WO2000065014A1 - Treating compositions comprising polysaccharides - Google Patents

Treating compositions comprising polysaccharides Download PDF

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Publication number
WO2000065014A1
WO2000065014A1 PCT/US2000/011016 US0011016W WO0065014A1 WO 2000065014 A1 WO2000065014 A1 WO 2000065014A1 US 0011016 W US0011016 W US 0011016W WO 0065014 A1 WO0065014 A1 WO 0065014A1
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WO
WIPO (PCT)
Prior art keywords
compositions
agents
composition
treating
polysacchande
Prior art date
Application number
PCT/US2000/011016
Other languages
French (fr)
Inventor
Mary Vijayarani Barnabas
Freddy Arthur Barnabas
Michael Stanford Showell
Johan Smets
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 US09/937,261 priority Critical patent/US6613733B1/en
Priority to JP2000614352A priority patent/JP2002543302A/en
Priority to MXPA01010947A priority patent/MXPA01010947A/en
Priority to EP00928348A priority patent/EP1173535A1/en
Priority to AU46599/00A priority patent/AU4659900A/en
Priority to BR0010587-2A priority patent/BR0010587A/en
Priority to CA002367960A priority patent/CA2367960A1/en
Publication of WO2000065014A1 publication Critical patent/WO2000065014A1/en

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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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/45—Shrinking resistance, anti-felting properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
    • D06P1/48—Derivatives of carbohydrates

Definitions

  • the present invention relates to treating compositions comp ⁇ sing a polysaccha ⁇ de, and to a method for treating fab ⁇ cs, natural fibers, such as cellulosic fibers, more particularly cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell, poly/cotton, other cotton blends and mixtures thereof , with such compositions for providing the fab ⁇ cs with improved color appearance and/or pill prevention and/or abrasion resistance and/or w ⁇ nkle resistance and/or shrinkage resistance compared to treating compositions without such polysaccha ⁇ des.
  • natural fibers such as cellulosic fibers, more particularly cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell, poly/cotton, other cotton blends and mixtures thereof , with such compositions for providing the fab ⁇ cs with improved color appearance and/or pill prevention and/or abrasion resistance and/or w ⁇ nkle resistance and
  • the present invention is a treating composition comp ⁇ sing polysaccha ⁇ des and a method for imparting color appearance and/or pill prevention and/or abrasion resistance and/or w ⁇ nkle resistance and/or shrinkage resistance properties to fabrics such as cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell, poly/cotton, other cotton blends and mixtures thereof.
  • a treating composition comprising polysaccharides
  • a method for treating a fabric in need of treatment comp ⁇ sing contacting the fab ⁇ c with an effective amount of a polysaccha ⁇ de-contaming treating composition such that the treating composition treats the fab ⁇ c
  • a preferred treating composition in accordance with the present invention comp ⁇ ses one or more polysaccharides and one or more cleanmg adjunct mate ⁇ als as desc ⁇ bed hereinafter, preferably selected from the group consisting of builders, bleaching agents, dye transfer inhibiting agents, chelants, dispersants, polysaccha ⁇ des, softening agents, suds suppressors, earners, enzymes, enzyme stabilizing systems, polyacids, soil removal agents, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bacte ⁇ cides, dyes, perfumes, b ⁇ ghteners and mixtures thereof, and optionally, but preferably further
  • the treating composition is in the form of powder or granules.
  • the treating composition may be in the form of a liquid such as an aqueous or non-aqueous heavy duty liquid detergent composition, a liquid for spray application, or a solid, such as a concentrated stick, for rubbing onto the fab ⁇ c.
  • the treating composition is applied to the fab ⁇ c through the wash and/or through the ⁇ nse cycles.
  • the treating composition can be applied to the fab ⁇ c p ⁇ or to the wash and/or after the wash and/or ⁇ nse cycles, such as dunng or p ⁇ or to ironing, if needed. All percentages and proportions herein are by weight, and all references cited herein are hereby incorporated by reference, unless otherwise specifically indicated.
  • the treating compositions of the present invention comp ⁇ se an "effective amount" of a polysacchande.
  • An "effective amount" of a polysaccha ⁇ de is any amount capable of measurably improving the color appearance and/or pill prevention and/or abrasion resistance and/or w ⁇ nkle resistance and/or sh ⁇ nkage resistance properties of a fab ⁇ c when it is washed. In general, this amount may vary quite widely.
  • Treating compos ⁇ t ⁇ on(s) herein is meant to encompass generally laundry and/or fab ⁇ c care compositions and/or fab ⁇ c conditioners.
  • the treating compositions of the present invention comp ⁇ se an effective amount of one or more polysaccharides and are preferably free of starch and/or starch denvatives and/or resins
  • the treating compositions further comp ⁇ se one or more cleaning adjunct mate ⁇ als
  • These treating compositions are useful in the methods of the present invention It is desirable that the polysacchande is present in the treating composition of the present invention in an amount m the range of from about 0 01% to about 50% by weight of the treating composition, more preferably from about 0 5% to about 10% by weight of the treating composition
  • the polysaccha ⁇ de is present in the wash, soaking and/or spray-treatment solution in amount m the range of from about 2 ppm to about 25000 ppm, more preferably from about 10 ppm to about 5000 ppm.
  • the treating composition can include conventional detergent ingredients, such as one or more of the following ingredients selected from the group consisting of surfactants, builders, bleaches, bleach activators, bleach catalysts, enzymes, enzyme stabilizing systems, soil release/removal agents, suds suppressors, polyacids, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bacte ⁇ cides, dyes, perfumes, earners and bnghteners Examples of such ingredients are generally desc ⁇ bed in U.S. Pat. No 5,576,282.
  • the treating compositions of the present invention can be in solid (powder, granules, bars, tablets), dimple tablets, liquid, paste, gel, spray, stick or foam forms.
  • the liquid forms can also be m a "concentrated” form which are diluted to form compositions with the usage concentrations, as given hereinbelow, for use in the "usage conditions".
  • Concentrated compositions compnse a higher level of polysacchande, typically from about 1% to about 99% > , preferably from about 2% to about 65%>, more preferably from about 3% to about 25%), by weight of the concentrated treating composition
  • Concentrated compositions are used m order to provide a less expensive product
  • a concentrated product i.e., when the polysacchande is from about 1%> to about 99%, by weight of the concentrated composition, it is preferable to dilute the composition, preferably with water, before treating a fab ⁇ c in need of treatment.
  • the water content of the "concentrated" form is less than 40%), more preferably less than 30%, most preferably less than 20%> by weight of the detergent composition.
  • the present invention also relates to polysaccha ⁇ de-containmg treating compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabnc articles and/or surfaces with said compositions containing the polysaccha ⁇ de and other optional ingredients at a level that is effective, yet is not discernible when dned on the surfaces
  • the spray dispenser compnses manually activated and non-manual powered (operated) spray means and a container containing the treating composition
  • the articles of manufacture preferably are m association with instructions for use to ensure that the consumer applies sufficient polysaccha ⁇ de to provide the desired benefit
  • Typical compositions to be dispensed from a sprayer contain a level of polysaccha ⁇ de of from about 0 01% to about 5%, preferably from about 0.05% to about 2%, more preferably from about 0 1% to about 1%, by weight of the usage composition.
  • the article of manufacture can simply comp ⁇ se a liquid or granular solid polysaccha ⁇ de-contaming treating composition and a suitable container
  • Wash-added compositions including liquid and granular detergent compositions and wash additive compositions typically contain a level of polysacchande of from about 0.01% to about 30%), preferably from about 0.5% to about 20%, more preferably from about 1% to about
  • Typical nnse-added compositions include liquid fab ⁇ c conditioner and other ⁇ nse additive compositions, contain a level of polysaccha ⁇ de of from about 0.01% to about 40%, preferably from about 0.3% to about 25%, more preferably from about 0.5% to about 25%, most preferably from about 1% to about 10%>, by weight of the ⁇ nse added compositions.
  • the articles of manufacture are in association with instructions for how to use the composition to treat fab ⁇ cs correctly, to obtain the desirable fabnc care results, for example, improved color appearance and/or pill prevention and or abrasion resistance and/or wnnkle resistance and/or sh ⁇ nkage resistance, while at the same time providing improved cleaning benefits, including, e.g., the manner and/or amount of composition to be used, and the preferred ways of stretching and/or smoothing, if any, the fab ⁇ cs.
  • the instructions be as simple and clear as possible. Accordingly, the use of pictures and/or icons to assist in explainmg the instructions is desirable.
  • Liquid or solid, preferably powder, polysacchande-contammg treating composition for treating fabnc in the ⁇ nse step m accordance with the present invention comp ⁇ se an effective amount of the polysaccha ⁇ de of the present invention, and optionally, fabnc softener actives, perfume, electrolytes, chlo ⁇ ne scavenging agents, dye transfer inhibiting agents, dye fixative agents, phase stabilizers, chemical stabilizers including antioxidants, sihcones, antimicrobial actives and/or preservatives, chelating agents, ammocarboxylate chelatmg agents, colorants, enzymes, b ⁇ ghteners, soil release agents, anti-encrustation agents, builders and/or mixtures thereof.
  • the composition is preferably packaged m association with instructions for use to ensure that the consumer knows what benefits can be achieved.
  • Yet another liquid or solid, preferably powder or granular, treating composition m accordance with the present invention to be used in the wash cycle comp ⁇ ses an effective amount of one or more polysaccha ⁇ des, and optionally, surfactants, builders, perfume, chlo ⁇ ne scavenging agents, dye transfer inhibiting agents, dye fixative agents, dispersants, detergent enzymes, heavy metal chelating agents, suds suppressors, fab ⁇ c softener actives, chemical stabilizers including antioxidants, sihcones, antimicrobial actives and/or preservatives, soil suspending agents, soil release agents, optical bnghteners, colorants, and the like, or mixtures thereof.
  • the composition is preferably packaged in association with instructions for use to ensure that the consumer knows what benefits can be achieved.
  • a preferred treating composition for treating fabric comp ⁇ ses an effective amount of one or more polysaccha ⁇ des, and optionally, perfume, fab ⁇ c lub ⁇ cants, adjunct fab ⁇ c shape retention polymers, lithium salts, hydrophilic plasticizers, odor control agents, antimicrobial actives and/or preservatives, surfactants, enzymes, or mixtures thereof.
  • Other optional ingredients can also be added, e.g., antioxidants, chelatmg agents, e.g., ammocarboxylate chelatmg agents, heavy metal chelating agents, antistatic agents, insect and moth repelling agents, dye transfer inhibiting agents, dye fixative agents, colorants, suds suppressors, and the like, and mixtures thereof.
  • the composition is typically applied to fab ⁇ c via a, e.g., dipping, soaking and/or spraying process followed by a drying step, including the process compnsing a step of treating or spraying the fab ⁇ c with the treating composition either outside or mside an automatic clothes dryer followed by, or concurrently with, the drying step m said clothes dryer.
  • the composition may be applied by spraying the fab ⁇ c with the treating composition p ⁇ or to and/or dunng ironing, if needed.
  • the composition may be applied by spraying the fab ⁇ c during dry cleaning.
  • the application can be done industnally by large scale processes on textiles and/or finished garments and clothings, or in consumer's home by the use of commercial product.
  • the treating compositions herein can be made by any suitable process known m the art. Examples of such processes are desc ⁇ bed in U.S. Pat. No. 5,576,282.
  • the treating compositions herein will preferably be formulated such that, dunng use m aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11.
  • Techniques for controllmg pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled m the art.
  • Aqueous based heavy duty laundry detergent compositions containing the polysaccha ⁇ de preferably contain a surfactant system comp ⁇ smg surfactants selected from the group consisting of noniomc detersive surfactants, anionic detersive surfactants, zwittenomc detersive surfactants, amine oxide detersive surfactants and mixtures thereof
  • the surfactant system typically comp ⁇ ses from about 0 01% to about 50%, preferably from about 0.2% to about 30% by weight of the detergent composition
  • compositions of the present invention are tablets
  • Such polysacchande-contammg treating composition tablets compnse an effective amount of one or more polysacchandes, and optionally, surfactants, builders, perfume, chlorine scavenging agents, dye transfer inhibiting agents, dye fixative agents, dispersants, detergent enzymes, heavy metal chelating agents, suds suppressors, fab ⁇ c softener actives, chemical stabilizers including antioxidants, sihcones, antimicrobial actives and/or preservatives, soil suspending agents, soil release agents, optical bnghteners, colorants, and the like, or mixtures thereof
  • the composition is preferably packaged m association with instructions for use to ensure that the consumer knows what benefits can be achieved.
  • the tablets can be used in pre-wash and/or pretreatment procedures as well as through the wash and/or nnse cycles.
  • the treating compositions of the present invention can be inco ⁇ orated into a spray dispenser, or concentrated stick form that can create an article of manufacture that can facilitate the cleaning and/or fabnc care or conditioning of fab ⁇ c.
  • the spray treatment is a "pre-treat", which is followed by a wash cycle, then the spray treatment treating compositions preferably comp ⁇ se from about 0.01% to about 50% of polysaccha ⁇ de by weight the of total treating composition, more preferably from about 0J%> to about 3% of polysacchande by weight of the total treating composition.
