid phase combination of materials is cooled to a temperature of from 0°C to 35 °C.
  • This cooling step serves to form a structured, surfactant-containing liquid base into which die particulate material of the detergent compositions herein can be added and dispersed.
  • Particulate material is added in a fourth process step by combining the particulate material with the liquid base which is maintained under conditions of shear agitation.
  • the liquid base which is maintained under conditions of shear agitation.
  • it is preferred tiiat a certain order of addition be observed.
  • any optional surfactants in solid particulate form can be added in the form of particles ranging in size from 0.2 to 1,000 microns.
  • particles of substantially all of an organic builder e.g., citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate
  • an organic builder e.g., citrate and/or fatty acid
  • an alkalinity source e.g., sodium carbonate
  • Otiier solid form optional ingredients can then be added to die composition at this point. Agitation of the mixture is continued, and if necessary, can be increased at tins point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
  • the particles of the highly preferred peroxygen bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation.
  • die peroxygen bleaching agent material By adding die peroxygen bleaching agent material last, or after all or most of die otiier components, and especially after alkalinity source particles, have been added, desirable stability benefits for the peroxygen bleach can be realized. If enzyme prills are inco ⁇ orated, they are preferably added to die nonaqueous liquid matrix last.
  • agitati on of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from 1 to 30 minutes.
  • one or more of the solid components may be added to the agitated mixture as a slurry of particles premixed with a minor portion of one or more of the liquid components.
  • a premix of a small fraction of the alcohol alkoxylate and/or nonaqueous, low-polarity solvent with particles of the organic builder material and/or die particles of die inorganic alkalinity source and/or particles of a bleach activator may be separately formed and added as a slurry to the agitated mixture of composition components. Addition of such slurry premixes should precede addition of peroxygen bleaching agent and/or enzyme particles which may tiiemselves be part of a premix slurry formed in analogous fashion.
  • compositions of this invention can be used to form aqueous washing solutions for use in tiie laundering and bleaching of fabrics.
  • an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering/bleaching solutions.
  • the aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.
  • An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from 500 to 7,000 ppm of composition in aqueous solution. More preferably, from 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.
  • a non-limiting example of a bleach-containing nonaqueous liquid laundry detergent is prepared having die composition as set forth in Table I.
  • Table I Component Wt. % Range (% wt.)
  • Protease enzyme 0.4 0-1.0 Na3 Citrate, anhydrous 4.3 3-6
  • bis-AQA-1 may be replaced by bis-AQA surfactants 2-22 or other bis- AQA surfactants herein.
  • composition is prepared by mixing the bis-AQA and LAS, then the hexylene glycol and alcohol ethoxylate, together at 54°C (130°F) for 1/2 hour. This mixture is then cooled to 29°C (85°F) whereupon tiie remaining components are added. The resulting composition is tiien stirred at 29°C (85°F) for anotiier 1/2 hour.
  • the resulting composition is a stable anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations.
  • 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
  • Sodium diethylenetriamine penta (phosphonate) ⁇ Sokolan CP-5 is maleic-acrylic copolymer 3 bis- AQA-1 ma y be replaced by an equivalent amount of bis-AQA surfactants bis-AQA2 through bis-AQA-22 or other bis-AQA surfactants herein.
  • ⁇ Balance comprises water (2% to 8%, including water of hydration), sodium sulfate, calcium carbonate, and other minor ingredients.
  • Modern automatic dishwashing detergents can contain bleaching agents such as hypochlorite sources; perborate, percarbonate or persulfate bleaches; enzymes such as proteases, lipases and amylases, or mixtures tiiereof; rinse-aids, especially nonionic surfactants; builders, including zeolite and phosphate builders; low-sudsing detersive surfactants, especially ethylene oxide/propylene oxide condensates.
  • bleaching agents such as hypochlorite sources; perborate, percarbonate or persulfate bleaches; enzymes such as proteases, lipases and amylases, or mixtures tiiereof; rinse-aids, especially nonionic surfactants; builders, including zeolite and phosphate builders; low-sudsing detersive surfactants, especially ethylene oxide/propylene oxide condensates.
  • Such compositions are typically in the form of granules or gels. If used in gel form
  • mixtures of bis-AQA surfactants which can be substituted for the bis-AQA surfactants listed in any of die foregoing Examples.
  • such mixtures can be used to provide a spectrum of performance benefits and/or to provide cleaning compositions which are useful over a wide variety of usage conditions.
  • the bis-AQA surfactants in such mixtures differ by at least 1.5, preferably 2.5- 20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10:1-1: 10.
  • Non- limiting examples of such mixtures are as follows.
  • compositions advantageously provide improved detergency performance (especially in a fabric laundering context) over a broader range of water hardness tiian do die cationic surfactants herein used individually.
  • shorter EO cationics e.g., E02
  • higher EO cationics e.g., E015
  • builders can optimize die performance "window" of anionic surfactants. Until now, however, broadening die window to encompass essentially all conditions of water hardness has been impossible to achieve.

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Abstract

L'invention concerne une composition détergente comprenant un adjuvant à base d'aluminosilicate, un tensioactif sans ammonium quaternaire alcoxylé et un tensioactif cationique avec ammonium quaternaire bis-alcoxylé.
EP97924741A 1996-05-17 1997-05-16 Composition detergente Withdrawn EP0906392A2 (fr)

Applications Claiming Priority (3)

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US1788396P 1996-05-17 1996-05-17
US17883P 1996-05-17
PCT/US1997/008314 WO1997044425A2 (fr) 1996-05-17 1997-05-16 Composition detergente

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EP97924743A Withdrawn EP0918833A1 (fr) 1996-05-17 1997-05-16 Composition detergente
EP97927653A Withdrawn EP0906405A1 (fr) 1996-05-17 1997-05-16 Composition de detergent
EP97924742A Withdrawn EP0906403A1 (fr) 1996-05-17 1997-05-16 Composition detergente
EP97926568A Withdrawn EP0907705A1 (fr) 1996-05-17 1997-05-16 Composition de detergent
EP97924741A Withdrawn EP0906392A2 (fr) 1996-05-17 1997-05-16 Composition detergente
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EP97927653A Withdrawn EP0906405A1 (fr) 1996-05-17 1997-05-16 Composition de detergent
EP97924742A Withdrawn EP0906403A1 (fr) 1996-05-17 1997-05-16 Composition detergente
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AR007169A1 (es) 1999-10-13
BR9710675A (pt) 1999-08-17
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ZA974226B (en) 1998-12-28
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BR9710676A (pt) 1999-08-17
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BR9710678A (pt) 1999-08-17
JPH11510554A (ja) 1999-09-14
CN1225678A (zh) 1999-08-11
BR9710445A (pt) 1999-08-17
CA2254948A1 (fr) 1997-11-27
CA2255006A1 (fr) 1997-11-20
WO1997044433A1 (fr) 1997-11-27
BR9710444A (pt) 1999-08-17
CA2255005A1 (fr) 1997-11-20
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AR014606A1 (es) 2001-03-28
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CA2254820A1 (fr) 1997-11-27
CA2254961A1 (fr) 1997-11-27
BR9709587A (pt) 2000-04-25
WO1997043394A3 (fr) 1997-12-24
EP0912686A2 (fr) 1999-05-06
CA2254947A1 (fr) 1997-11-27
CA2255003A1 (fr) 1997-11-27
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CN1230213A (zh) 1999-09-29
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CN1168812C (zh) 2004-09-29
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