EP0918834A2 - Composition detergente - Google Patents

Composition detergente

Info

Publication number
EP0918834A2
EP0918834A2 EP97925591A EP97925591A EP0918834A2 EP 0918834 A2 EP0918834 A2 EP 0918834A2 EP 97925591 A EP97925591 A EP 97925591A EP 97925591 A EP97925591 A EP 97925591A EP 0918834 A2 EP0918834 A2 EP 0918834A2
Authority
EP
European Patent Office
Prior art keywords
composition according
aqa
surfactant
surfactants
alkyl
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Withdrawn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
EP97925591A
Other languages
German (de)
English (en)
Inventor
Kaori Asano
Stuart Clive Askew
Hajime Baba
Andre Cesar Baeck
Jean-Luc Bettiol
Thomas Anthony Cripe
John Downing Curry
Schmidt, (De Rossett), Corey Elizabeth
Ian Martin Dodd
Richard Timothy Hartshorn
Jones Lynda Anne Speed
Rinko Katsuda
Frank Andrej Kvietok
Mark Hsiang-Kuen Mao
Michael Alan John Moss
Susumu Murata
Royohei Ohtani
Rajan Keshav Panandiker
Kakumanu Pramod
Khizar Mohamed Khan Sarnaik
Christian Arthur Jacques Kamiel Thoen
Peter Robert Foley
Sanjeev Krishnadas Manohar
Mitsuyo Okamoto
Kenneth William Willman
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 EP0918834A2 publication Critical patent/EP0918834A2/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Withdrawn legal-status Critical Current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
    • C11D3/16—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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/645—Mixtures of compounds all of which are cationic
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to detergent compositions which comprise selected mixtures of anionic surfactants and selected ethoxylated quaternary ammonium compounds.
  • laundry detergents and other cleaning compositions present a considerable challenge, since modern compositions are required to remove a variety of soils and stains from diverse substrates.
  • laundry detergents typically 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 soils and stains.
  • surfactants and surfactant combinations exhibit optimal performance on certain types of soils and stains, they can actually diminish performance on other soils.
  • surfactants which remove greasy/oily soils from fabrics can sometimes be sub- optimal for removing particulate soils, such as clay.
  • alkoxylated quaternary ammonium (AQA) compounds can be used in laundry detergents to boost performance.
  • AQA alkoxylated quaternary ammonium
  • low levels of these AQA compounds provide superior cleaning performance when used in certain combinations with conventional alkyl sulfate and alkyl benzene sulfonate surfactants at specified ratios and proportions.
  • the present invention provides an improvement in laundry cleaning performance without the need to develop new, expensive surfactant species.
  • the AQA surfactants used in the present manner provide substantial advantages to the formulator over cationic surfactants known heretofore.
  • the AQA surfactants herein are compatible with the preferred alkyl sulfate and alkyl benzene sulfonate detersive surfactants.
  • the AQA surfactants are formulatable over a broad pH range from 5 to 12.
  • the AQA surfactants can be prepared as 30% (wt.) solutions which are pumpable, and therefore easy to handle in a manufacturing plant.
  • AQA surfactants with degrees of ethoxylation above 5 are sometimes in a liquid form and can be provided as 100% neat materials.
  • the ability of the AQA surfactants herein to be provided as high concentrate solutions provides a substantial economic advantage in transportation costs.
  • the AQA surfactants are also compatible with various perfume ingredients, unlike other quats known in the art.
  • the AQA surfactants herein appear to minimize or eliminate redeposition of fatty acids/oily materials present in an aqueous laundry liquor back onto fabrics which have been previously soiled with body soils. Accordingly, the AQA surfactants herein have now been found to prevent the redeposition of polar lipids from an aqueous laundry bath back onto fabrics from whence body soils have been removed through the laundering process. Stated otherwise, in a laundering liquor, the AQA surfactants herein remove such polar lipids and keep them suspended in the aqueous medium, rather than allowing them to redeposit onto the cleaned fabrics.
  • the AQA surfactants herein are surprisingly compatible with the polyanionic materials such as polyacrylates and acrylate/maleate copolymers which are used to provide a builder and/or dispersant function with many conventional detersive surfactants.
  • Other advantages for the AQA surfactants herein include their ability to enhance enzymatic cleaning and fabric care performance in a laundering liquor. While not intending to be limited by theory, it is speculated that enzymes may be partially denatured by conventional anionic surfactants. It is further speculated that the AQA surfactants herein somehow interact with the anionic surfactants to inhibit that degradation.
  • AQA surfactants herein provide substantial cleaning enhancement with respect to clay soil removal from fabrics, as compared with conventional detergent mixtures. Again, while not intending to be limited by theory, it may be speculated that conventional cationic surfactants associate with the clay in "close-packed” fashion and render the clay more difficult to remove.
  • the alkoxylated AQA surfactants are believed to provide more open associations with clays, which are then more readily removed from fabric surfaces.
  • the compositions herein containing the AQA surfactants provide improved performance over conventional cationic surfactants with special regard to clay soil removal. Still further advantages for the AQA surfactants herein have been discovered. For example, in bleaching compositions which comprise a bleach activator (as disclosed herein) it appears that some sort of ion pair or other associative complex is formed with the per-acid released from the activator.
  • compositions without bleach the formulator my choose to use somewhat higher levels of AQA to provide enhanced performance benefits.
  • AQA surfactants herein to modify the solution characteristics of conventional anionic surfactants such as alkyl sulfates or alkyl benzene sulfonates to allow more of the surfactants to be available to perform their cleaning function. This is particularly true in situations faced by the formulator where the detergent composition is "underbuilt” with respect to calcium and/or magnesium water hardness ions. Under such circumstances, it is preferred to use sufficient AQA surfactant to provide from about 10 ppm to about 50 ppm of the AQA surfactants in the wash liquor.
  • compositional usage ranges from about 1% to about 5%, by weight, in fully-formulated detergent compositions.
  • concentration can vary with product usage rates and the amount of other surfactant present in the wash liquor.
  • the AQA level may be as high as 100-150 ppm in solution. This still only translates to 3-4% AQA surfactant in the finished detergent composition.
  • AQA surfactants herein containing about 2 ethylene oxide (EO) groups perform extremely well under circumstances of low water hardness or when well-built detergent compositions are used. However, under circumstances of high hardness (about 170 ppm calcium carbonate, and higher) it is more preferred to use AQA surfactants with at least about 5 EO groups. Moreover, for some soils and stains, such as fecal matter, AQA surfactants having on the order of 10-20 EO groups are preferred. Accordingly, it has now been discovered that mixtures of AQA surfactants can be blended and used to provide a broad spectrum of cleaning performance over a wide variety of soils and stains and under a wide range of usage conditions. Representative, but non-limiting, examples of such combinations of AQA surfactants are disclosed in the Examples hereinafter.