  • the spray treatment compositions are desired to do the cleaning, as in the case of wash, then the spray treatment compositions preferably compnse from about 2 ppm to about 10000 ppm of the polysaccha ⁇ de by weight of the total treating composition, more preferably from about 200 ppm to about 5000 ppm of the polysaccha ⁇ de by weight of the total treating composition. In the latter case, a bnef ⁇ nse, not a full wash cycle, is desirable after treatment.
  • Such spray treatment compositions are typically packaged m a spray dispenser.
  • the spray-treatment compositions herein are typically packaged m spray dispensers.
  • the spray dispensers can be any of the manually activated means for producing a spray of liquid droplets as is known in the art, e.g. t ⁇ gger-type, pump-type, non-aerosol self-pressu ⁇ zed, and aerosol-type spray means. It is preferred that at least about 70%, more preferably, at least about 80%, most preferably at least about 90% of the droplets have a particle size of smaller than about 200 microns.
  • the spray dispenser can be an aerosol dispenser.
  • Said aerosol dispenser comp ⁇ ses a container which can be constructed of any of the conventional materials employed in fab ⁇ catmg aerosol containers.
  • the dispenser must be capable of withstanding internal pressure in the range of from about 20 to about 110 p.s.i.g., more preferably from about 20 to about 70 p.s l.g.
  • the one important requirement concerning the dispenser is that it be provided with a valve member which will permit the treating compositions of the present invention contained m the dispenser to be dispensed in the form of a spray of very fine, or finely divided, particles or droplets.
  • a more complete description of commercially available suitable aerosol spray dispensers appears m U.S. Pat. Nos.. 3,436,772, Stebbms, issued Apr.8, 1969; and 3,600,325, Kaufman et al., issued Aug. 17, 1971.
  • the spray dispenser is a self-pressu ⁇ zed non-aerosol container having a convoluted lmer and an elastomenc sleeve.
  • a more complete desc ⁇ ption of suitable self- pressu ⁇ zed spray dispensers can be found in U.S. Pat. Nos.: 5, 111,971, Wmer, issued May 12, 1992; and 5,232,126, Wmer, issued Aug. 3, 1993.
  • Another type of suitable aerosol spray dispenser is one wherem a bar ⁇ er separates the w ⁇ nkle reducing composition from the propellant (preferably compressed air or nitrogen), as is disclosed in U.S. Pat. No. 4,260,110, issued Apr. 7, 1981, incorporated herein by reference.
  • Such a dispenser is available from EP Spray Systems, East Hanover, NJ. More preferably, the spray dispenser is a non-aerosol, manually activated, pump-spray dispenser.
  • the spray dispenser is a non-aerosol, manually activated, pump-spray dispenser.
  • the spray dispenser is a manually activated tngger-spray dispenser.
  • tngger-spray dispenser A more complete disclosure of commercially available suitable dispensing devices appears in U.S. Pat. Nos.: 4,082,223, Nozawa, issued Apr. 4, 1978; 4,161,288, McKmney, issued Jul. 7, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984; and 4,819,835, Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr. 19, 1994.
  • a broad array of tngger sprayers or finger pump sprayers are suitable for use with the compositions of this invention. These are readily available from suppliers such as Calmar, Inc., City of Industry, California; CSI (Continental Sprayers, Inc.), St. Peters, Missou ⁇ ; Berry Plastics Corp., Evansville, Indiana - a distributor of Guala ® sprayers; or Seaquest Dispensing, Cary, 111.
  • the preferred trigger sprayers are the blue inserted Guala ® sprayer, available from Berry Plastics Corp., the Calmar TS800-1A® sprayers, available from Calmar Inc., or the CSI T7500® available from Continental Sprayers Inc., because of the fine uniform spray charactenstics, spray volume and pattern size.
  • Any suitable bottle or container can be used with the trigger sprayer, the preferred bottle is a 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape to the Cmch® bottle. It can be made of any mate ⁇ als such as high density polyethylene, polypropylene, polyvmyl chlo ⁇ de, polystyrene, polyethylene terephthalate, glass or any other matenal that forms bottles.
  • a finger pump can be used with canister or cylindrical bottle
  • the preferred pump for this application is the cylmd ⁇ cal Euromist ⁇ ® from Seaquest Dispensing.
  • Fab ⁇ cs preferably finished garments, can be treated with the polysacchande-contammg treating compositions by any method known m the art that accomplishes contacting the fabnc with the polysacchande-contammg treating composition.
  • a preferred embodiment of the present invention is a method for treating a fabnc m need of treatment, wherem the method comp ⁇ ses contacting the fab ⁇ c with an effective amount of polysacchande-contammg treating composition such that the treating composition treats the fabnc.
  • the polysaccha ⁇ de treating composition is m contact with the fab ⁇ c for an "effective amount of time", which herein means the amount of time required for the polysacchande-contammg treating composition to adequately treat a fab ⁇ c such that the fab ⁇ c acquires improved color appearance and/or pill prevention and/or abrasion resistance and/or w ⁇ nkle resistance and/or sh ⁇ nkage resistance properties.
  • time can vary quite widely, however, a preferred range of time is from about 5 minutes to about 60 minutes, more preferably from about 10 minutes to about 30 minutes.
  • Suitable methods include, but are not limited to, washing the fabnc in a solution containing the polysacchande-contammg treating composition.
  • the washing can be manual or automatic, such as m a washing machine.
  • the washing machine used m the method desc ⁇ bed herein can be any conventional washing machine known in the art. In addition, it can be a specially designed washing machine such as the washing machine desc ⁇ bed in U.S. Patent No. 5,520,025 to Joo et al.
  • Suitable methods include, but are not limited to, soaking the fab ⁇ c in a solution containing the polysacchande-contammg treating composition; spraying the fab ⁇ c with a solution containing the polysacchande-contammg treating composition; rubbing the fabnc with a solid containing the polysacchande-contammg treating composition; dipping the fab ⁇ c m a solution containing the polysacchande-contammg treating composition; rolling the polysacchande-contammg treating composition onto the fab ⁇ c, spreading the polysacchande- contammg treating composition onto the fabnc and brushing the polysacchande-contammg treating composition onto the fab ⁇ c
  • the invention herein also encompasses a laundering pretreatment process for fabrics which have been soiled or stained comprising directly contacting said stains and/or soils with a highly concentrated
  • the cleanmg composition remains m contact with the soil/stam for a penod of from about 30 seconds to 24 hours p ⁇ or to washing the pretreated soiled/stamed substrate m conventional manner. More preferably, pretreatment times will range from about 1 to 180 minutes.
  • Such methods can be used m industrial applications, such as in the textile industry, or in residential (domestic) applications, preferably, the methods are used m the residential (domestic) applications.
  • compositions of the present invention maintains the color appearance and/or pill prevention and/or abrasion resistance and/or wnnkle resistance and/or shrinkage resistance of a fab ⁇ c in need of treatment through multiple wash cycles.
  • the present invention also encompasses the inclusion of instructions on the use of the polysacchande-contammg treating compositions with the packages containing the treating compositions herein or with other forms of advertising associated with the sale or use of the treating compositions.
  • the instructions may be mcluded m any manner typically used by consumer product manufactu ⁇ ng or supply companies. Examples include providing instructions on a label attached to the container holding the composition; on a sheet either attached to the container or accompanying it when purchased; or in advertisements, demonstrations, and/or other wntten or oral instructions which may be connected to the purchase of the treating compositions.
  • the instructions may include information relating to the temperature of the wash water; washing time; recommended settings on the washing machine; recommended amount of the treating composition to use; pre-soakmg procedures; and spray-treatment procedures.
  • a product comp ⁇ smg a polysacchande-contammg treating composition the product further including instructions for using the treating composition to treat a fab ⁇ c in need of treatment, the instructions including the step of: contacting said fabric with an effective amount of said treating composition for an effective amount of time such that said composition treats said fab ⁇ c.
  • the product may be a laundry detergent composition, a fabric care composition or fab ⁇ c conditioner. Furthermore, the product may be contained m a spray dispenser.
  • Polysaccha ⁇ des herein is meant natural polysaccha ⁇ des, and does not include polysaccha ⁇ de denvatives or modified polysaccha ⁇ des.
  • Suitable polysacchandes for use in the treating compositions of the present invention include, but are not limited to, gums, arabmans, galactans, seeds and mixtures thereof.
  • Suitable polysacchandes that are useful in the present invention include polysaccha ⁇ des with a degree of polymenzation (DP) over 40, preferably from about 50 to about 100,000, more preferably from about 500 to about 50,000, constituting sacchandes preferably include, but are not limited to, one or more of the following saccharides: isomaltose, isomaltotnose, isomaltotetraose, isomaltooligosaccha ⁇ de, fructoohgosacchande, levoohgosacchandes, galactoohgosaccha ⁇ de, xyloohgosacchande, gentioohgosaccha ⁇ des, disaccha ⁇ des, glucose, fructose, galactose, xylose, mannose, sorbose, arabmose, rhamnose, fucose, maltose, sucrose, lactose, maltulose, nbose, lyxo
  • the polysacchandes can be extracted from plants, produced by organisms, such as bactena, fungi, prokaryotes, eukaryotes, extracted from animals and/or humans.
  • organisms such as bactena, fungi, prokaryotes, eukaryotes, extracted from animals and/or humans.
  • xanthan gum can be produced by Xanthomonas campestris, gellan by Sphingomonas paucimobilis, xyloglucan can be extracted from tamannd seed.
  • the polysaccha ⁇ des can be linear, or branched in a vanety of ways, such as 1-2, 1-3, 104, 1-6, 2-3 and mixtures thereof. It is desirable that the polysaccha ⁇ des of the present invention have a molecular weight m the range of from about 10,000 to about 10,000,000, more preferably from about 50,000 to about 1,000,000, most preferably from about 50,000 to about 500,000.
  • the polysaccha ⁇ de is selected from the group consisting of: tamannd gum (preferably consisting of xyloglucan polymers), guar gum, locust bean gum (preferably consisting of galactomannan polymers), and other mdustnal gums and polymers, which include, but are not limited to, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psylhum seed, qumce seed, xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, schizophyllan, chitm, hydroxyalkyl cellulose, arabman (preferably from sugar beets), de-branched arabman (preferably from sugar beets), arabmoxylan (preferably from rye and wheat flour), galactan (preferably from lupin and potatoes), pectic galactan (preferably from potatoes), galactomannan (preferably from carob, and including both low
  • polysaccharides can also be treated (preferably enzymatically) so that the best fractions of the polysaccha ⁇ des are isolated. More preferred polysaccharides have a ⁇ -lmked backbone.
  • Xyloglucan polymer is a highly preferred polysacchande for use in the laundry and/or fabric care compositions of the present invention.
  • Xyloglucan polymer is preferably obtained from tamannd seed polysaccha ⁇ des.
  • the preferred range of molecular weights for the xyloglucan polymer is from about 10,000 to about 1,000,000, more preferably from about 50,000 to about 200,000.
  • Polysacchandes when present, are normally incorporated in the treating composition of the present invention at levels from about 0.1% to about 25%, preferably from about 0J%> to about 10% by weight of the treating composition.
  • Polysaccha ⁇ des have a high affinity for binding with cellulose. Without wishing to be bound by theory, it is believed that the binding efficacy of the polysacchandes to cellulose depends on the type of linkage, extent of branching and molecular weight. The extent of binding also depends on the nature of the cellulose (i.e., the ratio of crystalline to amorphous regions in cotton, rayon, linen, etc.).
  • the natural polysacchandes can be modified with amines (pnmary, secondary, tertiary), amides, esters, ethers, alcohols, carboxylic acids, tosylates, sulfonates, sulfates, nitrates, phosphates and mixtures thereof. Such a modification can take place in position 2, 3 and/or 6 of the glucose unit.
  • modified or de ⁇ vatized polysacchandes can be included in the compositions of the present invention m addition to the natural polysacchandes.
  • Nonhmitmg examples of such modified polysaccha ⁇ des include: carboxyl and hydroxymethyl substitutions (e.g., glucuromc acid instead of glucose); ammo polysacchandes (amine substitution, e.g., glucosamme instead of glucose); C ⁇ -C 6 alkylated polysacchandes; acetylated polysacchande ethers; polysaccha ⁇ des having ammo acid residues attached (small fragments of glycoprotein); polysaccha ⁇ des containing silicone moieties.
  • carboxyl and hydroxymethyl substitutions e.g., glucuromc acid instead of glucose
  • ammo polysacchandes amine substitution, e.g., glucosamme instead of glucose
  • C ⁇ -C 6 alkylated polysacchandes acetylated polysacchande ethers
  • polysaccha ⁇ des having ammo acid residues attached small fragments of glycoprotein
  • modified polysaccha ⁇ des are commercially available from Carbomer and include, but are not limited to, ammo alginates, such as hexanediamme alginate, amine functionahzed celluloselike 0-methyl-(N-lJ2-dodecaned ⁇ amme) cellulose, biotm hepa ⁇ n, carboxymethylated dextran, guar polycarboxyhc acid, carboxymethylated locust bean gum, caroxymethylated xanthan.
