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WO1998015607A2 - Diamines quaternisees alkoxylees, ingredients pour compositions detergentes - Google Patents

Diamines quaternisees alkoxylees, ingredients pour compositions detergentes Download PDF

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Publication number
WO1998015607A2
WO1998015607A2 PCT/US1997/017309 US9717309W WO9815607A2 WO 1998015607 A2 WO1998015607 A2 WO 1998015607A2 US 9717309 W US9717309 W US 9717309W WO 9815607 A2 WO9815607 A2 WO 9815607A2
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WO
WIPO (PCT)
Prior art keywords
units
alkyl
formula
mixtures
moiety
Prior art date
Application number
PCT/US1997/017309
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English (en)
Other versions
WO1998015607A3 (fr
Inventor
Jay Ian Kahn
Kakumanu Pramod
Jennifer Ann Leupin
Daniel Stedham Connor
Kinuko Yasuda
Rajan Keshav Panandiker
Francesco De Buzzaccarini
Josephine Ling Kong-Chan
Eugene Paul Gosselink
Ryohei Ohtani
Chanchal Kumar Ghosh
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU46533/97A priority Critical patent/AU4653397A/en
Priority to BR9712498-2A priority patent/BR9712498A/pt
Priority to JP10517567A priority patent/JP2000503723A/ja
Priority to CA002267294A priority patent/CA2267294A1/fr
Priority to EP97945302A priority patent/EP0929628A2/fr
Publication of WO1998015607A2 publication Critical patent/WO1998015607A2/fr
Publication of WO1998015607A3 publication Critical patent/WO1998015607A3/fr

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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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • the present invention relates to detergent compositions which comprise selected ingredients, including selected quatemized ethoxylated, alkylene diiamine compounds.
  • laundry detergents and other cleaning compositions present a considerable challenge, since modem compositions are required to remove a variety of soils and stains from diverse substrates.
  • laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashers, and the like all require the proper selection and combination of ingredients in order to function effectively.
  • such detergent compositions will contain one or more types of surfactants which are designed to loosen and remove certain soils and stains.
  • some detergent adjuncts and surfactants 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.
  • the soils once removed from the substrate should be dispersed or suspended in the wash liquor to minimize redeposition on the substrate.
  • Clay soil particles generally comprise negatively charged layers of aluminosilicates and positively charged cations (e.g. calcium) which are positioned between and hold together the negatively charged layers.
  • a variety of models can be proposed for compounds which would have clay soil removal properties.
  • One model requires that the compound have two distinct characteristics. The first is the ability of the compound to adsorb onto the negatively charged layers of the clay particle. The second is the ability of the compound, once adsorbed, to push apart (swell) the negatively charged layers so that the clay particle loses its cohesive force and can be removed in the wash water.
  • a model proposed for the anti-redeposition action of the positively charged anti-redeposition compounds is as follows. Adsorption of the positively charged molecule on the surface of clay particles in the wash water gives the particles the dispersancy properties of the molecule. As more and more of these compounds adsorb onto the suspended clay soil particles, the latter become encased within a hydrophilic layer. As such, the hydrophilically encased soil is prevented from redepositing on fabrics, in particular hydrophobic fabrics such as polyester, during the laundering cycle.
  • AQD alkoxylated quaternary diamine
  • the AQD soil removal/dispersants used in the present manner provide substantial advantages to the formulator over other dispersants known heretofore.
  • the AQD dispersants herein are compatible with the preferred alkyl sulfate, alkyl ethoxylated sulfate, and amidopropylamine detersive surfactants.
  • the AQD dispersants are formulatable over a broad pH range from 5 to 12.
  • the AQD dispersants are also compatible with various perfume ingredients, unlike other quats known in the art.
  • the AQD dispersants 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 AQD dispersants 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 AQD dispersants herein remove such polar lipids and keep them suspended in the aqueous medium, rather than allowing them to redeposit onto the cleaned fabrics.
  • the AQD dispersants 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.
  • the combination of the AQD dispersants herein with specific ethoxylated polyethyleneimines with a MW of less than about 5,000 provide synergistic cleaning benefits.
  • Other advantages for the AQD dispersant 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.
  • the AQD dispersants 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. In contrast, the alkoxylated AQD dispersants are believed to provide more open associations with clays, which are then more readily removed from fabric surfaces. Whatever the reason, the compositions herein containing the AQD dispersants provide improved performance over conventional dispersants with special regard to clay soil removal.
  • compositions without bleach the formulator my choose to use somewhat higher levels of AQD dispersants to provide enhanced performance benefits.
  • These benefits may be associated with the ability of the AQD dispersants herein to modify the solution characteristics of conventional anionic surfactants such as alkyl sulfates or alkyl ethoxylated sulfates to allow more of the surfactants to be available to perform their cleaning function.
  • the detergent composition is "underbuilt” with respect to calcium and/or magnesium water hardness ions
  • Mixtures of AQD dispersants 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 AQD dispersants are disclosed in the Examples hereinafter.
  • the AQD dispersants used in the manner of the present invention, successfully address many of the problems associated with the formulation of modem, high- performance detergent compositions.
  • these dispersants 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 relates to cleaning compositions comprising or prepared by combining an effective amount of certain alkoxylated (especially ethoxylated) quaternary poly amine dispersants and one or more detersive (including fabric care) adjuncts, as disclosed hereinafter.
  • alkoxylated quaternary diamine (AQD) dispersants used in the present invention are of the general formula:
  • R is selected from linear or branched C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-Ci2 dialkylarylene, [(CH2CH2 ⁇ ) q CH2CH2J- and - CH 2 CH(OH)CH2 ⁇ -(CH2CH2 ⁇ ) q CH2CH(OH)CH2j- where q is from about 1 to about 100.
  • Each R ⁇ is independently selected from C1-C4 alkyl, C7-C12 alkylaryl, or A.
  • A is of the formula:
  • R3 where R3 is selected from H or C1-C3 alkyl, n is from about 5 to about 100 and B is selected from H, C1-C4 alkyl, acetyl, or benzoyl; X is a water soluble anion
  • R is selected from C4 to Cg alkylene
  • R ⁇ is selected from C ⁇ -C2 alkyl or C2-C3 hydroxyalkyl
  • A is:
  • R3 where R3 is selected from H or methyl, and n is from about 10 to about 50.
  • R is linear or branched Cg
  • Rl is methyl
  • R3 is H
  • n is from about 20 to about 50.