  • the AQA surfactants used in the manner of the present invention, successfully address many of the problems associated with the formulation of modern, high-performance detergent compositions.
  • the AQA surfactants allow the formulation of effective laundry compositions which can be used to remove a wide variety of soils and stains under a wide spectrum of usage conditions.
  • the present invention encompasses a composition of matter comprising a mixture of, or prepared by combining, a cationic surfactant and a member selected from each of two classes of anionic surfactants, said surfactants having the respective formulae:
  • R* is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms
  • R ⁇ is an alkyl group containing from one to three carbon atoms, preferably methyl
  • R J and R ⁇ can vary independently and are selected from hydrogen (preferred), methyl and ethyl
  • R is a linear or branched alkyl or alkenyl moiety having from about 10 to about 20 carbon atoms, preferably C12 to Cjg alkyl or as found in secondary alkyl sulfates
  • R ⁇ is C ⁇ Q-C ⁇ alkylbenzene, preferably C j j -C j 3 alkylbenzene
  • M + and M' + can vary independently and are selected from alkali metals, alkaline earths, alkanolammonium and ammonium
  • X" is an anion such as chloride, bro
  • a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy (i.e.. -CH2CH2O-), propoxy, butoxy and mixed ethoxy/propoxy; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30. preferably 1 to about 4, and most preferably to about 4; preferably both p and q are 1.
  • the weight ratio of (I) to (II) + (III) is preferably about 1 : 100 to about
  • the weight ratio of (II):(III) is preferably 4: 1-1 :4, more preferably 2: 1-1 :2.
  • the weight ratio of R ⁇ to R ⁇ is preferably from 1 :13-1 :5.
  • AQA compounds wherein the hydrocarbyl substituent R' is Cg-C j i , especially C ⁇ Q, enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials.
  • the Cg-Cn AQA surfactants may be preferred by some formulators.
  • the levels of the AQA surfactants used to prepare finished laundry detergent compositions can range from about 0.1% to about 5%, typically from about 0.45% to about 2.5%, by weight.
  • the composition comprises: surfactants (I), (II) and (III) in a weight ratio of (I) to (II + III) in a weight range of at least about 1 : 10.
  • said anionic surfactant (II) is a C ⁇ -Cjg primary or secondary alkyl sulfate (AS) and said anionic surfactant (III) is an alkyl benzene sulfonate with cx C ⁇ ⁇ -C ⁇ , branched or linear alkyl chain.
  • the composition also comprises a nonionic surfactant which is a member selected from the group consisting of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglucosides, and mixtures thereof.
  • a nonionic surfactant which is a member selected from the group consisting of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglucosides, and mixtures thereof.
  • compositions herein comprise: (a) from about 0.25% to about 3%, by weight, of Coco Methyl EO2 as surfactant (I); (b) from about 3% to about 40%, by weight, of straight chain or branched chain primary or secondary AS as surfactant (II);
  • the invention also encompasses fully formulated detergent compositions comprising adjunct ingredients and at least about 3%. by weight, of the aforesaid detersive surfactant system, said surfactant system comprising a cationic surfactant, a mixture of anionic surfactants, and optional nonionic surfactants, all as disclosed above, and adjunct ingredients including those selected from the group consisting of builders, enzymes, soil release polymers, bleaches, clay soil removal/antiredeposition agents, polymeric dispersing agents, brighteners, dye transfer inhibiting agents, suds suppressors, fabric softeners, and other adjuncts disclosed herein, as well as detersive surfactants not encompassed by surfactants (I)- (IV), e.g., a member selected from the group consisting of soaps, oleyl sulfate, alkyl alkoxy sulfates, alkyl alkoxy carboxylates, sulfated
  • the AQA surfactants used in the manner of the present invention also provide an improved method for removing the following soils and stains from fabrics: blood; greasy food stain; particulate stain; body soils (including fabric "dinginess” caused by small, but noticeable, stain/soil accumulations over time) and other stains noted herein.
  • Such stains and soils are removed from fabrics such as cotton, polyester/cotton blends (P/C) and double-knit polyester (DKPE).
  • the method comprises contacting fabrics in need of removal of such soils with an effective amount of the compositions herein, in the presence of water, and preferably with agitation.
  • Various suitable usage levels and methods are disclosed hereinafter.
  • the AQA surfactants herein, especially the preferred CocoMeEO2 are disclosed hereinafter.
  • AQA-1 hereinafter
  • the AQA surfactants herein, especially AQA-1 provide improved (even synergistic) performance with amylase and cellulase enzymes. This improvement is seen especially in the absence of bleach.
  • this invention provides a means for enhancing the removal of greasy/oily soils by combining a lipase enzyme with an AQA surfactant.
  • Greasy/oily "everyday "soils are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter.
  • This invention also provides improved cleaning and fabric care benefits by combining a cellulytic enzyme with an AQA surfactant.
  • a cellulytic enzyme In older/worn cotton fabrics or other cellulosic fabrics the sheathes around individual fibres degrade to form gelatinous/amorphous cellulose "glues" which entrap dirt.
  • the glue acts as an ideal substrate for deposition/retention of greasy /oily body soils (e.g., on collars and pillowcases) which are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter. Removal of these hydrophobic soils from worn fabrics is thus very difficult and low levels of residual stain often remain on the fabric after washing. Again, after successive wearing/washing these soils build up, leading to yellowing and more entrapment of dirt.
  • detergent compositions containing the AQA surfactants and cellulytic enzymes deliver superior cleaning and whiteness performance vs. products containing either ingredient alone.
  • cellulytic enzymes e.g., cellulases and/or endoglucanases
  • these benefits appear to be the result of the effective penetration of hydrophobic body soils by the AQA surfactants.
  • This boosts access of the cellulytic enzymes which degrade the amorphous cellulose glue (which binds the soil on the fabric) around the fibers. As the glue dissolves, the entrapped dirt is released and whiteness is restored.
  • the combined cellulytic/AQA system also provides softness benefits vs. the cationic or enzyme alone; effective depilling and ungluing of worn fibers leads to improved fabric softness feel.
  • This invention also provides detergent compositions which deliver effective cleaning of greasy/oily everyday soils via use of percarbonate bleach with an AQA surfactant as disclosed herein.
  • Percarbonate which delivers peroxide bleach into the wash, is a cornerstone technology of modern, ultra-compact granular laundry detergent formulas.
  • Peroxide bleach is very hydrophilic and, while it cannot match the bleaching effectiveness delivered by peracids (formed for example from peroxide interaction with TAED), it is effective at decoloration of pigments (e.g., in particulates or beverage stains) and also can help remove the color from the organic residues associated with body soils.