  • ammo alginates such as hexanediamme alginate, amine functionahzed celluloselike 0-methyl-(N-lJ2-dodecaned ⁇ amme) cellulose, biotm hepa ⁇ n, carboxymethylated dextran, guar polycarboxyhc acid, carboxymethylated locust bean gum, caroxymethylated xanthan.
  • chitosan phosphate chitosan phosphate sulfate, diethylammoethyl dextran, dodecylamide alginate, sialic acid, glucuromc acid, galacturonic acid, mannuronic acid, guluromc acid, N-acetylglucosamme, N-acetylgalactosamine, and mixtures thereof.
  • the polysaccha ⁇ de polymers can be linear, like m hydroxyalkylcellulose, the polymer can have an alternating repeat like in carrageenan, the polymer can have an interrupted repeat like in pectin, the polymer can be a block copolymer like in algmate, the polymer can be branched like in dextran, the polymer can have a complex repeat like in xanthan. Desc ⁇ ptions of the polymer definitions are give in "An introduction to Polysaccha ⁇ de Biotechnology", by M> Tombs and S.E. Harding, TJ.Press 1998. Oligosaccharides
  • compositions of the present invention may include ohgosacchandes.
  • Suitable ohgosacchandes that are useful m the present invention include ohgosacchandes with a degree of polymenzation (DP) of less than 20, preferably from about 1 to about 15, more preferably from about 2 to about 10, constituting monosacchandes preferably include, but are not limited to, one or more of the following monosacchandes: glucose, fructose, galactose, xylose, mannose, arabmose, rhamnose, nbose, lyxose, allose, altrose, gulose, idose, talose, and/or their denvatives
  • Preferred ohgosacchandes have a molecular weight in the range of from about 300 to about 8000. Branched ohgosacchandes are preferred over linear ohgosacchandes.
  • Nonhmiting examples of suitable ohgosacchandes can be obtained commercially from any of the suppliers - Carbomer (fructo-ohgosaccha ⁇ des, levo-ohgosacchandes, mulm, dextra 5000, cellosacchandes, etc.,), Gram Processing Corporation (maltodextnn), Pharmacica Biotech (Dextran senes), Palatinit (isomalt) and Showa Sangyo (Isomalto-500).
  • Ohgosacchandes when present, are normally incorporated in the cleaning composition at levels from about 1% to about 25%, preferably from about 2% to about 10% by weight of the laundry and/or fab ⁇ c care composition.
  • the treating compositions of the present invention comp ⁇ se an effective amount of the polysacchande, and preferably one or more of the above-desc ⁇ bed preferred ingredients, and optionally one or more of the following conventional cleaning adjunct mate ⁇ als either to improve the performance of the polysacchande, e.g., in the areas of w ⁇ nkle control, anti-wear, soil release, tensile strength and the like, or to provide additional benefits, such as odor control, antimicrobial, and the like.
  • the useful optional cleaning adjunct matenals are those that are compatible with the polysaccha ⁇ de, m that they do not interfere and/or substantially or significantly dimmish the benefits provided by the polysacchande.
  • Surfactant System - Detersive surfactants can be, and preferably are included m the treating compositions of the present invention. When present, surfactants comp ⁇ se at least 0.01%, preferably at least about 0.1%, more preferably at least about 0.5%, most preferably at least about 1% to about 60%., more preferably to about 35%, most preferably to about 30% by weight of the treating composition depending upon the particular surfactants used and the desired effects.
  • the detersive surfactant can be noniomc, anionic, ampholytic, zwitte ⁇ omc, cationic, semi-polar noniomc, and mixtures thereof, nonhmitmg examples of which are disclosed in U.S.
  • Preferred treating compositions comp ⁇ se anionic detersive surfactants or mixtures of anionic surfactants with other surfactants, especially noniomc surfactants.
  • Anionic surfactants are highly preferred for use with the treating compositions of the present invention.
  • Nonhmitmg examples of surfactants useful herein include the conventional Cn-C j alkyl benzene sulfonates and pnmary, secondary and random alkyl sulfates, the C jQ -Cig alkyl alkoxy sulfates, the C j o- ig alkyl polyglycosides and their corresponding sulfated polyglycosides, Cj2-C ⁇ g alpha-sulfonated fatty acid esters, C ⁇ -Cj alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C ⁇ -Cj betames and sulfobetames ("sul- taines”), CjQ- i amine oxides, and the like.
  • the surfactant is preferably formulated to be compatible with enzyme and bleaching components, if any, present in the composition.
  • the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
  • Noniomc Surfactants Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the noniomc surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • Commercially available noniomc surfactants of this type include Igepal ⁇ M CO-630, marketed by the GAP Corporation; and T ⁇ tonTM X-45, X-l 14, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of p ⁇ mary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the noniomc surfactant of the noniomc surfactant systems of the present invention.
  • noniomc surfactants of this type include TergitolTM 15-S-9 (the condensation product of C ⁇ ⁇ - C * i5 l ear alcohol with 9 moles ethylene oxide), 24-L-6 NMW (the condensation product of C j 2-Ci4 pnmary alcohol with 6 moles ethylene oxide with a narrow molecular weight dist ⁇ bution), both marketed by Union Carbide Corporation; Neodol ⁇ ⁇ 45-9 (the condensation product of C-[4-Ci5 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of
  • noniomc surfactant of the surfactant systems of the present invention are the alkylpolysaccha ⁇ des disclosed in U.S. Patent No. 4,565,647.
  • Preferred alkylpolyglycosides have the formula: wherein R-2 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 1J to about 10, preferably from about 1J to about 3, most preferably from about 1.3 to about 2J.
  • 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 noniomc surfactant systems of the present invention.
  • compounds of this type include certain of the commercially-available Plurafac *M LF404 and Pluromc * M surfactants, marketed by BASF.
  • noniomc surfactant of the noniomc surfactant system of the present invention are condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme include certain of the commercially available TetromcTM compounds, marketed by BASF.
  • Preferred for use as the noniomc surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of p ⁇ mary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccha ⁇ des, and mixtures thereof. Most preferred are C -Ci 4 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-C j alcohol ethoxylates (preferably C ⁇ Q avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
  • Highly preferred noniomc surfactants are polyhydroxy fatty acid amide surfactants of the formula- R 2 - C(O) - NCR 1 ) - Z wherem R 1 is H, or R 1 is C * ⁇ _4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl or a mixture thereof, R 2 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
  • R 2 is a straight C * j j_i5 alkyl or C * [6_ ⁇ 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 animation reaction.
  • Anionic Surfactants - Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C -C2f j carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting mate ⁇ als would include natural fatty substances as derived from tallow, palm oil, etc.
  • alkyl ester sulfonate surfactant especially for laundry applications, compnse alkyl ester sulfonate surfactants of the structural formula :
  • R 3 is a C -C2f j hydrocarbyl, preferably an alkyl, or combination thereof
  • R 4 is a Ci -Cg hydrocarbyl, preferably an alkyl, or combination thereof
  • M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamme, diethanolamme, and t ⁇ ethanolamme.
  • R 3 is Cj ⁇ -Cig alkyl
  • R 4 is a Ci -Cg hydrocarbyl, preferably an alkyl, or combination thereof
  • M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium
  • R 4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R 3 ⁇ s C * ⁇ o-Ci6 -alkyl.
  • alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherem R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-
  • alkyl chains of C12-C16 are preferred for lower wash temperatures (e.g. below about 50°C) and Cj ⁇ -i alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).
  • anionic surfactants useful for detersive purposes include salts of soap, C -C22 p ⁇ mary of secondary alkanesulfonates, C -C24 olefmsulfonates, sulfonated polycarboxyhc acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as desc ⁇ bed m Bntish patent specification No 1,082,179, Cg-C24 alkylpolyglycolethersulfates
  • alkyl glycerol sulfonates containing up to 10 moles of ethylene oxide
  • alkyl glycerol sulfonates containing up to 10 moles of ethylene oxide
  • alkyl glycerol sulfonates containing up to 10 moles of ethylene oxide
  • alkyl glycerol sulfonates containing up to 10 moles of ethylene oxide
  • alkyl glycerol sulfonates containing up to 10 moles of ethylene oxide
  • fatty acyl glycerol sulfonates fatty acyl glycerol sulfonates
  • fatty oleyl glycerol sulfates alkyl phenol ethylene oxide ether sulfates
  • paraffin sulfonates alkyl phosphates, lsethionates such as the acyl lsethionates, N-acyl taurates, alkyl succina
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C ⁇ Q-
  • C24 alkyl or hydroxyalkyl group having a C1 -C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C ⁇ -C ⁇ 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-ammomum cation.
  • a metal cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl, t ⁇ methyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdmium cations and those denved from alkylammes such as ethylamme, diethylamine, t ⁇ ethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C ⁇ -C-j alkyl polyethoxylate (1.0) sulfate (Ci2-C * ⁇ gE(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (C 12 -C 18 E(2J5)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate (C 12 -C 18 E(3.0)M), and C * i2-C * alkyl polyethoxylate (4.0) sulfate (Cj2-C ⁇ E(4.0)M), wherem M is conveniently selected from sodium and potassium.
  • the treating compositions of the present invention typically compnse from about 1%, preferably from about 3% to about 40%, preferably about 20% by weight of such anionic surfactants
  • Cationic Surfactants - Cationic detersive surfactants suitable for use in the treating compositions of the present invention are those having one long-chain hydrocarbyl group
  • examples of such cationic surfactants include the ammonium surfactants such as alkylt ⁇ methylammonium halogemdes, and those surfactants having the formula [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ]2R 5 N+X-
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures
  • R 4 IS selected from the group consisting of C1 -C4 alkyl, C1-C4 hydroxyalkyl, benzyl nng structures formed by joining the two R 4 groups, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH wherein R" is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R- ⁇ is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R? is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula (1): R1 R2R3R4N + X" wherem R is Cg-C- j g alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4 ⁇ ) x H where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.
  • the preferred alkyl chain length for R ⁇ is Cj2" C15 particularly where the alkyl group is a mixture of chain lengths de ⁇ ved from coconut or palm kernel fat or is de ⁇ ved synthetically by olefin build up or OXO alcohols synthesis.
  • Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulfate, acetate and phosphate ions.
  • Suitable quaternary ammonium compounds of formulae (1) for use herein are include, but are not limited to: coconut t ⁇ methyl ammonium chlo ⁇ de or bromide; coconut methyl dihydroxyethyl ammonium chlo ⁇ de or bromide; decyl t ⁇ ethyl ammonium chlonde; decyl dimethyl hydroxyethyl ammonium chlo ⁇ de or bromide; C12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chlo ⁇ de or bromide; mynstyl t ⁇ methyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chlo ⁇ de or bromide; lauryl dimethyl (ethenoxy)4 ammonium chlo ⁇ de or bromide; chohne esters
  • CH2-CH2-O-C-C12-14 alkyl and R2R3R4 are methyl
  • cationic surfactants useful herein are also desc ⁇ bed in U.S. Patent 4,228,044, Cambre, issued October 14, 1980 and m European Patent Application EP 000,224.
  • the treating compositions of the present invention typically comp ⁇ se from about 0.2%, preferably from about 1% to about 25%, preferably to about 8%. by weight of such cationic surfactants.
  • Ampholytic Surfactants - Ampholytic surfactants are also suitable for use in the treating compositions of the present invention.
  • the treating compositions of the present invention typically comp ⁇ se from about 0J% > , preferably from about 1% to about 15%., preferably to about 10% by weight of such ampholytic surfactants.
  • Zwittenonic Surfactants - Zwitte ⁇ onic surfactants examples of which are descnbed in
  • the treating compositions of the present invention typically comp ⁇ se from about 0J%>, preferably from about 1% to about 15%), preferably to about 10% by weight of such zwittenonic surfactants.
  • Semi-polar Noniomc Surfactants are a special category of noniomc surfactants which include water-soluble amine oxides having the formula:
  • R 3 (OR 4 ) x N(R 5 ) 2 wherem R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R-> is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group contammg from about 1 to about 3 ethylene oxide groups (the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a nng structure); water- soluble phosphine oxides contammg one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-
  • the amine oxide surfactants m particular include Cjo-Cjg alkyl dimethyl amine oxides and Cg-C * i2 alkoxy ethyl dihydroxy ethyl amine oxides
  • the treating compositions of the present invention typically comp ⁇ se from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such semi-polar noniomc surfactants.
  • the treating compositions of the present invention may further comp ⁇ se a cosurfactant selected from the group of pnmary or tertiary amines. Suitable p ⁇ mary amines for use herein include amines according to the formula R]NH2 wherem R ⁇ is a Cg-C ⁇ preferably
  • Co-Cjo alkyl chain or R X(CH2) n X is -0-,-C(0)NH- or -NH- ;
  • R is a Cg-C ⁇ alkyl chain n is between 1 to 5, preferably 3.