  • AQD's can be synthesized following the methods outline in US. Patent No. 4,664,848, or other ways known to those skilled in the art.
  • the levels of the AQD dispersants used to prepare finished laundry detergent compositions can range from about 0.1% to about 10%, typically from about 0.4% to about 5%, by weight.
  • the present invention encompasses the use of the aforesaid AQD dispersants to enhance the overall cleaning performance of detergent compositions which contain otherwise known ingredients. It has now been discovered that the overall cleaning performance of such detergent compositions can be improved by the incorporation of relatively small quantities of the AQD dispersants. Surprisingly, laundry cleaning performance with respect not only to greasy soils, but also body soil, builder sensitive soil, bleach sensitive soil, as well as food stains and sock soil is enhanced.
  • the usage levels and mode of use of the AQD dispersants in detergent formulations of various types will depend on the desires of the formulator. Representative, but non- limiting, examples of such formulations include the following.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a specific surfactants, including alkyl sulfate (AS) and alkyl alkoxylated, especially ethoxylated, sulfates (AES).
  • AS alkyl sulfate
  • AES ethoxylated, sulfates
  • the compositions with AQD dispersants and these surfactants are substantially free of (i.e., have less than 5%, preferably less than 1%) of linear alkyl benzene sulfonate (LAS).
  • LAS linear alkyl benzene sulfonate
  • the AQD is combined with linear alkyl benzene sulfonate.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and selected amine surfactants, such as amidopropyldimethylamines.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a polyester or oligoester soil release agent, especially a non-cotton soil release polymer or agent.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a polyethoxyated polyethyleneamine polymers or ethoxylated polyethyleneimine (PEI) polymers with a molecular weight of less than about 5,000, preferably less than about 2,000, more preferably from about 600 to about 1,000.
  • PEI polyethoxylated polyethyleneimine
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and an amylase or lipase enzyme, or mixtures thereof.
  • examples of such formulations include the following:
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and chelants, especially ethylenediaminedisuccinate (EDDS) chelant.
  • EDDS ethylenediaminedisuccinate
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a cellulase or protease enzyme, or mixtures thereof.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and an alkyl polyglycoside or polyhydroxy fatty acid amide surfactant.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a non-aqueous liquid carrier matrix.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a detergent granule having a bulk density of 650 g/L, or greater.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a source of magnesium ions, calcium ions, or mixtures thereof.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a dye-transfer inhibitor.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a manganese, cobalt or iron bleach catalyst.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a zeolite P or "MAP" builder.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a Mineral Builder.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and an oxygen bleach such as percarbonate bleach.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and one or more bleach activators.
  • Detergent compositions which comprise conventional detersive ingredients, an AQD dispersant and a photobleach.
  • the AQD dispersants used in the manner of the present invention also provide an improved method for removing and suspending the following soils and stains from fabrics: 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 AQD compounds herein have the advantage that they are commercially available and are compatible with the various detersive ingredients such as builders, detersive enzymes, and the like, which are used in many modem, high quality, fully-formulated laundry detergents. Moreover, the AQD compounds exhibit satisfactory stability in the presence of the bleach ingredients commonly used in laundry detergent-plus-bleach compositions. Importantly, the AQD dispersants herein exhibit superior performance with respect to the removal of body soils and everyday soils such as sock soil. In short, 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 AQD dispersants herein provide improved fabric cleaning performance in the presence of bleach. This improvement in cleaning is seen at usage levels as low as 3 parts per million (ppm) of the AQD in the laundry liquor and is believed to be associated with increased perhydrolysis.
  • the AQD dispersants herein provide improved (even synergistic) performance with amylase, especially Duramyl®, and lipase, especially Lipolase Ultra®, 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 AQD dispersant.
  • Greasy/oily "everyday "soils are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter.
  • lipase enzymes can be used to convert any remaining triglycerides to fatty acids through- the-wash.
  • Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co.
  • Lipase P Lipase P
  • Lipase P Lipase P
  • suitable lipases are lipases such as Ml Lipase ⁇ and Lipomax ⁇ - (Gist-Brocades).
  • suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • Chromobacter viscosum e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan
  • Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoy
  • Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826.
  • D native lipase ex Humicola lanuginosa aspartic acid
  • L Leucine
  • the substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • the Humicola lanuginosa strain DSM 4106 is used.
  • the lipase variant (D96L) may be added in an amount corresponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor.
  • Lipase enzyme is incorporated into the composition in accordance with the invention at a level of from 50 LU to 8500 LU per liter wash solution.
  • the variant D96L is present at a level of from 100 LU to 7500 LU per liter of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.
  • the lipases and or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
  • amylase enzymes include those described in WO95/26397 and in co- pending application by Novo Nordisk PCT/DK96/00056. These enzymes are incorporated into 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 total weight composition.
  • Specific amylase enzymes for use in the detergent compositions of the present invention therefore include :
  • ⁇ -amylases characterised 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.
  • Phadebas® ⁇ -amylase activity assay is described at pages 9-10, WO95/26397.
  • ⁇ -amylases according (a) comprising the amino sequence shown in the SEQ ID listings in the above cited reference, or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown in the SEQ ID listing.
  • ⁇ -amylases according (a) comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-T -Tyr-Leu-Pro-Asn- Asp.
  • a polypeptide is considered to be X% homologous to the parent amylase if a comparison of the respective amino acid sequences, performed via algorithms, such as the one described by Lipman and Pearson in Science 227, 1985, p. 1435, reveals an identity of X%
  • ⁇ -amylases according (a-c) wherein the ⁇ -amylase is obtainable from an alkalophilic Bacillus species; and in particular, from any of the strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.
  • the term "obtainable from” is intended not only to indicate an amylase produced by a Bacillus strain byt also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in an host organism transformed with said DNA sequence.
  • Variants of the following parent ⁇ -amylases which (i) have one of the amino acid sequences shown in corresponding respectively to those ⁇ -amylases in (a-e), or (ii) displays at least 80% homology with one or more of said amino acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an ⁇ -amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence wich hybridizes with the same probe as a DNA sequence encoding an ⁇ -amylase having one of said amino acid sequence; in which variants :
  • At least one amino acid residue of said parent ⁇ -amylase has been deleted; and/or 2.at least one amino acid residue of said parent ⁇ -amylase has been replaced by a different amino acid residue; and/or 3. at least one amino acid residue has been inserted relative to said parent ⁇ -amylase; said variant having an ⁇ -amylase activity and exhibiting at least one of the following properties relative to said parent ⁇ -amylase : increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or ⁇ - amylolytic activity at neutral to relatively high pH values, increased ⁇ -amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for ⁇ -amylase variant to the pH of the medium.