  • compositions containing AQA surfactants and percarbonate bleach deliver superior cleaning and whiteness performance vs. products containing either technology alone. These benefits appear to be driven by the effective solubilization of the greasy oil soils by AQA, thereby allowing access of the hydrophilic peroxide bleach to the color bodies in the soil (e.g., entrapped pigments) and resulting in improved soil decoloration.
  • This invention also provides detergent compositions which deliver effective cleaning of greasy/oily everyday soils by means of hydrophobic bleach activators used in combination with a water-soluble AQA surfactant of the present type. Everyday soil cleaning and whiteness benefits for hydrophobic bleach activators and peracids have already been demonstrated.
  • This invention also provides compositions which deliver effective cleaning of greasy/oily soils via use of bleach catalysts using an AQA surfactant.
  • Bleach catalysts characterized by the presence of at least one transition metal atom
  • the catalysts deliver strong benefits on colored hydrophilic stains and hydrophilic everyday soils (i.e., socks).
  • the catalysts are typically used at extremely low levels in cleaning products.
  • products containing AQA and catalysts deliver superior cleaning and whiteness performance vs. products containing either technology alone, and are especially potent on everyday soils.
  • These benefits are believed to be driven by effective AQA solubilization on the greasy oil soils which allow access of the hydrophilic "catalyst" bleach to the color bodies in the soil, thereby leading to effective soil decolorization.
  • historical use of bleach catalysts was made difficult because of concerns about fabric damage. Using a dimanganese catalyst, known to cause fabric damage, it has now been found that the occurrence of fabric damage is much reduced when AQA cationics are present. Presumably, these cationics adsorb onto fabrics where they modify the surface charge and are available to ion-pair with the activated catalyst to minimize or prevent fabric damage.
  • this invention allows the use of high levels of insoluble inorganic builders, without fabric encrustation, using layered silicates with a water- soluble AQA surfactant.
  • Layered silicates are composed of discreet units some faces of which are negatively charged. It may be speculated that the positively charged head-group of AQA interacts, via electrostatic bond formation, with the negatively charged face to form a surfactant monolayer upon which a second "hydrophilic" surfactant layer builds up. This drives particle lift-off from fabrics, thereby minimizing encrustation which can otherwise result in a harsh "feel to the fabrics".
  • This invention also allows the formulation of high levels of insoluble inorganic or soluble (bi)carbonate builders in compositions containing relatively low polycarboxylate polymers, without driving fabric encrustation issues by using the different types of builder with an AQA surfactant as disclosed herein.
  • high molecular weight polycarboxylate polymers have been used as dispersants in granular laundry detergents. These polymers are, however, generally expensive.
  • the polymers, as well as being effective at soil suspension, also effectively control fabric encrustation by lifting off inorganics (including builders/precipitated carbonates) from fabrics.
  • Low polymer formulations known heretofore are prone to fabric encrustation shortcomings.
  • This invention also provides detergent compositions which deliver effective cleaning of greasy/oily "everyday” soils (and accidental soils), via use of polyethoxyated-polyamine polymers (PPP) with the AQA surfactants herein.
  • PPP polyethoxyated-polyamine polymers
  • greasy/oily "everyday” soils e.g., on collars, pillowcases
  • PPP polyethoxyated-polyamine polymers
  • Characteristic features of these materials include: (1 ) a reasonably low molecular weight "hydrophobic” polyamine backbone (which is slightly cationic in nature providing an affinity for soils and fabrics); and (2) pendant "hydrophilic" polyethoxylate groups which provide steric stabilization and greasy soil suspension. During the wash, these polymers work at the stain/wash liquor interface.
  • detergent compositions containing the AQA surfactants herein and ethoxylated polyamine polymers deliver superior cleaning and whiteness performance vs. compositions containing either technology alone.
  • Benefits for the mixed system are believed to be the result of: ( 1 ) AQA action on the stain surface to prevent lime soap formation and to lift off any calcium soaps present, thereby facilitating improved polymer deposition; (2) AQA providing solubilization deep into the soil, while the polymer acts as a "grease removal shuttle", stripping out the AQA-solubilized stain components and dispersing them into the wash liquor.
  • This invention also provides detergent compositions which deliver effective cleaning of greasy/oily everyday soils, by means of use of high levels of surfactant (optionally including branched surfactants) with an AQA surfactant.
  • high levels of surfactant optionally including branched surfactants
  • modern "ultra-compact" detergent compositions generally contain high levels of surfactants (nonionic and anionic) and are fairly effective at body soil cleaning.
  • anionic or mixed anionic/nonionic surfactants (optionally including branched surfactants) deliver superior cleaning performance vs. products containing either technology alone.
  • this invention provides detergent, bleach and other compositions which deliver improved perfume residuality on fabrics after the wash, via use of perfume with a water-soluble AQA surfactant.
  • Natural and synthetic fabrics can be characterized by the surface charge on their fibers. Cotton is hydrophilic with a net negative surface charge, whereas polyester is hydrophobic with a neutral surface charge.
  • Perfumes are a complex mixture of hydrophobic organic actives, including esters, alcohols, ketones, aldehydes, ethers, and the like. The fabric substantivity of different perfume actives depends on: (1) functionality (how polar they are); (2) the molecular weight of the active; and (3) the charge on the fabric fibers. Most perfume actives contain electron-rich oxygen atoms which will be attracted to electron deficient molecules/surfaces.
  • AQA surfactants with perfumes (characterized as having >10% of components with molecular weight >150) provides improved perfume fabric substantivity. While not intending to be limited by theory, it appears that, as well as increasing the hydrophobicity of anionic or anionic/nonionic surfactant systems, the AQA surfactants have high fabric substantivity (especially for cotton). The AQA surfactants appear to adsorb onto the fibers where they change the surface charge from neutral/negative to positive (or electron deficient). This modified fabric surface acts like a magnet to the electron rich domains of the perfume actives, thereby drawing them onto the fabrics where they are held electrostatically. This significantly increases perfume residuality. These benefits are most pronounced for perfume components having at least one oxygen atom and a molecular weight greater than 150. The level of such perfume ingredients should account for at least about 10% of the total perfume mixture to achieve the maximum benefit of this effect.
  • the alkoxylated quaternary ammonium (“AQA") compounds used according to the present invention enhance the cleaning performance of fabric laundry detergent compositions which contain select amounts of certain anionic surfactants.
  • the AQA compounds herein also have the advantage that they are commercially accessible and are compatible with the various detersive ingredients such as builders, detersive enzymes, and the like, which are used in many modern, high quality, fully-formulated laundry detergents.
  • the AQA compounds exhibit satisfactory stability in the presence of the bleach ingredients commonly used in laundry detergent-plus-bleach compositions.
  • the AQA surfactants herein exhibit superior performance with respect to the removal of body soils and everyday soils such as sock soil.