  • R ⁇ alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
  • Preferred amines according to the formula herein above are n-alkyl amines. Suitable amines for use herein may be selected from 1-hexylam ⁇ ne, 1-octylam ⁇ ne, 1-decylamme and laurylamme. Other preferred p ⁇ mary amines include C8-C10 oxypropylamine, octyloxypropylamme, 2-ethylhexyl-oxypropylamme, lauryl amido propylamme and amido propylamme.
  • the most preferred amines for use in the compositions herein are 1-hexylamme, 1- octylamme, 1-decylam ⁇ ne, 1-dodecylamme. Especially desirable are n-dodecyldimethylamme and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamme and cocoamido propylamme.
  • LFNIs - Low foaming noniomc surfactants (LFNT) which are descnbed in U.S. Patent
  • LFNI may be present in amounts from 0.01% to about 10% by weight, preferably from about 0.1% to about 10%, and most preferably from about 0.25% to about 4%.
  • LFNIs are most typically used in automatic dishwashing detergent compositions (ADDs) on account of the improved water-sheetmg action (especially from glass) which they confer to the ADD product. They also encompass non-sihcone, nonphosphate polyme ⁇ c matenals further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.
  • Preferred LFNIs include noniomc alkoxylated surfactants, especially ethoxylates de ⁇ ved from p ⁇ mary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers as descnbed in U.S. Patent Nos. 5,705,464 and 5,710,115.
  • noniomc alkoxylated surfactants especially ethoxylates de ⁇ ved from p ⁇ mary alcohols
  • PO/EO/PO polyoxypropylene/polyoxyethylene/polyoxypropylene reverse block polymers
  • LFNIs which may also be used include those POLY-TERGENT® SLF-18 noniomc surfactants from Ohn Corp., and any biodegradable LFNI having the melting point properties discussed heremabove. These and other noniomc surfactants are well known in the art, being descnbed m more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference herein.
  • Bleaching System The treating compositions of the present invention may comp ⁇ se a bleaching system.
  • Bleaching systems typically comp ⁇ se a "bleaching agent” (source of hydrogen peroxide) and an "initiator” or “catalyst"
  • bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%>, preferably to about 20%> by weight of the composition
  • the amount of bleach activator will typically be from about 0.1%, preferably from about 0 5% to about 60%, preferably to about 40% by weight, of the treating composition comprising the bleaching agent-plus-bleach activator.
  • Bleaching Agents Hydrogen peroxide sources are described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol 4, pp. 271-300 "Bleaching Agents (Survey)", and include the vanous forms of sodium perborate and sodium percarbonate, including vanous coated and modified forms.
  • the preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself.
  • perborate e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
  • sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
  • Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
  • a preferred percarbonate bleach comp ⁇ ses dry particles having an average particle size m 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 a silicate, borate or water-soluble surfactants.
  • Percarbonate is available from vanous commercial sources such as FMC, Solvay and Tokai Denka.
  • compositions of the present invention may also compnse as the bleaching agent a chlonne-type bleaching matenal.
  • Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC").
  • NaDCC sodium dichloroisocyanurate
  • chlonne-type bleaches are less preferred for compositions which comp ⁇ se enzymes.
  • peroxygen bleaching agents are used as all or part of the particulate matenal, they will generally compnse from about 0.1% to 30%> by weight of the composition. More preferably, peroxygen bleaching agent will compnse from about 1% to 20% by weight of the composition. Most preferably, peroxygen bleaching agent will be present to the extent of from about 5% to 20% by weight of the composition
  • the peroxygen bleach component in the composition is formulated with an activator (peracid precursor).
  • the activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1%>, most preferably from about 3% to about 20%, preferably to about 15%, more preferably to about 10%), most preferably to about 8%, by weight of the composition.
  • activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1: 1 to 10: 1, more preferably from about 1.5: 1 to 5J.
  • bleach activators when agglomerated with certain acids such as cit ⁇ c acid, are more chemically stable.
  • Preferred activators are selected from the group consisting of tetraacetyl ethylene diamme (TAED), benzoylcaprolactam (BzCL), 4-n ⁇ trobenzoylcaprolactam, 3-chlorobenzoyl- caprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C * [ Q -OBS), benzoylvalerolactam
  • TAED tetraacetyl ethylene diamme
  • BzCL benzoylcaprolactam
  • 4-n ⁇ trobenzoylcaprolactam 3-chlorobenzoyl- caprolactam
  • benzoyloxybenzenesulphonate BOBS
  • NOBS nonanoyloxybenzenesulphonate
  • PhBz phenyl benzoate
  • bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
  • Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) ammo hexanoyloxy] -benzene sulfonate sodium salt (NACA-OBS) an example of which is desc ⁇ bed m U.S. Patent No. 5,523,434, dodecanoyloxybenzenesulphonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or C ⁇ -OBS with unsaturation in the 10 position), and decanoyloxybenzoic acid
  • NOBS nonanoyloxybenzenesulphonate
  • NACA-OBS 4-[N-(nonaoyl) ammo hexanoyloxy] -benzene sulfonate sodium salt
  • LOBS or C12-OBS dodecanoyloxybenzenes
  • Preferred bleach activators are those desc ⁇ bed in U.S. 5,698,504 Christie et al., issued December 16, 1997; U.S. 5,695,679 Chnstie et al. issued December 9, 1997; U.S. 5,686,401 Willey et al., issued November 11, 1997; U.S. 5,686,014 Hartshorn et al., issued November 11, 1997; U.S. 5,405,412 Willey et al., issued Apnl 11, 1995; U.S. 5,405,413 Willey et al., issued Apnl 11, 1995; U.S. 5,130,045 Mitchel et al., issued July 14, 1992; and U.S. 4,412,934 Chung et al., issued November 1, 1983, and copendmg patent applications U. S. Senal Nos. 08/709,072, 08/064,564, all of which are incorporated herein by reference.
  • the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator m the present invention generally ranges from at least 1 : 1, preferably from about 20: 1, more preferably from about 10: 1 to about 1:1, preferably to about 3:1.
  • Quaternary substituted bleach activators may also be included.
  • the present cleaning compositions preferably comp ⁇ se a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
  • QSBA quaternary substituted bleach activator
  • QSP quaternary substituted peracid
  • Preferred QSBA structures are further described in U.S. 5,686,015 Willey et al, issued November 11, 1997; U.S. 5,654,421 Taylor et al., issued August 5, 1997; U.S. 5,460,747 Gosselmk et al., issued October 24, 1995, U.S. 5,584,888 Miracle et al., issued December 17, 1996; and U.S. 5,578,136 Taylor et al, issued November 26, 1996; all of which are incorporated herein by reference.
  • bleach activators useful herein are amide-substituted as descnbed m U.S. 5,698,504, U.S. 5,695,679, and U.S. 5,686,014 each of which are cited herein above.
  • Preferred examples of such bleach activators include: (6-octanam ⁇ docaproyl) oxybenzenesulfonate, (6-nonanam ⁇ docaproyl)oxybenzenesulfonate, (6-decanam ⁇ docaproyl)oxybenzenesulfonate and mixtures thereof.
  • bleaching results can be obtained from bleaching systems having with m-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5.
  • activators with electron- withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
  • Alkalis and buffe ⁇ ng agents can be used to secure such pH.
  • X is selected from substituted or unsubstituted, branched or linear C ⁇ -C20 alkyl, substituted or unsubstituted, branched or linear C2-C20 alkylene.
  • X is branched or linear C ⁇ -C12 alkyl, branched or linear C2 -C12 alkylene, more preferably branched or linear C * [ -Cg alkyl, branched or linear C2-C alkylene, most preferably linear C ⁇ -Cg alkyl.
  • A is selected from:
  • n is selected from the numbers 0, 1, 2, 3 or 4.
  • n is 0,1,2 or 3 and more preferably, OJ, or 2.
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, chlo ⁇ de, bromide, iodide, substituted or unsubstituted branched or linear Cj-C2o alkyl, substituted or unsubstituted branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl.
  • R 1 and R 2 are independently hydrogen, chlonde, substituted or unsubstituted branched or linear Ci -Cjg alkyl, substituted or unsubstituted branched or linear C2-C ⁇ g alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl.
  • R 1 and R 2 are independently hydrogen, unsubstituted branched or linear C j -Cig alkyl, unsubstituted branched or linear C2-C1 g alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted alkylphenyl substituted or unsubstituted alkylnapthyl. It is further preferred that one of R!
  • R 2 is hydrogen or unsubstituted branched or linear Cj-Cg alkyl and the other is either an unsubstituted branched or linear C1 -C16 alkyl or an unsubstituted branched or linear C2-C16 alkenyl.
  • L is a modified or unmodified lactam leaving group.
  • the lactams which are suitable as leaving groups in the present application have the genenc structure:
  • R N where R represents an optionally substituted alkenyl chain with at least two carbon atoms m the alkenyl chain.
  • This alkenyl chain forms a cyclic structure with the -N- and -C(O)-.
  • the term modified means that the alkenyl can be substituted at least once or that one or more of the alkenyl carbon atoms can be substituted by a suitable heterocycle or any combination of both.
  • Suitable heterocyclic chain substitutes are O, N, and S, with O being preferred.
  • Suitable substituents include, but are not limited to, C ⁇ -C alkyl, Cj-Cg alkenyl, Cj-Cg alkoxy, chlo ⁇ de, bromide, iodide.
  • the preferred substituents are Cj-Cg alkyl, Cj-Cg alkoxy and chlo ⁇ de.
  • the most preferred modified lactam leaving groups are: alpha-chlorocaprolactam, alpha-chloro- valerolactam, alpha,alpha-d ⁇ chlorolactam, alpha,alpha-d ⁇ chlorovalerolactam, alpha- methoxycaprolactam, alpha-methoxy-valerolactam,
  • lactams When the lactams are unmodified, it means that they are contain no substituents other that hydrogen and have no heterocyclic substitution of the alkenyl chain of R.
  • R is preferably an alkenyl chain of two to seven carbon atoms. It is preferred that the lactam leaving group will be unmodified. It is more preferred that the unsubstituted lactam leaving group will be either caprolactam or valerolactam. That is:
  • compositions and methods may utilize metal-containmg bleach catalysts that are effective for use in bleaching compositions. Preferred are manganese and cobalt-containing bleach catalysts.
  • One type of metal-contaming bleach catalyst is a catalyst system compnsmg a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediammetetraacetic acid, ethylenediammetetra (methylenephosphonic acid) and water-soluble salts thereof.
  • Such catalysts are disclosed m U.S. 4,430,243 Bragg, issued February 2, 1982.
  • compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed m U.S. Patent Nos. 5,576,282; 5,246.621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn IV 2( u - 0 )3(l,4J-t ⁇ methyl-l,4J-t ⁇ azacyclononane)2(PF 6 )2, Mn m 2( u - 0 )l( u - OAc )2( 1 .
  • Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are descnbed, for example, m U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L.
  • cobalt pentaarmne acetate salts having the formula [Co(NH3)5 ⁇ Ac] T y , wherem "OAc” represents an acetate moiety and “T y " is an anion, and especially cobalt pentaarmne acetate chlo ⁇ de, [Co(NH3)5 ⁇ Ac]Cl2; as well as [Co(NH3) 5 OAc](OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 )2; [Co(NH 3 ) 5 OAc](S0 4 ); [Co-
  • cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; in the Tobe article and the references cited therein; and m U.S. Patent 4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characte ⁇ zation of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem.. 18, 1497-1502 (1979); Inorg. Chem.. 21, 2881-2885 (1982); Inorg Chem.. 18, 2023-2025 (1979); Inorg.
  • Transition Metal Complexes of Macropolvcvchc Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycychc ngid ligand.
  • the phrase "macropolycychc ⁇ gid ligand” is sometimes abbreviated as "MRL" in discussion below.
  • the amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherem “ppb” denotes parts per billion by weight and "ppm” denotes parts per million by weight).
  • Suitable transition metals e g., Mn are illustrated hereinafter.
  • Macropolycychc means a MRL is both a macrocycle and is polycychc
  • Polycychc means at least bicychc.
  • the term “ngid” as used herein includes “having a superstructure” and “cross-b ⁇ dged”. "Rigid” has been defined as the constrained converse of flexibility: see D H. Busch., Chemical Reviews.. (1993), 93, 847-860, incorporated by reference.
  • ngid means that the MRL must be determmably more rigid than a macrocycle ("parent macrocycle") which is otherwise identical (having the same nng size and type and number of atoms m the mam ⁇ ng) but lacking a superstructure (especially linking moieties or, preferably cross-b ⁇ dgmg moieties) found m the MRL's.
  • parent macrocycle which is otherwise identical (having the same nng size and type and number of atoms m the mam ⁇ ng) but lacking a superstructure (especially linking moieties or, preferably cross-b ⁇ dgmg moieties) found m the MRL's.
  • Rigidity is well-known to be useful in compa ⁇ ng macrocycles; suitable tools for determining, measu ⁇ ng or companng rigidity include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al., Inorganica Chimica Acta. (1989). 164, 73-84.
  • Preferred MRL's herein are a special type of ultra- ⁇ gid ligand which is cross-b ⁇ dged.