  • amylases suitable herein include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPID ASE®, 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.
  • 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 11, measured versus the above-identified reference-point amylase. Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597.
  • Stability-enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly preferred amylases herein have the 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 incorporated WO 9402597, Novo, Feb.
  • 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.
  • the alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted CI Q-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C ⁇ -Cjg alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted CI Q-C24 al
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include ethanol-, triethanol-, methyl- , dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (C12- Ci5E(1.0)M), C12-C15 alkyl polyethoxylate (2.25) sulfate (C ⁇ 2 -C ⁇ 5 E(2.25)M), C 12 - C15 alkyl polyethoxylate (3.0) sulfate (Ci2-Ci5E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C12-C15E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a Cg-Cjg hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci fj-Ci alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a Cg-Cjg hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci fj-Ci alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substitute
  • methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • Commerical alkyl alkoxylate sulfates comprise a mixture of compounds with varying degrees of alkoxylation.
  • the lower the average degree of ethoxylation of a given sample, the higher the level of alkyl sulfate (EO 0) which may be present in the mixture.
  • the total amount of alkyl sulfate present in the detergent compositions herein include not only the alkyl sulfate added to the composition but also any alkyl sulfate which may be present in the alkyl alkoxyate sulfate surfactant mixture.
  • the benefits associated with the AQD dispersant, and its combination with ethoxylated polyethyleneimines (PEI), are greatly enhanced when the surfactant system of the detergent comprises sodium alkylethoxysulfate (AES) and nil alkyl sulfate and alkylbenzenesulfonate.
  • AES sodium alkylethoxysulfate
  • nil alkyl sulfate and alkylbenzenesulfonate By “nil” is meant less than 5%, preferably less than 1%.
  • amine - Suitable amine surfactants for use herein include amines according to the formula:
  • R 4 wherein R ⁇ is a C6-C12 alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-O(R5)) wherein R5 is H or methyl.
  • Preferred amines include the following:
  • R ⁇ is a C6-C12 alkyl group and R5 is H or CH3.
  • the amine is described by the formula:
  • Particularly preferred amines include those selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-Ci 2 bis(hydroxyethyl)amine, Cg-Ci 2 bis(hydroxyisopropyl)amine, and Cg-Ci 2 amido-propyl dimethyl amine, and mixtures.
  • This invention also provides detergent compositions which deliver effective cleaning of greasy/oily everyday soils via use of percarbonate bleach with an AQD dispersants as disclosed herein.
  • Percarbonate which delivers peroxide bleach into the wash, is a cornerstone technology of mode , 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 AQD dispersants and percarbonate bleach deliver superior cleaning and whiteness performance.
  • 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 AQD dispersant of the present type. Everyday soil cleaning and whiteness benefits for hydrophobic bleach activators and peracids have already been demonstrated. Such materials are, to a limited degree, able to penetrate complex/greasy oily soils. It has now been found that detergent and bleach compositions containing AQD and hydrophobic bleach activators (including preformed peracids) deliver superior cleaning and whiteness performance.
  • 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 AQD dispersants 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 AQD dispersants herein and polyethoxylated-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) AQD action on the stain surface to prevent lime soap formation and to lift off any calcium soaps present, thereby facilitating improved polymer deposition; (2) AQD providing solubilization deep into the soil, while the polymer acts as a "grease removal shuttle", stripping out the AQD-solubilized stain components and dispersing them into the wash liquor.
  • the preferred polyethoxylated-polyamines useful herein are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected by moieties having longer R units than the parent PAA's, PAI's, PEA's or PEI's.
  • a common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and teraethylenepentamine (TEPA).
  • the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
  • Preferred amine polymer backbones comprise R units that are C2 alkylene (ethylene) units, also known as polyethylenimines (PEI's).
  • Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4:1, however PEI's having a ratio of m to n of about 2: 1 are most preferred.
  • Preferred backbones, prior to modification have the general formula:
  • PEI's prior to modification, will have a molecular weight greater than about 200 daltons.
  • the relative proportions of primary, secondary and tertiary amine units in the polyamine backbone will vary, depending on the manner of preparation.
  • Each hydrogen atom attached to each nitrogen atom of the polyamine backbone chain represents a potential site for subsequent substitution, quatemization or oxidation.
  • polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951; all herein incorporated by reference.
  • modified cotton soil release polymers of the present invention comprising PEI's, are illustrated in Formulas I - IV:
  • Formula I depicts a cotton soil release polymer comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )7H, having the formula
  • Formula I This is an example of a cotton soil release polymer that is fully modified by one type of moiety.
  • Formula II depicts a cotton soil release polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ ) ⁇ H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides, said cotton soil release agent having the formula
  • Formula II Formula III depicts a cotton soil release polymer comprising a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quatemized.
  • the substituents are polyoxyalkyleneoxy units, -(CH2CH2 ⁇ )7H, or methyl groups.
  • the modified PEI cotton soil release polymer has the formula
  • Formula III Formula IV depicts a cotton soil release polymer comprising a PEI backbone wherein the backbone nitrogens are modified by substitution (i.e. by -(CH2CH2O)7H or methyl), quatemized, oxidized to N-oxides or combinations thereof.
  • the resulting cotton soil release polymer has the formula
  • not all nitrogens of a unit class comprise the same modification.
  • the present invention allows the formulator to have a portion of the secondary amine nitrogens ethoxylated while having other secondary amine nitrogens oxidized to N-oxides. This also applies to the primary amine nitrogens, in that the formulator may choose to modify all or a portion of the primary amine nitrogens with one or more substituents prior to oxidation or quatemization. Any possible combination of E groups can be substituted on the primary and secondary amine nitrogens, except for the restrictions described herein above.
  • the present invention employs an "effective amount" of the AQD dispersant to improve the performance of cleaning compositions which contain other adjunct ingredients.
  • an “effective amount” of the AQD dispersants 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 the target soils and stains.
  • the formulator will use sufficient AQD to at least directionally improve cleaning performance against such stains.
  • the formulator will use sufficient AQD to at least directionally improve cleaning performance against such soil.
  • the AQD dispersants 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 AQD dispersants are used herein in detergent compositions in combination with 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.
  • the amount of AQD dispersant used in a machine- wash laundering context can vary, depending on the habits and practices of the user, the type of washing machine, and the like.