  • the combination of the AQA surfactants with the specified anionic surfactants removes such soils from fabrics.
  • the specified combination of the AQA surfactants with otherwise conventional anionic surfactants provides excellent cleaning performance on a variety of other soils and stains, including food stains, particulate soils and greasy/oily stains.
  • the compositions herein provide improved performance for cleaning a broad spectrum of soils and stains including body soils from collars and cuffs, greasy soils, and enzyme/bleach sensitive stains such as spinach and coffee.
  • the compositions herein also provide excellent cleaning on builder sensitive stains such as clay, and thus are especially useful in a nil-P context.
  • the bis- alkoxylated cationics herein have sufficient solubility that they can be used in combination with mixed surfactant systems which are quite low in nonionic surfactants and which contain, for example, alkyl sulfate surfactants.
  • This can be an important consideration for formulators of detergent compositions of the type which are conventionally designed for use in automatic washing machines, especially of the type used in Japan, as well as under North American usage conditions.
  • such compositions will comprise an anionic (total LAS/AS) surfactant:nonionic surfactant weight ratio in the range from about 25:1 to about 1 :25, preferably about 20:1 to about 3:1.
  • European-type formulas which typically will comprise anionic: nonionic ratios in the range of about 10:1 to 1 : 10, preferably about 5: 1 to about 1 :5.
  • the present invention employs an "effective amount" of the AQA surfactants to improve the performance of cleaning compositions which contain other adjunct ingredients.
  • an “effective amount” of the AQA surfactants and adjunct ingredients herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the performance of the cleaning composition against at least some of target soils and stains.
  • the formulator will use sufficient AQA to at least directionally improve cleaning performance against such stains.
  • the formulator will use sufficient AQA to at least directionally improve cleaning performance against such soil.
  • the AQA surfactants can be used at levels which provide at least a directional improvement in cleaning performance over a wide variety of soils and stains, as will be seen from the data presented hereinafter.
  • the AQA surfactants are used herein in detergent compositions in combination with other detersive surfactants at levels which are effective for achieving at least a directional improvement in cleaning performance.
  • usage levels can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the type of washing machine.
  • a wash cycle of about 10 to about 14 minutes and a wash water temperature of about 10°C to about 50°C it is preferred to include from about 2 ppm to about 50 ppm, preferably from about 5 ppm to about 25 ppm, of the AQA surfactant in the wash liquor.
  • this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.1% to about 3.2%, preferably about 0.3% to about 1.5%, for a heavy-duty liquid laundry detergent.
  • a wash cycle of about 10 to about 60 minutes and a wash water temperature of about 30°C to about 95°C it is preferred to include from about 13 ppm to about 900 ppm, preferably from about 16 ppm to about 390 ppm, of the AQA surfactant in the wash liquor.
  • this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.4% to about 2.64%, preferably about 0.55% to about 1.1%, for a heavy-duty liquid laundry detergent.
  • a wash cycle of about 8 to about 15 minutes and a wash water temperature of about 5°C to about 25°C it is preferred to include from about 1.67 ppm to about 66.67 ppm, preferably from about 3 ppm to about 6 ppm, of the AQA surfactant in the wash liquor.
  • this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.25% to about 10%, preferably about 1.5% to about 2%, for a heavy-duty liquid laundry detergent.
  • usage rates of from about 18 g to about 35 g per wash load for dense ("compact") granular laundry detergents (density above about 650 , , l o
  • Cationic Surfactants The preferred bis-ethoxylated cationic surfactants herein are available under the trade name ETHOQUAD from Akzo Nobel
  • Step 1 of the reaction is preferably conducted in an aqueous medium.
  • Reaction temperatures are typically in the range of 140-200°C.
  • Reaction pressures are 50-1000 psig.
  • a base catalyst preferably sodium hydroxide can be used.
  • the mole ratio of reactants are 2: 1 to 1 : 1 amine to alkyl sulfate.
  • the process herein is preferably conducted using Cg-C] 3 alkyl sulfate, sodium salt.
  • the ethoxylation and quaternization reactions are conducted using conventional conditions and reactants.
  • Step 1 of reaction Scheme 5 results in products which are sufficiently soluble in the aqueous reaction medium that gels may form. While the desired product can be recovered from the gel.
  • an alternate, two-step synthesis Scheme 6, hereinafter, may be more desirable in some commercial circumstances.
  • the second step (ethoxylation) is preferably conducted using ethylene oxide and an acid such as HCI which provides the quaternary surfactant. As shown below, chlorohydrin i.e., chloroethanol, can also be reacted to give the desired bishydroxyethyl derivative.
  • the first step is preferably conducted in an aqueous medium. Reaction temperatures are typically in the range of 100-230° C.
  • Reaction pressures are 50-1000 psig.
  • a base preferably sodium hydroxide
  • the mole ratio of amine to alkyl sulfate is typically from 10: 1 to 1 : 1.5; preferably from 5:1 to 1: 1.1; more preferably from 2: 1 to 1 : 1.
  • the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble.
  • the second step of the process is conducted under conventional reaction conditions. Further ethoxylation and quatemization to provide AQA surfactants are conducted under standard reaction conditions.
  • Scheme 7 can optionally be conducted using ethylene oxide under standard ethoxylation conditions, but without catalyst, to achieve monoethoxylation.
  • the mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform.
  • the funnel is shaken well for a few minutes and then the mixture is allowed to separate.
  • the lower chloroform layer is drained and the chloroform evaporated off to obtain product.
  • Synthesis B Preparation of N,N-Bis(2-hvdroxyethyl)dodecylamine 1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the presence of base in the manner described in Synthesis A. The resulting 2- hydroxyethyldodecylamine is recovered and reacted with 1 -chloroethanol to prepare the title compound.
  • the glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180°C under 300-400 psig nitrogen for 3-4 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a few minutes and then allowed mixture to separate. The lower chloroform layer is drained and the chloroform is evaporated off to obtain product. The product is then reacted with 1 molar equivalent of ethylene oxide in the absence of base catalyst at 120-130°C to produce the desired final product.
  • the bis-substituted amines prepared in the foregoing Syntheses can be further ethoxylated in standard fashion. Quatemization with an alkyl halide to form the AQA surfactants herein is routine.
  • AQA surfactants used herein. It is to be understood that the degree of alkoxylation noted herein for the AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically yield mixtures of materials with differing degrees of ethoxylation. Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "EO2.5", “EO3.5”, and the like.
  • R ⁇ is C io-Cjg hydrocarbyl and mixtures thereof, preferably C J Q, C ⁇ J, C 14 alkyl and mixtures thereof, and X is any convenient anion to provide charge balance, preferably chloride.