  • cross-bndge is nonhmitingly illustrated in 1.11 herembelow.
  • the cross-b ⁇ dge is a -
  • Suitable metals in the ngid ligand complexes include Mn(U), Mn(ITf), Mn(IV), Mn(V),
  • transition-metals m the instant transition- metal bleach catalyst include manganese, iron and chromium. More generally, the MRL's (and the corresponding transition-metal catalysts) herein suitably comp ⁇ se:
  • a covalently connected non-metal superstructure capable of increasing the ⁇ gidity of the macrocycle, preferably selected from (1) a bndgmg superstructure, such as a linking moiety;
  • superstructure is used herein as defined in the literature by Busch et al., see, for example, articles by Busch in "Chemical Reviews”.
  • Preferred superstructures herein not only enhance the ngidity of the parent macrocycle, but also favor folding of the macrocycle so that it co-ordinates to a metal in a cleft.
  • Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated m Fig. 1 and Fig. 2 below, can be used.
  • n is an integer, for example from 2 to 8, preferably less than 6, typically 2 to 4, or
  • Fig. 2 wherem m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, tnalkylammomum, halogen, nitro, sulfonate, or the like.
  • the aromatic ⁇ ng in 1J0 can be replaced by a saturated nng, in which the atom m Z connecting into the ⁇ ng can contain N, O, S or C.
  • Suitable MRL's are further nonlimitingly illustrated by the following compound:
  • this ligand is named 5J2-d ⁇ methyl-l,5,8J2-tetraazab ⁇ cyclo[6.6J]hexadecane usmg the extended von Baeyer system. See “A Guide to lUPAC Nomenclature of Organic Compounds- Recommendations 1993", R. Panico, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.
  • Transition-metal bleach catalysts of Macrocychc Rigid Ligands which are suitable for use in the invention compositions can m general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or cleaning uses, and non-limitingly illustrated by any of the following:
  • Manganese(II) D ⁇ chloro-5-n-octyl-12-methyl-l,5,8J2-tetraaza-b ⁇ cyclo[6.6J]hexadecane
  • Manganese(II) Dichloro-5-n-butyl-12-methyl-l,5,8J2-tetraaza-bicyclo[6.6J]hexadecane
  • Manganese(II) D ⁇ chloro-5-n-octyl-12-methyl-l,5,8J2-tetraaza-b ⁇ cyclo[6.6J]hexadecane
  • 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 0J ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical compositions herein will compnse 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 bleaching compositions.
  • compositions herein may compnse one or more other bleach catalysts.
  • Preferred bleach catalysts are zwittenonic bleach catalysts, which are descnbed in U.S. Patent No. 5,576,282 (especially 3-(3,4-d ⁇ hydro ⁇ soqu ⁇ nolm ⁇ um) propane sulfonate.
  • Other bleach catalysts include cationic bleach catalysts are descnbed m U.S. Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO 95/13351, WO 95/13352, and WO 95/13353.
  • 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 m 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 0J ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical compositions herein will comp ⁇ se from about 0.0005% to about 0J%>, more preferably from about 0 004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions (e)
  • bleach catalyst especially manganese or cobalt catalysts
  • Preformed peracids are also suitable as bleaching agents, such as phtha mido-peroxy-caproic acid ("PAP") See for example U.S. Patent Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431.
  • Enzymes - The treating compositions herein may also optionally contain one or more types of detergent enzymes.
  • Such enzymes can include other proteases, amylases and hpases. They may be inco ⁇ orated into the non-aqueous liquid detergent compositions herein m the form of suspensions, "marumes" or "p ⁇ lls".
  • Another suitable type of enzyme compnses those in the form of slur ⁇ es of enzymes in noniomc surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL” or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP.” Suitable enzymes and levels of use are desc ⁇ bed m U.S. Pat. No. 5,576,282, 5,705,464 and 5,710,115.
  • Enzymes added to the compositions herein in the form of conventional enzyme p ⁇ lls are especially preferred for use herein.
  • Such pnlls will generally range m size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition.
  • P ⁇ lls in the compositions of the present invention have been found, m compa ⁇ son with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time.
  • compositions which utilize enzyme pnlls need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents.
  • enzymes added to the compositions herein may be in the form of granulates, preferably T-granulates.
  • Detersive enzyme means any enzyme having a cleaning, stam removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and hpases.
  • Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, hpases and peroxidases.
  • Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, xylanases, hpases, phosphohpases, esterases, cutmases, pectmases, keratanases, reductases, oxidases, phenoloxidases, hpoxygenases, hgnmases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabmosidases, hyaluromdase, chondroitmase, laccase, mannanases, xyloglucanases and known amylases, or mixtures thereof Examples of such suitable enzymes are disclosed in U.S. Patent Nos. 5,705,464,
  • Peroxidase enzymes are used m combination with oxygen sources, e.g percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates m the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, hgninase and haloperoxidase such as chloro- and bromo-peroxidase.
  • Suitable peroxidases and peroxidase-containmg detergent compositions are disclosed, for example, in U.S. Patent Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950, PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
  • Enhancers are generally comp ⁇ sed at a level of from 0.1% to 5% by weight of total composition.
  • Preferred enhancers are substituted phenthiazme and phenoxasme 10- Phenothiazmepropiomcacid (PPT), 10-ethylphenothiazine-4-carboxyhc acid (EPC), 10- phenoxazmepropionic acid (POP) and 10-methylphenoxazine (desc ⁇ bed in WO 94/12621) and substitued synngates (C3-C5 substitued alkyl sy ⁇ ngates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said peroxidases are normally incorporated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
  • Enzymatic systems may be used as bleaching agents.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or dunng the washing and/or nnsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
  • Other preferred enzymes that can be included m the cleanmg compositions of the present invention include hpases.
  • Suitable hpase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzen ATCC 19.154, as disclosed in Bntish Patent 1,372,034.
  • Suitable hpases include those which show a positive immunological cross-reaction with the antibody of the hpase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This hpase is available from Amano Pharmaceutical Co Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano- P".
  • hpases include Amano-CES, hpases ex Chromobacter viscosum, e g. Chromobacter viscosum var I ⁇ olyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum hpases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and hpases ex Pseudomonas gladioli.
  • Amano-CES hpases ex Chromobacter viscosum, e g. Chromobacter viscosum var I ⁇ olyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan
  • Chromobacter viscosum hpases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands
  • hpases ex Pseudomonas gladioli.
  • hpases such as Ml L ⁇ pase R anci L ⁇ pomax R (Gist-Brocades) and L ⁇ polase R and Lipolase Ultra-R Novo
  • hpolytic enzymes desc ⁇ bed in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever
  • cutinases [EC 3.L 50] which can be considered as a special kind of hpase, namely hpases which do not require mterfacial activation.
  • Lipases and/or cutinases when present, are normally incorporated in the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
  • phosphohpases may be incorporated into the cleaning compositions of the present invention.
  • suitable phosphohpases included: EC 3JJJ2 Phosphohpase Al; EC 3J.L4 Phosphohpase A2; EC 3.LL5 Lysophohpase; EC 3.1.4.3 Phosphohpase C; EC 3. 4.4.
  • Phospohpase D Commercially available phosphohpases include LECITASE® from Novo Nordisk A/S of Denmark and Phosphohpase A2 from Sigma. When phospohpases are mcluded m the compositions of the present invention, it is preferred that amylases are also included.
  • the combined action of the phosphohpase and amylase provide substantive stam removal, especially on greasy/oily, starchy and highly colored stams and soils.
  • the phosphohpase and amylase when present, are incorporated into the compositions of the present invention at a pure enzyme weight ratio between 4500:1 and 1:5, more preferably between 50: 1 and 1 :1.
  • Suitable proteases are the subtihsms which are obtained from particular strains of B subtilis and B. licheniformis (subtihsm BPN and BPN')
  • 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 Indust ⁇ es A/S of Denmark, hereinafter "Novo".
  • the preparation of this enzyme and analogous enzymes is desc ⁇ bed in GB 1,243,784 to Novo.
  • Proteolytic enzymes also encompass modified bacte ⁇ al senne proteases, such as those desc ⁇ bed in European Patent Application Senal Number 87 303761.8, filed Apnl 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bactenal senne protealytic enzyme which is called "Protease A" herein.
  • Protease C is a vanant of an alkaline senne protease from Bacillus in which Lysme replaced argimne at position 27, tyrosine replaced valme at position 104, senne replaced asparagme at position 123, and alanine replaced threonme at position 274.
  • Protease C is described in EP 90915958 4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase as described in U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase variant of the protease described in WO95/10591, having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtil
  • proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.
  • protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
  • a protease having decreased adso ⁇ tion and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
  • Other suitable proteases are described in EP 516 200 by Unilever.
  • proteases are described in PCT publications: WO 95/30010; WO 95/30011; and WO 95/29979. Suitable proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands).
  • Other particularly useful proteases are multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160,
  • protease variant includes a substitution set selected from the group consisting of:
  • the protease variant includes a substitution set selected from the group consisting of:
  • amylolytic enzymes when present, are inco ⁇ orated in the cleaning compositions of the present invention a level of from 0 0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0 00024%) to 0.048% pure enzyme by weight of the composition.
  • compositions of the present invention may also comp ⁇ se a mannanase enzyme.
  • the mannanase is selected from the group consisting of: three mannans-degrading enzymes : EC 3.2.1.25 : ⁇ -mannosidase, EC 3.2.1 78 : Endo-l,4- ⁇ -mannos ⁇ dase, referred therein after as "mannanase” and EC 3.2.1.100 : 1 ,4- ⁇ -mannob ⁇ os ⁇ dase and mixtures thereof.
  • the treating compositions of the present invention when a mannanase is present, comp ⁇ se a ⁇ -l,4-Mannos ⁇ dase (E.C. 3.2.1.78) referred to as Mannanase.
  • Mannanase or "galactomannanase” denotes a mannanase enzyme defined according to the art as officially being named mannan endo-l,4-beta-mannos ⁇ dase and having the alternative names beta-mannanase and endo-l,4-mannanase and catalyzing the reaction: random hydrolysis of 1,4- beta-D- mannosidic linkages in mannans, galactomannans, glucomannans, and galactoglucomannans.
  • Mannanases (EC 3.2.1.78) constitute a group of polysaccharases which degrade mannans and denote enzymes which are capable of cleaving polyose chains containing mannose units, i.e. are capable of cleaving glycosidic bonds in mannans, glucomannans, galactomannans and galactogluco-mannans.
  • Mannans are polysacchandes having a backbone composed of ⁇ -1,4- linked mannose; glucomannans are polysacchandes having a backbone or more or less regularly alternating ⁇ -1,4 linked mannose and glucose; galactomannans and galactoglucomannans are mannans and glucomannans with ⁇ -1,6 linked galactose sidebranches. These compounds may be acetylated.
  • the degradation of galactomannans and galactoglucomannans is facilitated by full or partial removal of the galactose sidebranches. Further the degradation of the acetylated mannans, glucomannans, galactomannans and galactogluco-mannans is facilitated by full or partial deacetylation. Acetyl groups can be removed by alkali or by mannan acetylesterases.
  • the oligomers which are released from the mannanases or by a combination of mannanases and ⁇ - galactosidase and/or mannan acetyl esterases can be further degraded to release free maltose by ⁇ -mannosidase and/or ⁇ -glucosidase.
  • Mannanases have been identified in several Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp. 3505-3510 (1990) desc ⁇ bes a beta-mannanase de ⁇ ved from Bacillus stearothermophilus in dimer form having molecular weight of 162 kDa and an optimum pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp.
  • JP-03047076 discloses a beta- mannanase de ⁇ ved from Bacillus sp., having a molecular weight of 373 kDa measured by gel filtration, an optimum pH of 8-10 and a pi of 5J-5 4.
  • JP-63056289 desc ⁇ bes the production of an alkaline, thermostable beta-mannanase which hydrolyses beta-l,4-D-mannopyranos ⁇ de bonds of e.g.
  • JP-63036774 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase at an alkaline pH.
  • JP-08051975 discloses alkaline beta-mannanases from alkalophihc Bacillus sp. AM- 001.
  • a purified mannanase from Bacillus amyloliquefaciens useful in the bleaching of pulp and paper and a method of preparation thereof is disclosed in WO 97/11164.
  • WO 91/18974 desc ⁇ bes a hemicellulase such as a glucanase, xylanase or mannanase active at an extreme pH and temperature.
  • WO 94/25576 discloses an enzyme from Aspergillus aculeatus, CBS 101.43, exhibiting mannanase activity which may be useful for degradation or modification of plant or algae cell wall matenal.
  • WO 93/24622 discloses a mannanase isolated from Trichoderma reseei useful for bleaching hgnocellulosic pulps.
  • An hemicellulase capable of degrading mannan- contammg hemicellulose is descnbed in W091/18974 and a pu ⁇ f ⁇ ed mannanase from Bacillus amyloliquefaciens is desc ⁇ bed in W097/11164.
  • the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase originating from a bacte ⁇ al source.