  • one heretofore unappreciated advantage of the AQD dispersants is their ability to provide at least directional improvements in performance over a spectrum of soils and stains.
  • compositions can also be formulated using an effective amount of the AQD dispersants in the manner of this invention.
  • Such compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surface cleaners, shampoos, personal cleansing bars, laundry bars, and the like. Since the habits and practices of the users of such compositions show minimal variation, it is satisfactory to include from about 0.25% to about 5%, preferably from about 0.45% to about 2%, by weight, of the AQD dispersants in such compositions.
  • Nonlimiting examples of anionic surfactants useful herein typically at levels from about 1% to about 55%, by weight, primary, branched-chain and random C10-C20 ⁇ kyl sulfates ("AS"), the Cio-C ⁇ g secondary (2,3) alkyl sulfates of the formula CH3(CH 2 ) x (CHOSO 3 " M ) CH3 and CH3 (CH 2 )y(CHOSO 3 " M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Cio-Cjg alpha-sulfonated fatty acid esters, the CiQ-Cj sulfated alkyl polyglycosides, the Cjn-Cig alkyl alkoxy sulfates ("AE X S"; especially
  • Ci2- ] betaines and sulfobetaines can also be included in the overall compositions.
  • C ⁇ 0-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10"C 16 soaps may be used.
  • Other conventional useful surfactants are listed in standard texts.
  • compositions of the invention are substantiall free of Cj i-Cj alkyl benzene sulfonates ("LAS").
  • LAS Cj i-Cj alkyl benzene sulfonates
  • 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), Ci n-Cig glycerol ethers, and the like.
  • AE alkoxylated alcohols
  • PFAA's polyhydroxy fatty acid amides
  • APG's alkyl polyglycosides
  • Ci n-Cig 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 15-S-9 (the condensation product of C11 -C15 linear alcohol with 9 moles ethylene oxide) and Tergitol M 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol M 23-3 (the condensation product of C12-C13 linear alcohol with 3 moles of ethylene oxide), Neodol TM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide) and Neodol ⁇ 45-5 (the condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; Kyro EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Gen
  • Another class of preferred nonionic surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
  • R ⁇ is H, or C 1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R ⁇ is C5.31 hydrocarbyl, and 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 C j ⁇ _i5 alkyl or l5-17 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 Ci2-C ⁇ g and C12-C14 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
  • R ⁇ 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. To prepare these compounds, 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 Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of ethylene oxide 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.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of 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 PluronicT surfactants, marketed by BASF.
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 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.
  • this type of nonionic surfactant include certain of the commercially available Tetronic ⁇ M compounds, marketed by BASF.
  • 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 AQD 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 amorphous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
  • silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non-structured-liquid types
  • borates e.g., for pH-buffering purposes
  • sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing detergent compositions.
  • Builder mixtures sometimes termed “builder systems” can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH- buffers or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein.
  • preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from 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 limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.
  • Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1, including, particularly for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp. under the tradename BRITESIL®, e.g., BRITESIL H2O; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline layered aluminium-free ⁇ -Na2Si ⁇ 5 morphology silicate marketed by Hoechst and is preferred especially in granular laundry compositions.
  • BRITESIL® e.g., BRITESIL H2O
  • layered silicates e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck.
  • layered silicates such as those having the general formula NaMSi x ⁇ 2 ⁇ +l-yH2 ⁇ 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 O ySi ⁇ 2 .zM'O wherein M is Na and/or K, M' is Ca and or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995.
  • Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and 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 incorporated in liquids, pastes or gels. Suitable for the present purposes are those having empirical formula: [M z (Al ⁇ 2) z (Si ⁇ 2) v ]'xH2 ⁇ wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
  • Aluminosilicates can be crystalline or amorphous, naturally-occurring or synthetically derived. An 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; carboxymethyloxysuccinic 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, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrates e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid detergents, due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations.
  • alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates, e.g., those of U.S. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable antiscaling properties.
  • detersive surfactants or their short-chain homologs also have a builder action. For unambiguous formula accounting purposes, when they have surfactant capability, these materials are summed up as detersive surfactants.
  • Prefe ⁇ ed 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, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (prefe ⁇ ed), 2-pentadecenylsuccinate, and the like.
  • Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C ⁇ -Cjg monocarboxylic acids, can also be incorporated into the compositions as surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity.
  • Other suitable polycarboxylates are disclosed in U.S. 4,144,226, Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.
  • Mineral Builders Waters of hydration or anions other than carbonate may be added provided that the overall charge is balanced or neutral.
  • a water-soluble cation selected from the group consisting of hydrogen, water- soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly prefe ⁇ ed.
  • noncarbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof.
  • Prefe ⁇ ed builders of this type in their simplest forms are selected from the group consisting of Na 2 Ca(CO3) , K2Ca(CO3)2, Na2Ca 2 (CO3)3, NaKCa(CO3) 2 , NaKCa2(CO3)3, K2Ca2(CO3)3, and combinations thereof.
  • An especially prefe ⁇ ed material for the builder described herein is Na2Ca(CO3)2 in any of its crystalline modifications.
  • Suitable builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any one or combinations of the following minerals:sammlungite, Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite, Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettnerite, Khanneshite, LepersonniteGd, Liottite, MckelveyiteY, Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite, and Zemkorite.
  • Prefe ⁇ ed mineral forms include
  • 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. Prefe ⁇ ed selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are prefe ⁇ ed, 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.
  • Prefe ⁇ ed detersive enzymes are hydrolases such as proteases, amylases and lipases.
  • Prefe ⁇ ed enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases.
  • Highly prefe ⁇ ed 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.
  • prefe ⁇ ed proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • an especially prefe ⁇ ed protease, refe ⁇ ed to as "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, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A.
  • 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®(Novo) are especially useful. See also WO 9117243 to Novo.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various techniques.
  • Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo. Enzyme Stabilizing System - 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 prefe ⁇ ed herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated.
  • Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts co ⁇ esponding 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 incorporated such that different enzymes have maximum compatibility.
  • Other conventional 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
  • 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.
  • Prefe ⁇ ed 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.
  • Prefe ⁇ ed 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 incorporated into the ester structure through one, two, three, four or more positions, without of course forming a densely crosslinked overall structure.
  • Suitable SRA's include: a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P.
  • ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • Gosselink et al for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5- sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • Gosselink et al 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from ni-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400.
  • SRA's also include simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; and the C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December 28, 1976 to Nicol, et al.
  • Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Cj-Cg vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. 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.