  • R ⁇ is derived from coconut (C 12-C 14 alkyl) fraction fatty acids
  • R2 is methyl and ApR 3 and A'qR 4 are each monoethoxy. This preferred type of compound is referred to herein as "CocoMeE02" or "AQA- 1 " in the above list.
  • Other preferred AQA compounds herein include compounds of the formula:
  • Rl is Cio-Cjg hydrocarbyl, preferably C 1 Q-C 14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride.
  • CH2CH2O units are replaced by butoxy (Bu), isopropoxy [CH(CH3)CH2 ⁇ ] and [CH2CH(CH 3 O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
  • Anionic Surfactants - The alkyl benzene sulfonate (“LAS") and primary (preferred; "AS”) or secondary alkyl sulfate components of the present compositions are well-known and widely-used commercial surfactants. As noted above, one of the important advantages of the present invention is the discovery that the AQA surfactants, when used in the manner disclosed herein, boost the performance of these otherwise conventional materials.
  • the LAS surfactant has an alkyl chain length typically in the Cjo-Ci 6 range, and commercially available LAS has an average alkyl chain length in the 1 1-13 range, usually around 11.5.
  • the AS surfactant has a chain length typically in the CJ Q-C20 ran 8 e » and many commercial sources of AS are in the 12-18 range. All such commercial LAS and AS materials may be used herein. Unsaturated sulfates such as oleyl sulfate can also be used.
  • Nonionic Surfactants typically at levels from about 1% to about 55%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), CiQ-Cj g glycerol ethers, and the like.
  • AE alkoxylated alcohols
  • PFAA's polyhydroxy fatty acid amides
  • APG's alkyl polyglycosides
  • CiQ-Cj g glycerol ethers and the like.
  • condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • nonionic surfactants of this type include: Tergitol ⁇ M 15-S-9 (the condensation product of C ⁇ 1-C15 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the condensation product of Cj2-C]4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Co ⁇ oration; Neodol ⁇ M 45.9 (the condensation product of C ,4- ⁇ 5 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12- C j 3 linear alcohol with 3 moles of ethylene oxide), Neodol ⁇ M 45.7 ( me condensation product of CJ4-C15 linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45.5 ( me condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; Kyro ⁇ M rfOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide
  • Another class of preferred nonionic surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
  • Rl is H, or C1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
  • R 2 is C5.31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R ⁇ is methyl
  • R2 is a straight Cl l-15 alkyl or C15.17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • Typical examples include the Cj2-C j g and C 12 -C i4 N-methylglucamides. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.
  • alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms
  • a polysaccharide e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-. and/or 6- positions on the preceding saccharide units.
  • the preferred alkylpolyglycosides have the formula: R2 ⁇ (C n H 2n O)t(glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl. hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3. most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1- position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include Igepal ⁇ M CO-630, marketed by the GAF Co ⁇ oration; and TritonTM X-45, X-l 14, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • alkylphenol alkoxylates e.g., alkyl phenol ethoxylates.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • PluronicTM surfactants also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
  • Examples of this type of nonionic surfactant include certain of the commercially available Tetronic ⁇ M compounds, marketed by BASF.
  • Additional Surfactants include the conventional the Cio-Cj g alkyl alkoxy sulfates ("AE X S"; especially EO 1-7), C iQ-C j g alkyl alkoxy carboxylates (especially the EO 1-5) and Cjo-Cjg alpha-sulfonated fatty acid esters.
  • C ⁇ -C j g betaines and sulfobetaines ("sultaines”), Cjn-C ig amine oxides, and the like, can also be used.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Ci ⁇ soaps may be used.
  • Other conventional useful surfactants are listed in standard texts.
  • adjunct ingredients which may be used in the compositions of this invention, but is not intended to be limiting thereof. While the combination of the AQA and the anionic surfactants with such adjunct compositional ingredients can be provided as finished products in the form of liquids, gels, bars, or the like using conventional techniques, the manufacture of the granular laundry detergents herein requires some special processing techniques in order to achieve optimal performance. Accordingly, the manufacture of laundry granules will be described hereinafter separately in the Granules Manufacture section (below), for the convenience of the formulator.
  • Builders - Detergent builders can optionally but preferably be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces.
  • Builders can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned.
  • Builder level can vary widely depending upon end use and physical form of the composition.
  • Built detergents typically comprise at least about 1% builder.
  • Liquid formulations typically comprise about 5% to about 50%, more typically 5% to 35% of builder.
  • Granular formulations typically comprise from about 10% to about 80%, more typically 15% to 50% builder by weight of the detergent composition.
  • Lower or higher levels of builders are not excluded. For example, certain detergent additive or high- surfactant formulations can be unbuilt.
  • Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amo ⁇ hous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water- soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
  • silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amo ⁇ hous-solid or non-structured-liquid types
  • borates e.g., for pH- buffering purposes
  • sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing detergent compositions.
  • Builder mixtures sometimes termed “builder systems” can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein.
  • preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60:1 to about 1 :80.
  • Certain preferred laundry detergents have said ratio in the range 0.90:1.0 to 4.0:1.0. more preferably from 0.95:1.0 to 3.0:1.0.
  • P-containing detergent builders often preferred where permitted by legislation include, but are not Hmited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.
  • Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1, including, particularly for automatic dishwashing pu ⁇ oses, solid hydrous 2-ratio silicates marketed by PQ Co ⁇ . under the tradename BRITESIL®, e.g., BRITESIL H2O; 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 ⁇ -Na2SiO5 mo ⁇ hology silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See preparative methods in German DE-A- 3,417,649 and DE-A-3,742,043.
  • Other layered silicates such as those having the general formula NaMSi x O2 x +i yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein.
  • Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the ⁇ , ⁇ and ⁇ layer-silicate forms.
  • Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.
  • crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM 2 ⁇ ySi ⁇ 2 .zM'O wherein M is Na and/or K, M 1 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 other 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.
  • Aluminosilicate builders are especially useful in granular detergents, but can also be inco ⁇ orated in liquids, pastes or gels. Suitable for the present pu ⁇ oses are those having empirical formula: [M z (AlO2) z (SiO2)v] xH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
  • Aluminosilicates can be crystalline or amo ⁇ hous, naturally-occurring or synthetically derived. An aluminosilicate production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Suitable organic detergent builders include polycarboxylate compounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • Polycarboxylate builders include the ether polycarboxylates. such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Lamberti et al, U.S.
  • Suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymefhyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid: as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy- methyloxysuccinic 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 pu ⁇ oses, when they have surfactant capability, these materials are summed up as detersive surfactants.
  • Preferred types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-l ,6- hexanedioates and the related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986.
  • Succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • Succinate builders also include: laurylsuccinate.
  • Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C ⁇ 2-C ⁇ g monocarboxylic acids
  • Other suitable polycarboxylates are disclosed in U.S. 4,144,226, Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3.723,322.