  • the laundry detergent composition of the present invention will compnse an alkaline mannanase selected from the mannanase from the strain Bacillus agaradhaerens NICMB 40482; the mannanase from Bacillus subtilis strain 168, gene yght; the mannanase from Bacillus sp. 1633 and/or the mannanase from Bacillus sp. AAI12.
  • mannanase for the inclusion in the detergent compositions of the present invention is the mannanase enzyme o ⁇ gmatmg from Bacillus sp. 1633 as descnbed m the co-pending Danish patent application No. PA 1998 01340.
  • alkaline mannanase enzyme is meant to encompass an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5.
  • the alkaline mannanase from Bacillus agaradhaerens NICMB 40482 is desc ⁇ bed in the co-pendmg U.S. patent application se ⁇ al No. 09/111,256. More specifically, this mannanase is: l) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or n) a polypeptide comp ⁇ sing an amino acid sequence as shown m positions 32-343 of SEQ ED NO:2 as shown in U.S. patent application se ⁇ al No.
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the ammo acid sequence of SEQ ID NO: 2 from ammo acid residue 32 to ammo acid residue 343 as shown in U.S. patent application senal No. 09/111,256;
  • the plasmid pSJ1678 comp ⁇ sing the polynucleotide molecule (the DNA sequence) encoding said mannanase has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Pmposes of Patent Procedure at the Deutsche Sammlung von Mikroorgamsmen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 18 May 1998 under the deposition number DSM 12180.
  • a second more preferred enzyme is the mannanase from the Bacillus subtilis strain 168, which is desc ⁇ bed m the co-pendmg U.S. patent application se ⁇ al No. 09/095,163. More specifically, this mannanase is:
  • 0 is encoded by the coding part of the DNA sequence shown m SED ID No. 5 shown in the U.S. patent application se ⁇ al No. 09/095,163 or an analogue of said sequence; and/or u) a polypeptide comp ⁇ sing an ammo acid sequence as shown SEQ DD NO: 6 shown in the U.S. patent application senal No. 09/095,163; or in) an analogue of the polypeptide defined in n) which is at least 70%> homologous with said polypeptide, or is de ⁇ ved from said polypeptide by substitution, deletion or addition of one or several am o acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in punfied form. Also encompassed m the corresponding isolated polypeptide having mannanase activity selected from the group consisting of:
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70%> identical to the ammo acid sequence of SEQ ED NO: 6 as shown in the U.S. patent application senal No. 09/095,163;
  • mannanase degenerate nucleotide sequences of (a), (b), (c) or (d).
  • a third more preferred mannanase is descnbed in the co-pendmg Danish patent application No. PA 1998 01340. More specifically, this mannanase is: l) a polypeptide produced by Bacillus sp. 1633; n) a polypeptide comp ⁇ sing an ammo acid sequence as shown in positions
  • isolated polynucleotide molecule selected from the group consisting of: (a) polynucleotide molecules encoding a polypeptide having mannanase activity and compnsmg a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 317 to nucleotide 1243 the Danish application No. PA 1998 01340;
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO:
  • a fourth more preferred mannanase is desc ⁇ bed in the Danish co-pend g patent application No. PA 1998 01341 More specifically, this mannanase is: l) a polypeptide produced by Bacillus sp AAI 12, n) a polypeptide comp ⁇ sing an ammo acid sequence as shown in positions 25-362 of SEQ ID NOJas shown in the Danish application No.
  • PA 1998 01341 or in) an analogue of the polypeptide defined in l) or n) which is at least 65% homologous with said polypeptide, is denved from said polypeptide by substitution, deletion or addition of one or several ammo acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in pu ⁇ fied form.
  • analogue of the polypeptide defined in l) or n) which is at least 65% homologous with said polypeptide is denved from said polypeptide by substitution, deletion or addition of one or several ammo acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in pu ⁇ fied form.
  • the corresponding isolated polynucleotide molecule selected from the group consisting of
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the ammo acid sequence of SEQ ID NO:
  • the mannanase when present, is inco ⁇ orated into the treating compositions of the present invention preferably at a level of from 0 0001% to 2%, more preferably from 0.0005% to 0 1%, most preferred from 0.001% to 0.02% pure enzyme by weight of the composition.
  • the compositions of the present invention may also comp ⁇ se a xyloglucanase enzyme
  • Suitable xyloglucanases for the pu ⁇ ose of the present invention are enzymes exhibiting endoglucanase activity specific for xyloglucan, preferably at a level of from about 0.001% to about 1%, more preferably from about 0.01% to about 0.5%, by weight of the composition.
  • endoglucanase activity means the capability of the enzyme to hydrolyze 1,4- ⁇ -D-glycos ⁇ d ⁇ c linkages present in any cellulosic matenal, such as cellulose, cellulose derivatives, lichenm, ⁇ -D-glucan, or xyloglucan.
  • the endoglucanase activity may be determined in accordance with methods known in the art, examples of which are descnbed m WO 94/14953 and hereinafter.
  • One unit of endoglucanase activity e.g. CMCU, AVIU, XGU or BGU
  • CMCU CMC
  • AVIU acid swollen Avicell
  • XGU xyloglucan
  • BGU cereal ⁇ -glucan
  • the reducing sugars are determined as descnbed in WO 94/14953 and hereinafter.
  • the specific activity of an endoglucanase towards a substrate is defined as umts/mg of protein.
  • the term "specific for xyloglucan” means that the endoglucanase enzyme exhibits its highest endoglucanase activity on a xyloglucan substrate, and preferably less than 75%) activity, more preferably less than 50%> activity, most preferably less than about 25% activity, on other cellulose-containing substrates such as carboxymethyl cellulose, cellulose, or other glucans.
  • the specificity of an endoglucanase towards xyloglucan is further defined as a relative activity determined as the release of reducing sugars at optimal conditions obtained by incubation of the enzyme with xyloglucan and the other substrate to be tested, respectively.
  • the specificity may be defined as the xyloglucan to ⁇ -glucan activity (XGU BGU), xyloglucan to carboxy methyl cellulose activity (XGU/CMCU), or xyloglucan to acid swollen
  • Avicell activity (XGU/ AVIU), which is preferably greater than about 50, such as 75, 90 or 100.
  • the term "derived from” as used herein refers not only to an endoglucanase produced by strain CBS 101.43, but also an endoglucanase encoded by a DNA sequence isolated from strain CBS 101.43 and produced m a host organism transformed with said DNA sequence.
  • homologue indicates a polypeptide encoded by DNA which hyb ⁇ dizes to the same probe as the DNA coding for an endoglucanase enzyme specific for xyloglucan under certain specified conditions (such as presoakmg in 5xSSC and prehyb ⁇ dizmg for 1 h at -40°C m a solution of 5xSSC, 5xDenhardt's solution, and 50 ⁇ g of denatured sonicated calf thymus DNA, followed by hyb ⁇ dization in the same solution supplemented with 50 ⁇ Ci 32-P-dCTP labelled probe for 18 h at -40°C and washing three times in 2xSSC, 0.2% SDS at 40°C for 30 minutes).
  • the term is intended to refer to a DNA sequence which is at least 70% homologous to any of the sequences shown above encoding an endoglucanase specific for xyloglucan, including at least 75%, at least 80%, at least 85%, at least 90% or even at least 95% with any of the sequences shown above.
  • the term is intended to include modifications of any of the DNA sequences shown above, such as nucleotide substitutions which do not give nse to another ammo acid sequence of the polypeptide encoded by the sequence, but which correspond to the codon usage of the host organism into which a DNA construct compnsmg any of the DNA sequences is introduced or nucleotide substitutions which do give nse to a different amino acid sequence and therefore, possibly, a different amino acid sequence and therefore, possibly, a different protein structure which might give nse to an endoglucanase mutant with different properties than the native enzyme.
  • Other examples of possible modifications are insertion of one or more nucleotides into the sequence, addition of one or more nucleotides at either end of the sequence, or deletion of one or more nucleotides at either end or within the sequence.
  • Endoglucanase specific for xyloglucan useful in the present invention preferably is one which has a XGU BGU, XGU/CMU and/or XGU/AVIU ratio (as defined above) of more than 50, such as 75, 90 or 100.
  • endoglucanase specific for xyloglucan is preferably substantially devoid of activity towards ⁇ -glucan and/or exhibits at the most 25% such as at the most 10% or about 5%, activity towards carboxymethyl cellulose and/or Avicell when the activity towards xyloglucan is 100%.
  • endoglucanase specific for xyloglucan of the invention is preferably substantially devoid of transferase activity, an activity which has been observed for most endoglucanases specific for xyloglucan of plant origin. Endoglucanase specific for xyloglucan may be obtained from the fungal species A aculeatus, as desc ⁇ bed in WO 94/14953.
  • Microbial endoglucanases specific for xyloglucan has also been desc ⁇ bed in WO 94/14953. Endoglucanases specific for xyloglucan from plants have been desc ⁇ bed, but these enzymes have transferase activity and therefore must be considered mfe ⁇ or to microbial endoglucanases specific for xyloglucan whenever extensive degradation of xyloglucan is desirable.
  • An additional advantage of a microbial enzyme is that it, in general, may be produced in higher amounts m a microbial host, than enzymes of other ongms.
  • the xyloglucanase when present, is inco ⁇ orated into the treating compositions of the invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0 001% to 0.02% pure enzyme by weight of the composition.
  • the above-mentioned enzymes may be of any suitable o ⁇ gm, such as vegetable, animal, bactenal, fungal and yeast o ⁇ gin Ongm can further be mesophihc or extremophihc (psychrophihc, psychrotrophic, thermophihc, barophihc, alkalophihc, acidophihc, halophihc, etc.).
  • Pu ⁇ fied or non-pu ⁇ fied forms of these enzymes may be used.
  • the vanants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
  • the va ⁇ ant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme va ⁇ ant is tailored to suit the particular cleaning application.
  • the isoelectnc point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase m isoelectnc point may help to improve compatibility with anionic surfactants.
  • the stability of the enzymes may be further enhanced by the creation of e.g. additional salt b ⁇ dges and enforcing calcium binding sites to increase chelant stability.
  • the enzymes can be added as separate single ingredients (p ⁇ lls, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • Other suitable cleanmg adjunct mate ⁇ als that can be added are enzyme oxidation scavengers. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polya ⁇ unes.
  • a range of enzyme mate ⁇ als and means for their mco ⁇ oration into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed m U.S. 4,101,457, and m U.S. 4,507,219. Enzyme matenals useful for liquid detergent formulations, and their mco ⁇ oration into such formulations, are disclosed in U.S. 4,261,868. Enzyme Stabilizers - Enzymes for use m treating compositions can be stabilized by vanous techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S.
  • Enzyme stabilization systems are also descnbed, for example, in U S 3,519,570
  • the enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are described in U.S. Pat. Nos 5,705,464, 5,710,115 and 5,576,282.
  • Builders - The treating compositions descnbed herein preferably comp ⁇ se one or more detergent builders or builder systems.
  • compositions will typically comp ⁇ se at least about 1%) builder, preferably from about 5%, more preferably from about 10% to about 80%>, preferably to about 50%, more preferably to about 30% by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Preferred builders for use in the treating compositions, particularly dishwashing compositions, described herein include, but are not limited to, water-soluble builder compounds, (for example polycarboxylates) as descnbed m U.S. Patent Nos. 5,695,679, 5,705,464 and 5,710,H5. Other suitable polycarboxylates are disclosed m U.S. Patent Nos. 4,144,226,
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly titrates.
  • Inorganic or P-contaimng detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammomum salts of polyphosphates (exemplified by the t ⁇ polyphosphates, pyrophosphates, and glassy polyme ⁇ c meta-phosphates), phosphonates (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and alummosihcates.
  • polyphosphates exemplified by the t ⁇ polyphosphates, pyrophosphates, and glassy polyme ⁇ c meta-phosphates
  • phosphonates see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137
  • compositions herein function su ⁇ nsmgly well even m the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt” situation that may occur with zeolite or layered silicate builders.
  • Suitable silicates include the water-soluble sodium silicates with an S ⁇ 0 2 :Na 2 0 ratio of from about 1.0 to 2.8, with ratios of from about 1.6 to 2.4 being preferred, and about 2.0 ratio being most preferred.
  • the silicates may be m the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an S ⁇ 0 2 :Na 2 0 ratio of 2.0 is the most preferred.
  • Silicates, when present, are preferably present in the treating compositions desc ⁇ bed herein at a level of from about 5% to about 50% by weight of the composition, more preferably from about 10% to about 40% by weight.
  • Partially soluble or insoluble builder compounds which are suitable for use in the treating compositions, particularly granular detergent compositions, include, but are not limited to, crystalline layered silicates, preferably crystalline layered sodium silicates (partially water- soluble) as desc ⁇ bed in U.S. Patent No. 4,664,839, and sodium alummosihcates (water- insoluble).
  • these builders are typically present at a level of from about 1% to 80% by weight, preferably from about 10% to 70% by weight, most preferably from about 20% to 60% by weight of the composition.