  • SRA is an oligomer having empirical formula (CAP) 2 (EG/PG) 5 (T) 5 (SIP) 1 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- 1 ,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • CAP empirical formula
  • CAP CAP
  • CAP preferably modified isethionates
  • 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.
  • a backbone comprising (a) at least one unit selected from the group consisting of dihydroxy
  • Prefe ⁇ ed 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.
  • Prefe ⁇ ed SRA esters in this class include the product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2- hydroxyethoxy)ethoxy ⁇ ethanesulfonate and/or sodium 2-[2- ⁇ 2-(2-hydroxyethoxy)- ethoxy ⁇ ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -O 3 S[CH 2 CH 2 O]3.5)- and B is a unit from 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 py ⁇ olidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S.
  • the non-cotton soil release polymers to be used in the laundry detergent compositions of the present invention are the following.
  • Prefe ⁇ ed non-cotton soil release agent - A Suitable for use in the laundry detergent compositions of the present invention are prefe ⁇ ed non-cotton soil release polymers comprising: a) a backbone comprising: i) at least one moiety having the formula:
  • R ⁇ is C2-Cg linear alkylene, C3-C6 branched alkylene, C5-C7 cyclic alkylene, and mixtures thereof;
  • R ⁇ is independently selected from hydrogen or -L-SO3'M + ;
  • L is a side chain moiety selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and mixtures thereof;
  • M is hydrogen or a salt forming cation;
  • i has the value of 0 or 1 ;
  • one or more capping units comprising: i) ethoxylated or propoxylated hydroxy
  • Rl is arylene, preferably a 1 ,4-phenylene moiety having the formula such that when A units and R ⁇ units are taken together in the formula A-R ⁇ -A they form a terephthalate unit having the formula
  • R2 units are ethyleneoxy or 1,2-propyleneoxy.
  • R ⁇ units are combined with terephthalate moieties to form (A-R ⁇ -A-R ⁇ ) units having the formula
  • R' and R" are either hydrogen or methyl provided that R' and R" are not both methyl at the same time.
  • R units are trifunctional, ester-forming, branching moieties having the formula
  • R 3 units comprise a glycerol moiety which is placed into the soil release polymer backbone to provide a branch point.
  • R- units are combined with terephthalate moieties to form units of the polymer backbone, for example, (A-R ⁇ -A- R3)-A-R1-A units, these units have the formula
  • one terephthalate residue is taken to be a part of the (A-Rl-A-R 3 ) unit while the second terephthalate comprises a part of another backbone unit, such as a (A-R1-A-R2) unit, a (A-R ⁇ A-R 5 ) unit, a -A-R ⁇ A-KR ⁇ Cap)] unit or a second (A-R ⁇ -A-R 3 ) unit.
  • the third functional group which is the beginning of the branching chain, is also typically bonded to a terephthalate residue also a part of a (A-R* -A-R2) unit, a (A-R ⁇ -A- R 5 ) unit, a -A-R ⁇ A-KR ⁇ Cap)] unit or another (A-Rl-A-R 3 ) unit.
  • R ⁇ units are R ⁇ , R 3 or R ⁇ units.
  • R ⁇ units are units having the formula
  • R ⁇ is C2-C6 linear alkylene, C3-C6 branched alkylene, and mixtures thereof; preferably R ⁇ is independently selected from hydrogen or -L-SO3"M + ; wherein L is a side chain moiety selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and mixtures thereof; M is hydrogen or a salt forming cation; i has the value of 0 or 1 ;
  • RlO units that are independently selected from hydrogen or -L-SO3"M + , provided no more than one -L- SO3"M + units is attached to an R ⁇ unit;
  • L is a side chain connecting moiety selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and mixtures thereof.
  • M is a cationic moiety selected from the group consisting of lithium, sodium, potassium, calcium, and magnesium, preferably sodium and potassium.
  • R ⁇ moieties are essentially RlO substituted C2-Cg alkylene chains.
  • the R5 units comprise either one C2-C6 alkylene chain substituted by one or more independently selected R*" moieties (prefe ⁇ ed) or two C2-Cg alkylene chains said alkylene chains joined by an ether oxygen linkage, each alkylene chain substituted by one or more independently selected R ⁇ moieties, that is R ⁇ may comprise two separate R9 units, each of which is substituted by one or more independently selected RlO moieties.
  • Preferably only one carbon atom of each R ⁇ moiety is substituted by an -L- SO3"M + unit with the remaining R ⁇ O substituents comprising a hydrogen atom.
  • each R" comprises a C2 alkylene moiety.
  • one R ⁇ moiety is -L- SO3'M + , preferably the C2 carbon is substituted by the -L-SO3"M + moiety, and the balance are hydrogen atoms, having therefore a formula:
  • R ⁇ moieties consist essentially of units
  • R ⁇ units having the index i equal to 0 wherein R ⁇ units are hydrogen and one R ⁇ units is equal to -L-SO3"M + , wherein L is a side chain connecting moiety selected from the group consisting of alkylene, alkenylene, alkoxyalkylene, oxyalkylene, arylene, alkylarylene, alkoxyarylene and mixtures thereof, refers to the prefe ⁇ ed compounds of the present invention wherein the RlO moieties consist of one -L-SO3"M + moiety and the rest of the Rl" moieties are hydrogen atoms, for example a
  • x for the purposes of the L moiety of the present invention, is from 0 to 20.
  • R ⁇ moieties includes the alkylene poly(oxyalkylene)oxyarylene containing monomer having the general formula
  • x is 0 to 20.
  • a further example of a prefe ⁇ ed monomer resulting in a prefe ⁇ ed R5 unit wherein i is equal to 0, are the sodiosulfopoly(ethyleneoxy)methyl-l,2- propanediols having the formula
  • the prefe ⁇ ed non-cotton soil release agents of the present invention in addition to the afore-mentioned R , R ⁇ , R 3 , R4, and R ⁇ units also comprise one or more capping groups, -(Cap).
  • the capping groups are independently selected from ethoxylated or propoxylated hydroxyethane and propanesulfonate units of the formula (MO3S)(CH2) m (R 1 1 O) n -, where M is a salt forming cation such as sodium or tetralkylammonium as described herein above, R Ms ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 1 to 20, preferably n is from 1 to about 4; sulfoaroyl units of the formula -(O)C(C6H4)(SO3 _ M + ), wherein M is a salt forming cation as described herein above; modified poly(oxyethylene)oxy monoalkyl ether units
  • Most prefe ⁇ ed end capping unit is the isethionate-type end capping unit which is a hydroxyethane moiety, (MO3S)(CH2) m (R 1 1 O) n -, preferably R 1 Ms ethyl, m is equal
  • the value of t is 0 or 1; the value of u is from about 0 to about 60; the value of v is from about 0 to about 35; the value of w is from 0 to 35.