  • Mineral Builders Waters of hydration or anions other than carbonate may be added provided that the overall charge is balanced or neutral.
  • a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred.
  • noncarbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof.
  • Preferred builders of this type in their simplest forms are selected from the group consisting of Na2Ca(CO3)2, K2Ca(CO3) 2 , Na 2 Ca2(CO 3 )3, NaKCa(CO 3 )2, NaKCa 2 (C0 3 ) 3 , K 2 Ca 2 (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.
  • MckelveyiteY Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Schrockingerite, Shortite, Surite, Tunisite, Chineseite, Tyrolite, Vishnevite, and Zemkorite.
  • Preferred mineral forms include Nyererite, Fairchildite and Shortite.
  • Enzymes - Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
  • Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
  • 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, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.
  • 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 and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • 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 Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo.
  • proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased 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.
  • protease D is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206.
  • 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 the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL ® in commercial use in 1993.
  • These preferred amylases herein share 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 about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 1 1 , measured versus the above- identified reference-point amylase.
  • Stability can be measured using any of the art- disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability-enhanced amylases can be obtained from Novo or from Genencor International. One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability-enhanced amylases vs. the 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 the 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 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 with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo.
  • Any 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. Other amylase enzymes include those described in WO 95/26397 and in co- pending application by Novo Nordisk PCT/DK96/00056.
  • Specific amylase enzymes for use in the detergent compositions of the present invention include ⁇ - amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay. (Such Phadebas® ⁇ -amylase activity assay is described at pages 9-10, WO 95/26397.) Also included herein are ⁇ -amylases which are at least 80% homologous with the amino acid sequences shown in the 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 the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in GB-A- 2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • CAREZYME® and CELLUZYME® are especially useful. See also WO 91 17243 to Novo.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P.” Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical 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 the benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions containing the AQA surfactants in the manner disclosed herein, especially when the D96L is used at levels in the range of about 50 LU to about 8500 LU per liter of wash solution.
  • Cutinase enzymes suitable for use herein are described in WO 8809367 A to
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash io other substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo- peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
  • a range of enzyme materials and means for their 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 their 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. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo. , ,
  • the enzyme-containing compositions herein may optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes.
  • Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
  • One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes 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 the grease-cutting action of certain types of surfactant.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
  • Stabilizing systems of certain cleaning compositions may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
  • chlorine bleach scavengers While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm. the available chlorine in the total volume of water that comes in contact with the enzyme, for example during dish- or fabric-washing, can be relatively large; accordingly, enzyme stability to chlorine in-use is sometimes problematic.
  • Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • special enzyme inhibition systems can be inco ⁇ orated 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.
  • the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment of the invention; even then, the scavenger is added only for optimum results.
  • the formulator will exercise a chemist's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as formulated, with other reactive ingredients.
  • ammonium salts such salts can be simply admixed with the 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 Agent - Known polymeric soil release agents. hereinafter “SRA” or “SRA's”, can optionally be employed in the present detergent compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%. typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the composition.
  • Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles thereby serving as an anchor for 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. 4,956,447), as well as noncharged monomer units and structures may be linear, branched or even star-shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active properties. Structures and charge distributions may be tailored for application to different fiber or textile types and for varied detergent or detergent additive products.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being inco ⁇ orated into the ester structure through one, two, three, four or more positions, without of course forming a densely crosslinked overall structure.
  • Suitable SRA's include: a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451 , November 6, 1990 to J.J. Scheibel and E.P.
  • ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycoi (“PG”) in a two-stage transesterification/ oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycoi
  • Gosselink et al 4,71 1,730, December 8, 1987 to Gosselink et al, for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethylenegiycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26. 1988 to Gosselink, such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink.
  • EG ethylene glycol
  • PG PG
  • DMT poly(ethylenegiycol)
  • Na-3,6-dioxa-8- hydroxyoctanesulfonate the nonionic-capped block polyester oligomeric compounds of U.S
  • DMT for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 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.
  • 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 the C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December 28, 1976 to Nicol, et ai.
  • Suitable SRA's characterised by poly( vinyl ester) hydrophobe segments include graft copolymers of poly( vinyl ester), e.g., C ⁇ -C ⁇ vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud. et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat units containing 10- 15% by weight of ethylene terephthalate together with 90-80% by weight of polyoxyethylene terephthalate, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. Another preferred SRA is an oligomer having empirical formula
  • CAP2(EG/PG)5(T)5(SIP) ⁇ which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-l ,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two end-cap units derived from sodium 2-(2- hydroxyethoxy)-ethanesulfonate.
  • Said SRA preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabiliser, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene- sulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis pot, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.
  • Suitable monomers for the above SRA include Na 2-(2-hydroxyethoxy)-ethanesulfonate. DMT, Na- dimethyl 5-sulfoisophthalate, EG and PG.
  • oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1 ,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof.
  • Preferred of such esters are those of empirical formula:
  • SEG and CAP monomers for the above esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate (“SEG”), Na-2- ⁇ 2-(2-hydroxyethoxy) ethoxy ⁇ ethanesulfonate (“SE3”) and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol.
  • Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2-hydroxyethoxy)- ethoxyjethanesulfonate and/or sodium 2-[2- ⁇ 2-(2-hydroxyethoxy)ethoxy ⁇ ethoxy]- ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ O 3 S[CH 2 CH 2 O]3.5)- and B is a unit from 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; (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With a proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.; (Ill) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly( vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S.
  • bleaching agents may be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning pu ⁇ oses that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof.
  • Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781 , Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1 , 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4.634,551, issued January 6, 1987 to Burns et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1 ,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 'micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in
  • amido-derived bleach activators are those of the formulae: R!N(R5)C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms. R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and 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 the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul- fonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof 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, inco ⁇ orated herein by reference.
  • a highly preferred activator of the benzoxazin- type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • R° is H or an alkyl, aryl, alkoxyaryl. or alkaryl group containing from 1 to about 12 carbon atoms.
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3.5.5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.
  • 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. 5,1 14,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn IV 2(u-O)3(l,4,7-trimethyl-l,4,7-triazacyclo- nonane)2(PF6)2, Mn I ⁇ 2(u-O) j (u-OAc)2( 1 ,4,7-trimethy 1- 1 ,4,7-triazacyclononane)2_ (ClO 4 ) 2 , Mn IV 4(u-O) 6 (l,4,7-triazacyclononane)4(ClO 4 )4, Mn ⁇ I Mn IV 4(u-O) ⁇ (u- OAc)2.(l ,4,7-trimethyl-l,4,7-triazacyclononane)2(ClO4)3, Mn IV (1.4,7-trimethyl- 1 ,4,7-triazacyclononane)- (OCH3)3(PF6),
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,1 14,61 1.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,1 17; 5,274,147; 5,153,161; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the 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 about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech.. (1983), 2, pages 1-94.