  • Crystalline layered sodium silicates having the general formula NaMS ⁇ x ⁇ 2 x + ⁇ -yH2 ⁇ wherem M is sodium or hydrogen, x is a number from about 1.9 to about 4, preferably from about 2 to about 4, most preferably 2, and y is a number from about 0 to about 20, preferably 0 can be used in the compositions descnbed herein.
  • Crystalline layered sodium silicates of this type are disclosed m EP-A-0164514 and methods for their preparation are disclosed in DE-A- 3417649 and DE-A-3742043.
  • the most preferred matenal is delta-Na2S ⁇ 5, available from Hoechst AG as NaSKS-6 (commonly abbreviated herein as "SKS-6").
  • Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-N_2S ⁇ 5 mo ⁇ hology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use in the compositions descnbed herein, but other such layered silicates, such as those having the general formula NaMS ⁇ x ⁇ 2 x + ⁇ -yH2 ⁇ wherem 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 be used in the compositions descnbed herein.
  • Vanous other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • the delta-Na2S ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a c ⁇ spemng agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • the crystalline layered sodium silicate material is preferably present m granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble lomzable matenal.
  • the solid, water-soluble lomzable matenal is preferably selected from organic acids, organic and inorganic acid salts and mixtures thereof.
  • Alummosihcate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Alummosihcate builders have the empi ⁇ cal formula:
  • the alummosihcate builder is an alummosihcate zeolite having the unit cell formula:
  • alummosihcate builders are preferably m hydrated form and are preferably crystalline, containing from about 10% to about
  • alummosihcate ion exchange mate ⁇ als can be crystalline or amo ⁇ hous in structure and can be naturally-occurring alummosihcates or synthetically denved
  • a method for producing alummosihcate ion exchange mate ⁇ als is disclosed in U.S. 3,985,669.
  • crystalline alummosihcate ion exchange matenal has the formula:
  • Zeolite A Na 12 [(Al ⁇ 2)i2(S ⁇ 2)i2]-xH 2 0 wherein x is from about 20 to about 30, especially about 27
  • the alummosihcate has a particle size of about OJ-10 microns in diameter.
  • Zeolite X has the formula:
  • Citrate builders e.g., citnc acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succimc acid builders include the C5-C20 alkyl and alkenyl succimc acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccimc acid.
  • succmate builders include- laurylsuccinate, my ⁇ stylsuccmate, palmitylsucc ate, 2- dodecenylsuccmate (preferred), 2-pentadecenylsuccmate, and the like. Laurylsuccinates are the preferred builders of this group, and are desc ⁇ bed m European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C * i2-C ⁇ monocarboxyhc acids
  • C * i2-C ⁇ monocarboxyhc acids can also be inco ⁇ orated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succmate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • Dispersants - One or more suitable polyalkyleneimine dispersants may be inco ⁇ orated into the treating compositions of the present invention. Examples of such suitable dispersants can be found in European Patent Application Nos.
  • any suitable clay/soil dispersent or anti- redepostion agent can be used in the treating compositions of the present invention.
  • polymeric dispersing agents which include polyme ⁇ c polycarboxylates and polyethylene glycols, are suitable for use m the present invention
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumanc acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalo c acid.
  • Particularly suitable polymeric polycarboxylates can be denved from acrylic acid Sucn acrylic acid-based polymers which are useful herein are the water- soluble salts of polymenzed 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 mate ⁇ als. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, m U.S. 3,308,067.
  • Acry c/maleic-based copolymers may also be used as a preferred component of the dispersmg/anti-redeposition agent.
  • Such mate ⁇ als 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 mate ⁇ als which are descnbed in European Patent Application No. 66915, published December 15, 1982, as well as m EP 193,360, published September 3, 1986, which also descnbes such polymers comp ⁇ sing hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acryhc/vinyl alcohol te ⁇ olymers.
  • Such matenals are also disclosed in EP 193,360, including, for example, the 45/45/10 te ⁇ olymer of acryhc/maleic/vmyl alcohol.
  • Another polyme ⁇ c matenal which can be included is polyethylene glycol (PEG).
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these pu ⁇ oses range from about 500 to about 100,000, preferably from about 1,000 to about 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.
  • soil release agents may optionally comp ⁇ se one or more soil release agents.
  • soil release agents will generally comp ⁇ se from about 0.01%, preferably from about 0.1%, more preferably from about 0.2% to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition
  • suitable soil release polymers are disclosed m U.S Patent Nos 5,728,671, 5,691,298, 5,599,782; 5,415,807; 5,182,043, 4,956,447; 4,976,879, 4,968,451, 4,925,577; 4,861,512; 4,877,896; 4,771,730; 4,711,730; 4,721,580, 4,000,093; 3,959,230; and 3,893,929; and European Patent Application 0 219 048. Further suitable soil release agents are desc ⁇ bed in U.S. Patent Nos. 4,201,824;
  • the treating compositions of the present invention herein may also optionally contain a chelatmg agent which serves to chelate metal ions and metal expedities which would otherwise tend to deactivate the bleaching agent(s).
  • a chelatmg agent which serves to chelate metal ions and metal interruptionties which would otherwise tend to deactivate the bleaching agent(s).
  • Useful chelating agents can include ammo carboxylates, phosphonates, ammo phosphonates, polyfunctionally-substituted aromatic chelatmg agents and mixtures thereof. Further examples of suitable chelating agents and levels of use are descnbed in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282.
  • 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 comp ⁇ se from about 0.1% to about 15%, more preferably from about 0.1% to about 3.0% by weight of the treating compositions herein.
  • Suds suppressor - Another optional ingredient is a suds suppressor, exemplified by sihcones, and silica-sihcone mixtures. Examples of suitable suds suppressors are disclosed in U.S. Patent Nos. 5,707,950 and 5,728,671. These suds suppressors are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • Softening agents - Fab ⁇ c softening agents can also be inco ⁇ orated into the treating compositions of the present invention.
  • Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in U.S. 5,019,292.
  • Organic softening agents include the water insoluble tertiary amines as disclosed in GB-A-1 514 276 and EP-B-011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-026 527 and EP-B-026 528 and di-long-chain amides as disclosed in EP-B-0 242 919.
  • Other useful organic ingredients of fabnc softening systems include high molecular weight polyethylene oxide matenals as disclosed in EP-A-0 299 575 and 0 313 146
  • Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15%) by weight, with the matenal being added as a dry mixed component to the remainder of the formulation.
  • Organic fabnc softening agents such as the water-msoluble tertiary amines or dilong chain amide materials are inco ⁇ orated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide matenals and the water soluble cationic mate ⁇ als are added at levels of from 0.1% to 2%, normally from 0.15% to 1 5% by weight.
  • These mate ⁇ als are normally added to the spray dned portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.
  • Biodegradable quaternary ammonium compounds as descnbed in EP-A-040 562 and EP- A-239 910 have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlo ⁇ des and methyl sulfates.
  • Non-hmitmg examples of softener-compatible amons for the quaternary ammonium compounds and amine precursors include chlonde or methyl sulfate.
  • the treating compositions of the present invention can also include compounds for inhibiting dye transfer from one fab ⁇ c to another of solubihzed and suspended dyes encountered dunng fabnc launde ⁇ ng and conditioning operations involving colored fab ⁇ cs.
  • Polymeric dye transfer inhibiting agents The treating compositions according to the present invention can also comp ⁇ se from
  • polyme ⁇ c dye transfer inhibiting agents 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05%> to 1% by weight of polyme ⁇ c dye transfer inhibiting agents.
  • Said polyme ⁇ c dye transfer inhibiting agents are normally inco ⁇ orated into treating compositions in order to inhibit the transfer of dyes from colored fabrics onto fabncs washed therewith.
  • These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabncs before the dyes have the opportunity to become attached to other articles in the wash.
  • Especially suitable polyme ⁇ c dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrohdone and N-vmyhmidazole, polyvmylpyrrohdone polymers, polyvinyloxazohdones and polyvinylimidazoles or mixtures thereof. Examples of such dye transfer inhibiting agents are disclosed m U.S. Patent Nos. 5,707,950 and 5,707,951.
  • Additional suitable dye transfer inhibiting agents include, but are not limited to, cross- linked polymers.
  • Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been desc ⁇ bed in the Journal of Polymer Science, volume 22, pages 1035-1039.
  • the cross-linked polymers are made m such a way that they form a three-dimensional ngid structure, which can entrap dyes in the pores formed by the three- dimensional structure.
  • the cross-linked polymers entrap the dyes by swelling
  • Such cross-linked polymers are descnbed in the co-pendmg European patent application 94870213 9. Addition of such polymers also enhances the performance of the enzymes according the invention.
  • Hydrogen Bond Breaking Agents Suitable hydrogen bond breaking agents including, but not limited to, plant expansin and urea can optionally be inco ⁇ orated into the treating compositions of the present invention.
  • pH and Buffenng Vanation Many of the treating compositions desc ⁇ bed herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low buffe ⁇ ng capacity, or may be substantially unbuffered. Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled m the art.
  • Mate ⁇ als - Other cleaning adjunct mate ⁇ als optionally mcluded in the treating compositions of the present invention can include one or more matenals for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions.
  • Adjuncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct matenals compnse, m total, from about 30%.
  • compositions include other active ingredients such as clay soil removal/anti- redeposition agents, bnghteners, dyes, perfumes, structure elasticizmg agents, earners, hydrotropes, processing aids, fillers, germicides, alkalinity sources, solubilizing agents and/or pigments.
  • active ingredients such as clay soil removal/anti- redeposition agents, bnghteners, dyes, perfumes, structure elasticizmg agents, earners, hydrotropes, processing aids, fillers, germicides, alkalinity sources, solubilizing agents and/or pigments.
  • Suitable examples of such other cleaning adjunct mate ⁇ als and levels of use are found in U.S. Patent Nos. 5,576,282, 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101.
  • compositions of the present invention are not necessa ⁇ ly meant to limit or otherwise define the scope of the invention.
  • the enzyme levels are expressed by percent of pure enzyme by weight of the total composition and unless otherwise specified, the cleaning adjunct matenals are expressed as percent of cleaning adjunct mate ⁇ als by weight of the total compositions
  • the polysacchandes can be any suitable polysacchande disclosed heremabove. Further, in the following examples some abbreviations known to those of ordinary skill in the art are used, consistent with the disclosure set forth herein, and or are defined m below
  • Nonionic C13- 15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxy lation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by
  • Neodol 45-13 C14-C15 linear primary alcohol ethoxylate sold by Shell
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size between
  • Citric Anhydrous citric acid PB1 Anhydrous sodium perborate monohydrate bleach, empirical formula NaB0 .H 2 ⁇ 2 PB4 Anhydrous sodium perborate tetrahydrate
  • TAED Tetraacetyl ethylene diamine.
  • NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
  • Photoactivated Bleach Sulfonated zinc phtalocyanine encapsulated in dextrin soluble polymer.
  • Amylase Amylolytic enzyme described hereinbefore.
  • DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino-1.3.5-triazin-2-yl) stilbene-2 : 2'-disulfonate .
  • SRP 1 Sulfobenzoyl or sodium isethionate end capped esters with oxyethylene oxy and terephtaloyl backbone.
  • Perfume contains mainly ingredients having a boiling point of less than about 250°C.
  • Perfume contains mainly ingredients having a boiling point of about 250°C or higher.
  • Perfume contains mainly ingredients having a ClogP of about 3.0 or less.
  • Concentrated compositions of Examples Et are diluted with water to obtain usage compositions for, e.g., spraying, soaking, dipping, cellulosic fabrics.
  • Example HJ Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
  • DC-2-5932 silicone microemulsion (25% active) from Dow Corning with a particle size of about 24 nm, a cationic surfactant system, and a silicone with an internal phase viscosity of about 1,200 cps.
  • Copolymer B ' 0.5 - 0.3 — ⁇
  • DC-2-5932 silicone microemulsion (25% active) from Dow Coming with a particle size of about 24 nm, a cationic surfactant system, and a silicone with an internal phase viscosity of about 1J00 cps.
  • Acrylic acid/tert-butyl acrylate copolymer with an approximate acrylic acid/tert-butyl acrylate weight ratio of about 25/75 and an average molecular weight of from about 70,000 to about 100,000.
  • Acrylic acid/tert-butyl acrylate copolymer with an approximate acrylic acid/tert-butyl acrylate weight ratio of about 35/65 and an average molecular weight of from about 60,000 to about 90,000.
  • Acrylic acid tert-butyl acrylate copolymer with an approximate acrylic acid/tert-butyl acrylate weight ratio of about 20/80 and an average molecular weight of from about 80,000 to about 110,000.
  • Neodol 23-3 0.25 - 0.2 - -
  • Sihcone-containmg copolymer having (N,N,N-t ⁇ methylammon ⁇ oethyl methacrylate chlo ⁇ de)/N,N-d ⁇ methylacrylam ⁇ de/(PDMS macromer - 15,000 approximate molecular weight) at an approximate 40/40/20 weight ratio, and of average molecular weight of about 150,000.
  • Example Ve is a concentrated composition, to be diluted for use.
  • compositions of Examples I to VII are sprayed onto clothing using, e.g., the TS-800 sprayer from Calmar, and allowed to evaporate off of the clothing.