  • the following structure is an example of the prefe ⁇ ed non-cotton soil release polymers of the present invention.
  • 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.
  • a backbone comprising (a) at least one unit selected from the group consisting of
  • CAP terephthaloyl
  • SIP sulfoisophthaloyl
  • CAP poly(ethyleneglycol)
  • DEG di(oxyethylene)oxy units
  • SEG represents units derived from the sulfoethyl ether of glycerin and related moiety units
  • B represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone
  • x is from about 1 to about 12
  • y' is from about 0.5 to about 25
  • y" is from 0 to about 12
  • y'" is from 0 to about 10
  • Prefe ⁇ ed 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.
  • Prefe ⁇ ed SRA esters in this class include the product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2-hydroxy- ethoxy)ethoxy ⁇ ethanesulfonate and or sodium 2-[2- ⁇ 2-(2-hydroxyethoxy)ethoxy ⁇ - ethoxyjethanesulfonate, 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 CH2 ⁇ ]3.5)- and B is a unit from glycerin and the mole ratio EG/PG is about 1.7: 1 as measured by conventional gas chromatography after complete hydrolysis.
  • a second prefe ⁇ ed class of 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
  • ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG ,2-propylene glycol
  • Suitable for use in the laundry detergent compositions of the present invention are prefe ⁇ ed non-cotton soil release polymers comprising: a) one or two terminal units selected from the group consisting of i) -(CH 2 )q(CHSO3M)CH2SO 3 M, ii) -(CH2)q(CHS ⁇ 2M)CH2SO 3 M, iii) -CH 2 CH 2 SO 3 M, iv) and mixtures thereof; wherein q has the value from 1 to about 4,
  • M is a water soluble cation, preferably sodium; b) a backbone comprising: i) arylene units, preferably terephthalate units having the formula:
  • n is from about 1 to about 20; and iii) 1 ,2-propyleneoxy units having the formula:
  • n is from about 1 to about 20
  • the prefe ⁇ ed backbone of this prefe ⁇ ed non-cotton soil release polymer has a backbone comprising arylene repeat units which alternate with the ethyleneoxy and 1 ,2-propyleneoxy units, such that the mole ratio of ethyleneoxy to 1 ,2-propyleneoxy units is from 0:1 to about 0.9:0.1, preferably from about 0:1 to about 0.4:0.6, more preferably the arylene units alternate with essentially 1 ,2-propyleneoxy units.
  • Prefe ⁇ ed non-cotton soil release agent - C Suitable for use in the laundry detergent compositions of the present invention are prefe ⁇ ed non-cotton soil release polymers having the formula
  • Cap [(A-R 1 -A-R 2 ) u (A-R 3 -A-R 2 ) v -A-R4-A-](Cap) wherein A is a carboxy linking moiety, preferably A is a carboxy linking moiety having the formula
  • Rl is an arylene moiety, preferably 1,4- ⁇ henylene moiety having the formula
  • Rl moieties wherein for Rl moieties, the degree of partial substitution with arylene moieties other than 1 ,4-phenylene should be such that the soil release properties of the compound are not adversely affected to any great extent. Generally, the partial substitution which can be tolerated will depend upon the backbone length of the compound.
  • R 2 moieties are ethylene moieties or substituted ethylene moieties having C ⁇ -C4 alkyl or alkoxy substituents.
  • the term "the R 2 moieties are essentially ethylene moieties or substituted ethylene moieties having C 1 -C4 alkyl or alkoxy substituents” refers to compounds of the present invention where the R 2 moieties consist entirely of ethylene or substituted ethylene moieties or a partially substituted with other compatible moieties. Examples of these other moieties include 1 ,3-propylene, 1,4- butylene, 1,5-pentylene, or 1 ,6-hexylene, 1 ,2-hydroxyalkylenes and oxyalkylenes.
  • the degree of partial substitution with these other moieties should be such that the soil release properties of the compounds are not adversely affected to any great extent.
  • polyesters made according to the present invention with a 75:25 mole ratio of diethylene glycol (-CH2CH2OCH2CH2-) to ethylene glycol (ethylene) have adequate soil release activity.
  • suitable substituted C2-C ⁇ g hydrocarbylene moieties can include substituted C2-C ⁇ 2 alkylene, alkenylene, arylene, alkarylene and like moieties,
  • the substituted alkylene or alkenylene moieties can be linear, branched or cyclic.
  • the R 3 can all be the same (e.g. all substituted arylene) or a mixture (e.g. a mixture of substituted arylenes and substituted alkylenes).
  • Prefe ⁇ ed R 3 moieties are those which are substituted 1,3-phenylene, preferably 5-sulfo-l,3-phenylene.
  • R 3 moieties are also - A-[(R -A-R 4 )]-Cap wherein R 4 is R 1 , R 3 , and mixtures thereof.
  • the prefe ⁇ ed (Cap) moieties comprise units having the formula
  • R ⁇ is C1-C4 alkylene, or the moiety -R 2 -A-R6- wherein R ⁇ is C2-C12 alkylene, alkenylene, arylene or alkarylene moiety, X is C ⁇ -C4 alkyl, preferably methyl; the indices m and n are such that the moiety -CH2CH2O- comprises at least 50% by weight of the moiety
  • R 2 moieties are essentially ethylene moieties, 1 ,2-propylene moieties, and mixtures thereof;
  • the R 3 moieties are all potassium or preferably sodium 5-sulfo-l,3- phenylene moieties;
  • the R 4 moieties are Rl or R 3 moieties, or mixtures thereof;
  • each X is ethyl, methyl, preferably methyl;
  • each n is from about 12 to about 43; when w is 0, u + v is from about 3 to about 10; when w is at least 1, u + v + w is from about 3 to about 10.
  • Cap [(A-Rl-A-R 2 ) u (A-R -A-R 2 ) v -A-R 4 -A-](Cap) are further described in detail in U.S. Patent 4,702,857, Gosselink, issued October 27, 1987 and incorporated herein by reference.
  • any other anionic non-cotton soil release agent is suitable for use in the compositions of the present invention alone or in combination except for carboxy- methylcellulose (CMC) which cannot be used alone. If the formulator selects CMC for use as an anionic soil release agent in the laundry detergent compositions of the present invention, carboxymethylcellulose must be present in an amount greater than 0.2% by weight, of the composition.