  • the most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] T v , wherein "OAc” represents an acetate moiety and "T y " is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH3)5OAc](OAc)2; [Co(NH 3 ) 5 OAc](PF6)2; [Co(NH3) 5 OAc](SO 4 ); [Co(NH3)5OAc](BF 4 )2; and [Co(NH 3 )5OAc](NO 3 )2 (herein "PAC").
  • the automatic dishwashing compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical automatic dishwashing compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.
  • 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 about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.
  • 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 11 1,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 1 11,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • Patent 4,548,744, Connor issued October 22, 1985.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. See U.S. Patent 4,891 ,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.
  • Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Polymeric Dispersing Agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water- soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl. U.S. Patent 3,308,067, issued march 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7.000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1 : 1 , more preferably from about 10: 1 to 2: 1.
  • Water- soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/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.
  • polyethylene glycol Another polymeric material which can be included is polyethylene glycol
  • PEG polystyrene resin
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these pu ⁇ oses range from about 500 to about 100,000, preferably from about 1,000 to about
  • 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 about 10,000.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be inco ⁇ orated at levels typically from about 0.01% to about 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5- dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. 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. Other 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-na ⁇ tho[l ,2-d]triazoles; 4,4'-bis-(l,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the amino- coumarins.
  • these brighteners include 4-methyl-7-diethyI- amino coumarin; l,2-bis(benzimidazol-2-yl)ethylene; 1 ,3-diphenyl-pyrazolines; 2,5- bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[l,2-d]oxazole; and 2-(stilben-4-yl)- 2H-naphtho[l ,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, 4g
  • manganese phthalocyanine peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%. and more preferably from about 0.05% to about 2%.
  • the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A x -P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units;
  • x is 0 or 1; and
  • R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures:
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10: 1 to 1 :1 ,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1 ,000.000: more preferred 1,000 to 500.000; most preferred 5.000 to 100,000. This preferred class of materials can be referred to as "PVNO". W ⁇ 4 Q 9
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 1 13.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4: 1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone 5 (“PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, inco ⁇ orated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having 0 an average molecular weight from about 500 to about 100,000, preferably from about 1 ,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50: 1 , and more preferably from about 3: 1 to about 10: 1.
  • the detergent compositions herein may also optionally contain from about 5 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • R ⁇ is selected from anilino. N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • 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 Co ⁇ oration. Tinopal- UN PA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino- 6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
  • R] is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the 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) with such selected optical brighteners (e.g., Tinopal UNPA- GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor.
  • Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines. alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.
  • MGDA water-soluble methyl glycine diacetic acid
  • these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be inco ⁇ orated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration 5?
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • 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-C4o ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 1 10°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4.265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • Other silicone suds suppressors are disclosed in U.S. Patent 3,455.839 which relates to compositions and processes for defoaming aqueous solutions by inco ⁇ orating therein small amounts of polydimethylsiloxane fluids.
  • German Patent Application DOS 2,124,526 Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25 °C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiOj/2 units and to Si ⁇ 2 units of from about 0.6: 1 to about 1.2:1 ; and
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene- polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1 ) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorgano
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400. and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 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 glycolxopolymer of polyethylene-polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably -do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC LI 01.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,1 18 and EP 150,872.
  • the secondary alcohols include the C ⁇ -Ci ⁇ alkyl alcohols having a C ] -C i 6 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5: 1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • the compositions herein will generally comprise from 0% to about 10% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to about 5%, by weight, of the detergent composition.
  • fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • Alkoxylated Polycarboxylates Alkoxylated Polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are 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 acrylate units. The side- chains are of the formula -(CH2CH2O) m (CH2) n CH3 wherein m is 2-3 and n is 6- 12. The side-chains are ester-linked to the polyacrylate "backbone” to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with 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 - Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from about 0.01% to about 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from about 0.0001% to about 90% of a finished perfume composition.
  • Example VIII Several perfume formulations are set forth in Example VIII, hereinafter.
  • Non-limiting examples of 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 1,6,10- trimethyl-2,5,9-cyclododecatrien-l-yl ketone; 7-acetyl- 1,1, 3, 4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl- 1,1 -dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-l,l,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-l,l,2,6-tetramethyl indane; 1
  • perfume materials are those that provide the largest odor improvements in finished product compositions containing cellulases.
  • These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3- (para-tert-butylphenyl)-propionaldehyde; 7-acetyl- 1,2,3 ,4,5,6,7,8-octahydro- 1,1 , 6,7- tetramethyl naphthalene; benzyl salicylate; 7-acetyl- 1,1 , 3, 4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)- propionaldehyde; 1, 3,4,6,7, 8-hexahydro-4,6,6, 7,8,
  • perfume materials include essential oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
  • Still other perfume chemicals include phenyl ethyl alcohol, 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.
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
  • suds boosters such as the C ⁇ Q-C ⁇ alkanolamides can be inco ⁇ orated into the compositions, typically at 1%-10% levels.
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • water-soluble magnesium and/or calcium salts such as MgCb, MgSO4, CaCl2, CaSO4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C 13.15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • EO 7 ethoxylated alcohol
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 1 1, preferably between about 7.5 and 10.5.
  • Liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9.0.
  • Laundry products are typically at pH 9-1 1. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • PEG4000 Polyethylene glycol; average molecular weight 4000
  • SRA-1 Soil release agent methyl cellulose; molecular weight about
  • the formulator wishes to prepare an admixable particle containing the alkoxylated cationics for use in, for example, a high density granular detergent, it is preferred that the particle composition not be highly alkaline. Processes for preparing high density (above 650 g/I) granules are described in U.S. Patent 5,366,652. Such particles may be formulated to have an effective in-use pH of 9, or below, to avoid the odor of impurity amines.
  • Examples I and II illustrate granular detergent compositions of the invention.
  • the AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any surfactants AQA-2 through AQA-22 or other AQA surfactants herein.
  • CocoMeEO2* 0.47 3.13 Builder-Alkalinity SKS-6 3.29 21.94 Copolymer 7.10 47.36 Zeolite 8.40 56.03
  • AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any surfactants AQA-2 through AQA-22 or other AQA surfactants herein.
  • the individual surfactants are weighed and mixed in the 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 the 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, Cotton dress shirt ( 1 )
  • DKPE is double-knit polyester.
  • DMO is dirty motor oil.
  • Test Results I show the performance of compositions according to the present invention using CoCoMeEO2 plus a mixture of LAS/AS and Test Results II show the performance using CoCoMeEOlO* plus LAS/AS, as compared with CoCoMeEO2/LAS.
  • performance is measured against various soil types, i.e., body soil, builder sensitive soil, bleach sensitive soil, surfactant sensitive soil and socks.