  • This mixture is heated to 180°C and maintained at that temperature overnight under argon as methanol distills from the reaction vessel.
  • the material is transfe ⁇ ed to a 500ml, single neck, round bottom flask and heated gradually over about 20 minutes to 240°C in a Kugelrohr apparatus (Aldrich) at about 0.1 mm Hg and maintained there for 110 minutes.
  • the reaction flask is then allowed to air cool quite rapidly to near room temperature under vacuum ( ⁇ 30 min.)
  • the reaction affords 24.4g of the desired oligomer as a brown glass.
  • a 13 C-NMR(DMSO-d 6 ) shows a resonance for -C(O)OCH2CH2O(O)C- at -63.2 ppm (diester) and a resonance for -C(O)OCH2CH2OH at -59.4 ppm (monoester).
  • the ratio of the diester peak to monoester peak is measured to be 8.
  • Resonances at ⁇ 51.5 ppm and ⁇ 51.6 ppm representing the sulfoethoxy groups (-CH2SO3Na) are also present.
  • a lH-NMR(DMSO-d6) shows a resonance at -7.9 ppm representing terephthalate aromatic hydrogens.
  • 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 purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of 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, Bums 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 prefe ⁇ ed bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bums et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., OXONE, manufactured commercially by DuPont
  • OXONE manufactured commercially by DuPont
  • a prefe ⁇ ed 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.
  • Mixtures of 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 co ⁇ esponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • Highly prefe ⁇ ed amido-derived bleach activators are those of the formulae: R N(R 5 )C(O)R 2 C(O)L or RlC(O)N(R5)R 2 C(O)L wherein RMs 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 prefe ⁇ ed leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly prefe ⁇ ed activator of the benzoxazin-type is:
  • Still another class of prefe ⁇ ed bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam " , decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam,
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
  • Prefe ⁇ ed examples of these catalysts include Mn ⁇ 2( u "0)3( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2(PF6)2, Mn ⁇ O ⁇ O) 1 ( u "
  • 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 prefe ⁇ ed cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] T y , wherein "OAc” represents an acetate moiety and “Ty” is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH3)5OAc](OAc)2; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ; [Co(NH 3 ) 5 OAc](SO 4 ); [Co(NH3) 5 OAc](BF 4 )2; and [Co(NH 3 ) 5 OAc](NO3)2 (herein "
  • 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%.
  • prefe ⁇ ed 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 prefe ⁇ ed clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111 ,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. See U.S. Patent 4,891,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.
  • Another type of prefe ⁇ ed 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 prefe ⁇ ed 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 terpolymers.
  • Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal- antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated 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-naptho[l,2-d]triazoles; 4,4'-bis-(l,2,3-triazol-2- yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- 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 py ⁇ olidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpy ⁇ olidone and N-vinylimidazole, 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%.
  • Prefe ⁇ ed polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, py ⁇ ole, imidazole, py ⁇ olidine, piperidine and derivatives thereof
  • the N-O group can be represented by the following general structures: O O
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more prefe ⁇ ed 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.
  • the average molecular weight is within the range of 500 to 1,000,000; more prefe ⁇ ed 1,000 to 500,000; most prefe ⁇ ed 5,000 to 100,000.
  • This prefe ⁇ ed class of materials can be refe ⁇ ed to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4.
  • Copolymers of N-vinylpy ⁇ olidone and N-vinylimidazole polymers are also prefe ⁇ ed 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 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpy ⁇ olidone 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 polyvinylpy ⁇ olidone (“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, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered 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 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-hydroxy ethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt- forming cation such as sodium or potassium.
  • R ⁇ is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s- triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the prefe ⁇ ed 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 Corporation.
  • R ⁇ is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM- GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. 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.
  • 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, nitrilotri- acetates, 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. Prefe ⁇ ed, 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. Prefe ⁇ ed compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2- dihydroxy-3 ,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • 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 incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • 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 ⁇ -C4o ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to terra- alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a prefe ⁇ ed 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.
  • Another prefe ⁇ ed category of non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto 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.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C;
  • siloxane resin composed of (CH3)3SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiO ⁇ /2 units and to Si ⁇ 2 units of from about 0.6:1 to about 1.2:1;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (prefe ⁇ ed), 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 uds 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 prefe ⁇ ed 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.
  • Prefe ⁇ ed is a weight ratio of between about 1 : 1 and 1 :10, most preferably between 1:3 and 1:6, of polyethylene glycol opolymer of polyethylene-polypropylene glycol.
  • the prefe ⁇ ed silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2- alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the Cg-Ci ⁇ kyl alcohols having a Ci -Ci g chain.
  • a prefe ⁇ ed 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.
  • 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.
  • from about 0.5% to about 3% of 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., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(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 concu ⁇ ently 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.
  • 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-l,l,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, 1,2,3,3, 5-hexamethyl indane; 5-acetyl-3-isopropyl- 1,1,2,6-tetramethyl indane; 1-do
  • 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-l,2,3,4,5,6,7,8-octahydro-l,l,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta- naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8- hexahydro-4,6,6,6,
  • perfume materials include essential oils, resinoids, and resins from a variety of sources including, but not limited to: Pern balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
  • Still other perfume chemicals include phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2-(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 Cin-Ci g alkanolamides can be incorporated 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 MgCl2, 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 C13.15 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 prefe ⁇ ed 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 11, 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 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the formulator wishes to prepare an admixable particle containing the alkoxylated cationics for use in, for example, a high density granular detergent, it is prefe ⁇ ed that the particle composition not be highly alkaline. Processes for preparing high density (above 540 g/1) granules are described in U.S. Patent 5,366,652. Such particles may be formulated to have an effective pH in-use of 9, or below, to avoid the odor of impurity amines.
  • compositions can contain various particulate detersive ingredients (e.g., bleaching agents, as disclosed hereinabove) stably suspended therein.
  • particulate detersive ingredients e.g., bleaching agents, as disclosed hereinabove
  • Such non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • the AQD dispersants are incorporated in the compositions at the levels and in the manner described hereinabove for the manufacture of other laundry detergent compositions.
  • compositions of this invention can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics.
  • an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering/bleaching solutions.
  • the aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.
  • An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.
  • liquid detergent compositions are made :
  • Amylase (300KNU/g) 0.2 0.2 0.1
  • liquid detergent compositions are made :
  • Amylase (300 KNU/g) 0.1 0.4 0.14
  • liquid detergent compositions are made :
  • Ethoxylated polyethyleneimine E20 having an average MW of approximately 600

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Abstract

L'invention porte sur des diamines quaternisées d'alkylène et leurs mélanges utilisés dans des compositions détergentes.
PCT/US1997/017309 1996-10-07 1997-09-24 Diamines quaternisees alkoxylees, ingredients pour compositions detergentes WO1998015607A2 (fr)

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AU46533/97A AU4653397A (en) 1996-10-07 1997-09-24 Alkoxylated, quaternized diamine detergent ingredients
BR9712498-2A BR9712498A (pt) 1996-10-07 1997-09-24 Ingredientes de detergente de aminaquaternizados, alcoxilados
JP10517567A JP2000503723A (ja) 1996-10-07 1997-09-24 アルコキシル化した四級化ジアミン洗剤成分
CA002267294A CA2267294A1 (fr) 1996-10-07 1997-09-24 Diamines quaternisees alkoxylees, ingredients pour compositions detergentes
EP97945302A EP0929628A2 (fr) 1996-10-07 1997-09-24 Diamines quaternisees alkoxylees, ingredients pour compositions detergentes

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US2789996P 1996-10-07 1996-10-07
US60/027,899 1996-10-07

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WO2002018527A1 (fr) * 2000-09-01 2002-03-07 Unilever Plc Composition d'entretien pour tissus
US6677289B1 (en) 1999-07-16 2004-01-13 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
EP1419230A4 (fr) * 2001-08-03 2004-09-29 Lg Household & Health Care Ltd Systeme tensioactif complexe
EP1574562A4 (fr) * 2002-12-16 2006-03-01 Kao Corp Compositions detergentes
EP1735416A1 (fr) * 2004-04-08 2006-12-27 Clariant Produkte (Deutschland) GmbH Produits de lavage et de nettoyage comprenant des agents de fixation de la couleur et des polymeres facilitant le lavage
US7163985B2 (en) 2002-09-12 2007-01-16 The Procter & Gamble Co. Polymer systems and cleaning compositions comprising the same
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9023784B2 (en) 2012-09-13 2015-05-05 Ecolab Usa Inc. Method of reducing soil redeposition on a hard surface using phosphinosuccinic acid adducts
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
EP3194554A4 (fr) * 2014-05-12 2018-04-25 The Procter and Gamble Company Composition de nettoyage anti-microbienne
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
EP3835396A1 (fr) * 2019-12-09 2021-06-16 The Procter & Gamble Company Composition de détergent comportant un polymère
EP4003603A1 (fr) * 2019-07-24 2022-06-01 Basf Se Composition de collecteur
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing

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CA2967680A1 (fr) * 2014-12-12 2016-06-16 The Procter & Gamble Company Composition nettoyante liquide
TR201909310T4 (tr) * 2015-02-06 2019-07-22 Basf Se Alkoksillenmiş polietilenimin hidrofilik olarak modifiye edilmiş lifler.
JP6684558B2 (ja) * 2015-09-03 2020-04-22 ライオン株式会社 衣料用液体洗浄剤
JP2019104924A (ja) * 2019-02-19 2019-06-27 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 抗菌洗浄組成物
CN116529285B (zh) * 2020-12-23 2025-05-13 巴斯夫股份公司 两亲性烷氧基化多胺及其用途

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CZ354698A3 (cs) * 1996-05-03 1999-04-14 The Procter & Gamble Company Kapalné detergentové prostředky, které obsahují zvláště vybrané modifikované polyaminové polymery

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US6677289B1 (en) 1999-07-16 2004-01-13 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6903059B2 (en) 1999-07-16 2005-06-07 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
WO2002018527A1 (fr) * 2000-09-01 2002-03-07 Unilever Plc Composition d'entretien pour tissus
EP1419230A4 (fr) * 2001-08-03 2004-09-29 Lg Household & Health Care Ltd Systeme tensioactif complexe
US7163985B2 (en) 2002-09-12 2007-01-16 The Procter & Gamble Co. Polymer systems and cleaning compositions comprising the same
US7442213B2 (en) 2002-09-12 2008-10-28 The Procter & Gamble Company Methods of cleaning a situs with a cleaning composition comprising a polymer system
EP1574562A4 (fr) * 2002-12-16 2006-03-01 Kao Corp Compositions detergentes
US7566688B2 (en) 2002-12-16 2009-07-28 Kao Corporation Detergent composition
EP1735416A1 (fr) * 2004-04-08 2006-12-27 Clariant Produkte (Deutschland) GmbH Produits de lavage et de nettoyage comprenant des agents de fixation de la couleur et des polymeres facilitant le lavage
US9670434B2 (en) 2012-09-13 2017-06-06 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US10377971B2 (en) 2012-09-13 2019-08-13 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11952556B2 (en) 2012-09-13 2024-04-09 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11859155B2 (en) 2012-09-13 2024-01-02 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US11053458B2 (en) 2012-09-13 2021-07-06 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US10358622B2 (en) 2012-09-13 2019-07-23 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US9023784B2 (en) 2012-09-13 2015-05-05 Ecolab Usa Inc. Method of reducing soil redeposition on a hard surface using phosphinosuccinic acid adducts
US11001784B2 (en) 2012-09-13 2021-05-11 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
US9540595B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points
EP3194554A4 (fr) * 2014-05-12 2018-04-25 The Procter and Gamble Company Composition de nettoyage anti-microbienne
EP4003603A1 (fr) * 2019-07-24 2022-06-01 Basf Se Composition de collecteur
EP3835396A1 (fr) * 2019-12-09 2021-06-16 The Procter & Gamble Company Composition de détergent comportant un polymère
WO2021118814A1 (fr) * 2019-12-09 2021-06-17 The Procter & Gamble Company Composition détergente comprenant un polymère

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JP2000503723A (ja) 2000-03-28
AR010251A1 (es) 2000-06-07
HUP9904548A3 (en) 2001-11-28
BR9712498A (pt) 2001-12-04
CA2267294A1 (fr) 1998-04-16
TR199900753T2 (xx) 1999-07-21
WO1998015607A3 (fr) 1998-05-28
ZA978603B (en) 1998-03-18
CN1239984A (zh) 1999-12-29
EP0929628A2 (fr) 1999-07-21
MA24368A1 (fr) 1998-07-01
HUP9904548A2 (hu) 2000-05-28

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