  • EO10 indicates two poly-EO chains with an overall average of 10 EO units in the molecule, typically "(but not restricted to) about 5 per chain.
  • compositions of Examples I and II are modified by removing the bleach system (NOBS/PB j ).
  • the AQA level is adjusted to about 1.5% of the composition (range 0.5-5%). Quite satisfactory cleaning performance on a variety of soils and stains is secured even in the absence of bleach.
  • compositions of Examples I, II and III can also be provided in the form of tablets by means of standard tabletting and compaction apparatus.
  • EXAMPLE IV
  • a detergent bar is prepared with the surfactant mixture is prepared using conventional extrusion techniques, and comprises the following: Ingredient % (wt.) Range (% wt.)
  • Sodium diethylenetriamine penta (phosphonate) ⁇ Sokolan CP-5 is maleic-acrylic copolymer ⁇ Balance comprises water (about 2% to 8%, including water of hydration), sodium sulfate, calcium carbonate, and other minor ingredients.
  • the AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any surfactants AQA-2 through AQA-22 or other AQA surfactants herein.
  • EXAMPLE V The following illustrates mixtures of AQA surfactants which can be substituted for the AQA surfactants listed in any of the foregoing Examples. As disclosed hereinabove, 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. Preferably, the AQA surfactants in such mixtures differ by at least about 1.5, preferably 2.5-20, total EO units. Ratio ranges(wt.) for such mixtures are typically in the 10: 1 to 1 : 10 range. Non-limiting examples of such mixtures are as follows.
  • compositions herein can comprise detersive non-AQA surfactants and optional builders at usage levels and ranges as disclosed hereinabove, said compositions also comprising an effective amount of one or more of the following combinations of ingredients:
  • Percarbonate bleach 1 OO- 1 : 1, preferably 1 :20-1 :5 Branched alkyl sulfate 100-1 :2, preferably 1 : 10-1 :3
  • MAP Zeolite P 1 :300- 1 :1, preferably 1 :100-1 :5
  • Polymeric Dispersant* *** 1 :10-10:1, preferably 1 :5-1:1
  • laundry detergent compositions prepared using one or more foregoing combinations of ingredients can optionally be built with any non-phosphate or phosphate builders, or mixtures thereof, typically at levels of from 5% to about 70%, by weight of finished composition.
  • any non-phosphate or phosphate builders, or mixtures thereof typically at levels of from 5% to about 70%, by weight of finished composition.
  • the "tallow” chain length AS is particularly useful under hot water conditions, up to the boil.
  • "Coconut” AS is preferred for cooler wash temperatures.
  • the mixtures of alkyl sulfate/anionic surfactants noted above are modified by inco ⁇ orating a nonionic non-AQA surfactant therein at a weight ratio of anionic (total) to nonionic in the range of about 25: 1 to about 1 :5.
  • the nonionic surfactant can comprise any of the conventional classes of ethoxylated alcohols or alkyl phenols, alkylpolyglycosides or polyhydroxy fatty acid amides (less preferred), or mixtures thereof, such as those disclosed hereinabove.
  • Highly preferred combinations of the foregoing non-AQA surfactants will comprise from about 3% to about 60%, by weight, of the total finished laundry detergent composition.
  • the finished compositions will preferably comprise from about 0.25% to about 3.5%, by weight, of the AQA surfactant.
  • EXAMPLE VIII This Example provides perfume formulations (A-C) for inco ⁇ oration into any of the foregoing Examples of AQA-containing detergent compositions, but is not intended to be limiting thereof.
  • the various ingredients and levels are set forth below.
  • Total 100.0 100.0 100.0 100.0 The foregoing perfume compositions are admixed or sprayed-onto (typically at levels up to about 2% by weight of the total detergent composition) any of the AQA surfactant-containing cleaning compositions disclosed herein. Improved deposition and/or retention of the perfume or individual components thereof on the surface being cleaned is thus secured.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des tensioactifs cationiques alcoxylés et des mélanges de ceux-ci qui sont utilisés dans des compositions détergentes comprenant un mélange de tensioactifs d'alkyle sulfate et d'alkylbenzène sulfonate.
EP97925591A 1996-05-17 1997-05-16 Composition detergente Withdrawn EP0918834A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US1788496P 1996-05-17 1996-05-17
US17884 1996-05-17
PCT/US1997/008279 WO1997044420A2 (fr) 1996-05-17 1997-05-16 Composition detergente

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EP0918834A2 true EP0918834A2 (fr) 1999-06-02

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EP (1) EP0918834A2 (fr)
JP (1) JPH11511793A (fr)
KR (1) KR20000011102A (fr)
CN (1) CN1225672A (fr)
AR (1) AR007771A1 (fr)
AU (1) AU3068397A (fr)
BR (1) BR9709320A (fr)
CA (1) CA2254955A1 (fr)
HU (1) HUP9902979A2 (fr)
MX (1) MX9809625A (fr)
WO (1) WO1997044420A2 (fr)
ZA (1) ZA974222B (fr)

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Publication number Priority date Publication date Assignee Title
US5994285A (en) * 1999-06-14 1999-11-30 Colgate-Palmolive Co. Liquid laundry detergent composition containing ethoxylated amine quaternary surfactant
KR20050077583A (ko) 2004-01-28 2005-08-03 삼성전자주식회사 제빙장치
DE602005006796D1 (de) * 2005-08-05 2008-06-26 Procter & Gamble Teilchenförmige Textilbehandlungsmittelzusammensetzung enthaltend Silikone, Schichtsilikate und anionische Tenside
CA2908771C (fr) * 2013-05-02 2019-05-21 Ecolab Usa Inc. Composition detergente concentree pour une meilleure elimination de l'amidon dans des applications de lavage de vaisselle
JP2015196701A (ja) * 2014-03-31 2015-11-09 花王株式会社 固体洗浄剤
CN114892178B (zh) * 2022-05-12 2023-11-03 武汉奥邦表面技术有限公司 一种无硅无磷环保水基除油剂及其应用

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DE3366705D1 (en) * 1982-03-01 1986-11-13 Procter & Gamble Detergent composition
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See references of WO9744420A2 *

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CA2254955A1 (fr) 1997-11-27
MX9809625A (en) 1999-03-01
AU3068397A (en) 1997-12-09
WO1997044420A3 (fr) 1997-12-24
CN1225672A (zh) 1999-08-11
AR007771A1 (es) 1999-11-24
ZA974222B (en) 1998-12-28
WO1997044420A2 (fr) 1997-11-27
JPH11511793A (ja) 1999-10-12
HUP9902979A2 (en) 2000-01-28
BR9709320A (pt) 1999-08-10
KR20000011102A (ko) 2000-02-25

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