  • compositions of Examples I to VH (diluted when appropnate) are sprayed onto
  • compositions of Examples I to VH (diluted when approp ⁇ ate) contained in rechargeable battery-operated Solo Spraystar sprayers are sprayed onto large surfaces of fab ⁇ c, such as several pieces of clothing, and allowed to evaporate off of these surfaces.
  • the level of coverage is uniform and the ease and convenience of application is supe ⁇ or to conventional manually operated t ⁇ gger sprayers.
  • compositions of Examples I to VII are used for soaking or dipping of fab ⁇ cs which are then optionally wrung or squeezed to remove excess liquid and subsequently dned.
  • ⁇ nse added fab ⁇ c care compositions in accordance with the present invention are used for soaking or dipping of fab ⁇ cs which are then optionally wrung or squeezed to remove excess liquid and subsequently dned.
  • the cellulase consists essentially of a homogeneous endoglucanase component, which is lmmunoreactive with an antibody raised against a highly punfied 43 kD cellulase denved from Humicola insolens, DMS 1800, or which is homologous to said 43 kD endoglucanase; the cellulase solution used provides about 5,000 CEVU's per gram.
  • Nil bleach-contammg laundry detergent fab ⁇ c care compositions of particular use in the washing of colored clothing are provided:
  • Example XII imples of liquid detergent fabric care compositions according to the present i nventic
  • Example X__ Examples of syndet bar fabnc detergent fab ⁇ c care compositions in accord with the present invention:
  • syndet bar fabric detergent fabric care compositions in accord with the present invention:
  • Example XV The following detergent formulations, according to the present invention, are prepared where XVa and XVc are phosphorus-containing detergent compositions, and XVb is a zeolite-containing detergent composition:
  • Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0
  • Example XVII The following liquid detergent formulations, according to the present invention are prepared: xv ⁇ a xv ⁇ b xviic xv ⁇ xv ⁇ xv ⁇ xv ⁇ g xv ⁇ h d e f
  • Rapeseed fatty _ _ _ 5.0 _. 4.0 4.0 acids Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 1.0 1.0 Dodecenyl/ 12 0 10.0 - - 15.0 - - - tetradecenyl succimc acid
  • Component A B C D Polysaccharide 0.5 0.2 1 2
  • Phosphate (as sodium 23.00 23.00 23.00 23.00 tripolyphosphates) Sodium carbonate 23.00 23.00 23.00 23.00 Sodium silicate 14.00 14.00 14.00 14.00 Zeolite 8.20 820 8.20 8 JO
  • Zeolite A (1-10 micrometer) 26.00 26.00 26.00 26.00 26.00 Cl2"Cl4 secondary (2,3) alk yl sulfate, 5.00 5.00 5.00 5.00
  • Fillers e.g., silicates; carbonates; perfumes; water Up to 100 Up to 100
  • Soil release polymer 0.41 0.41 0.31 Polysaccharide 1 0.75 3 Cellulase 0.33 0.33 0.24 Protease 0.1 0.05 0.15 AE-Flake 0.40 0.40 0.29 Liquid Spray-on Perfume 0.42 0.42 0.42
  • Example XXVU The following granular laundry detergent compositions XXVIH A-C are of particular utility under European machine wash conditions were prepared in accord with the invention:
  • Example XXIX The following formulations are examples of compositions in accordance with the invention, which may be in the form of granules or in the form of a tablet.
  • Example XXX Granular laundry detergent compositions XXX A-E are of particular utility under Japanese machine wash conditions and are prepared in accordance with the invention:
  • Citric acid monohydrate 10.0 15.0
  • Borax premix (Borax MEA/Pdiol/CitricAcid) 2.50 -

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Abstract

The present invention relates to treating compositions, preferably laundry and/or fabric and/or color care compositions comprising polysaccharides, and methods of using such compositions to provide improved color appearance and/or pill prevention and/or abrasion resistance and/or wrinkle resistance and/or shrinkage resistance benefits, while at the same time providing improved cleaning benefits, over laundry and/or fabric and/or color care compositions without such polysaccharides.

Description

TREATING COMPOSITIONS COMPRISING POLYSACCHARIDES
TECHNICAL FIELD
The present invention relates to treating compositions compπsing a polysacchaπde, and to a method for treating fabπcs, natural fibers, such as cellulosic fibers, more particularly cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell, poly/cotton, other cotton blends and mixtures thereof , with such compositions for providing the fabπcs with improved color appearance and/or pill prevention and/or abrasion resistance and/or wπnkle resistance and/or shrinkage resistance compared to treating compositions without such polysacchaπdes.
BACKGROUND OF THE INVENTION
Consumer desirability for fabπc garments that "look like new", or in other words, fabπc garments that retain their "new" appearance, especially with respect to their color appearance has πsen.
However, colored garments, especially cotton, rayon and lmen garments, have a tendency to wear and show appearance losses. A portion of this color loss may be attπbuted to abrasion m the laundeπng process, particularly in automatic washing machines and automatic laundry dryers Accordingly, there is a need for treating compositions that provide, refurbish, restore and/or improve the color appearance and/or pill prevention and/or abrasion resistance and/or wπnkle resistance and/or shrinkage resistance of fabπcs.
SUMMARY OF THE INVENTION
The present invention is a treating composition compπsing polysacchaπdes and a method for imparting color appearance and/or pill prevention and/or abrasion resistance and/or wπnkle resistance and/or shrinkage resistance properties to fabrics such as cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell, poly/cotton, other cotton blends and mixtures thereof. In accordance with one aspect of the present invention, a treating composition comprising polysaccharides is provided In accordance with yet another aspect of the present invention, a method for treating a fabric in need of treatment compπsing contacting the fabπc with an effective amount of a polysacchaπde-contaming treating composition such that the treating composition treats the fabπc is provided A preferred treating composition in accordance with the present invention compπses one or more polysaccharides and one or more cleanmg adjunct mateπals as descπbed hereinafter, preferably selected from the group consisting of builders, bleaching agents, dye transfer inhibiting agents, chelants, dispersants, polysacchaπdes, softening agents, suds suppressors, earners, enzymes, enzyme stabilizing systems, polyacids, soil removal agents, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bacteπcides, dyes, perfumes, bπghteners and mixtures thereof, and optionally, but preferably further compπsing a surfactant. Preferably, the treating composition is in the form of powder or granules. However, the treating composition may be in the form of a liquid such as an aqueous or non-aqueous heavy duty liquid detergent composition, a liquid for spray application, or a solid, such as a concentrated stick, for rubbing onto the fabπc.
Preferably, the treating composition is applied to the fabπc through the wash and/or through the πnse cycles. However, the treating composition can be applied to the fabπc pπor to the wash and/or after the wash and/or πnse cycles, such as dunng or pπor to ironing, if needed. All percentages and proportions herein are by weight, and all references cited herein are hereby incorporated by reference, unless otherwise specifically indicated.
DETAILED DESCRIPTION OF THE INVENTION Definitions
The treating compositions of the present invention compπse an "effective amount" of a polysacchande. An "effective amount" of a polysacchaπde is any amount capable of measurably improving the color appearance and/or pill prevention and/or abrasion resistance and/or wπnkle resistance and/or shπnkage resistance properties of a fabπc when it is washed. In general, this amount may vary quite widely.
"Treating composιtιon(s)" herein is meant to encompass generally laundry and/or fabπc care compositions and/or fabπc conditioners.
Pohsaccharide-Containing Treating Composition
In a preferred embodiment, the treating compositions of the present invention compπse an effective amount of one or more polysaccharides and are preferably free of starch and/or starch denvatives and/or resins Preferably, the treating compositions further compπse one or more cleaning adjunct mateπals These treating compositions are useful in the methods of the present invention It is desirable that the polysacchande is present in the treating composition of the present invention in an amount m the range of from about 0 01% to about 50% by weight of the treating composition, more preferably from about 0 5% to about 10% by weight of the treating composition Furthermore, it is desirable that the polysacchaπde is present in the wash, soaking and/or spray-treatment solution in amount m the range of from about 2 ppm to about 25000 ppm, more preferably from about 10 ppm to about 5000 ppm.
The treating composition can include conventional detergent ingredients, such as one or more of the following ingredients selected from the group consisting of surfactants, builders, bleaches, bleach activators, bleach catalysts, enzymes, enzyme stabilizing systems, soil release/removal agents, suds suppressors, polyacids, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bacteπcides, dyes, perfumes, earners and bnghteners Examples of such ingredients are generally descπbed in U.S. Pat. No 5,576,282. Forms of Compositions
The treating compositions of the present invention can be in solid (powder, granules, bars, tablets), dimple tablets, liquid, paste, gel, spray, stick or foam forms.
The liquid forms can also be m a "concentrated" form which are diluted to form compositions with the usage concentrations, as given hereinbelow, for use in the "usage conditions". Concentrated compositions compnse a higher level of polysacchande, typically from about 1% to about 99%>, preferably from about 2% to about 65%>, more preferably from about 3% to about 25%), by weight of the concentrated treating composition Concentrated compositions are used m order to provide a less expensive product When a concentrated product is used, i.e., when the polysacchande is from about 1%> to about 99%, by weight of the concentrated composition, it is preferable to dilute the composition, preferably with water, before treating a fabπc in need of treatment. Preferably, the water content of the "concentrated" form is less than 40%), more preferably less than 30%, most preferably less than 20%> by weight of the detergent composition.
The present invention also relates to polysacchaπde-containmg treating compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabnc articles and/or surfaces with said compositions containing the polysacchaπde and other optional ingredients at a level that is effective, yet is not discernible when dned on the surfaces The spray dispenser compnses manually activated and non-manual powered (operated) spray means and a container containing the treating composition The articles of manufacture preferably are m association with instructions for use to ensure that the consumer applies sufficient polysacchaπde to provide the desired benefit Typical compositions to be dispensed from a sprayer contain a level of polysacchaπde of from about 0 01% to about 5%, preferably from about 0.05% to about 2%, more preferably from about 0 1% to about 1%, by weight of the usage composition.
For wash-added and πnse-added methods, the article of manufacture can simply compπse a liquid or granular solid polysacchaπde-contaming treating composition and a suitable container
Wash-added compositions, including liquid and granular detergent compositions and wash additive compositions typically contain a level of polysacchande of from about 0.01% to about 30%), preferably from about 0.5% to about 20%, more preferably from about 1% to about
12%), by weight of the wash added compositions. Typical nnse-added compositions, including liquid fabπc conditioner and other πnse additive compositions, contain a level of polysacchaπde of from about 0.01% to about 40%, preferably from about 0.3% to about 25%, more preferably from about 0.5% to about 25%, most preferably from about 1% to about 10%>, by weight of the πnse added compositions.
Preferably the articles of manufacture are in association with instructions for how to use the composition to treat fabπcs correctly, to obtain the desirable fabnc care results, for example, improved color appearance and/or pill prevention and or abrasion resistance and/or wnnkle resistance and/or shπnkage resistance, while at the same time providing improved cleaning benefits, including, e.g., the manner and/or amount of composition to be used, and the preferred ways of stretching and/or smoothing, if any, the fabπcs. It is important that the instructions be as simple and clear as possible. Accordingly, the use of pictures and/or icons to assist in explainmg the instructions is desirable.
Liquid or solid, preferably powder, polysacchande-contammg treating composition for treating fabnc in the πnse step m accordance with the present invention compπse an effective amount of the polysacchaπde of the present invention, and optionally, fabnc softener actives, perfume, electrolytes, chloπne scavenging agents, dye transfer inhibiting agents, dye fixative agents, phase stabilizers, chemical stabilizers including antioxidants, sihcones, antimicrobial actives and/or preservatives, chelating agents, ammocarboxylate chelatmg agents, colorants, enzymes, bπghteners, soil release agents, anti-encrustation agents, builders and/or mixtures thereof. Again, the composition is preferably packaged m association with instructions for use to ensure that the consumer knows what benefits can be achieved.
Yet another liquid or solid, preferably powder or granular, treating composition m accordance with the present invention to be used in the wash cycle compπses an effective amount of one or more polysacchaπdes, and optionally, surfactants, builders, perfume, chloπne scavenging agents, dye transfer inhibiting agents, dye fixative agents, dispersants, detergent enzymes, heavy metal chelating agents, suds suppressors, fabπc softener actives, chemical stabilizers including antioxidants, sihcones, antimicrobial actives and/or preservatives, soil suspending agents, soil release agents, optical bnghteners, colorants, and the like, or mixtures thereof. Again, the composition is preferably packaged in association with instructions for use to ensure that the consumer knows what benefits can be achieved.
A preferred treating composition for treating fabric compπses an effective amount of one or more polysacchaπdes, and optionally, perfume, fabπc lubπcants, adjunct fabπc shape retention polymers, lithium salts, hydrophilic plasticizers, odor control agents, antimicrobial actives and/or preservatives, surfactants, enzymes, or mixtures thereof. Other optional ingredients can also be added, e.g., antioxidants, chelatmg agents, e.g., ammocarboxylate chelatmg agents, heavy metal chelating agents, antistatic agents, insect and moth repelling agents, dye transfer inhibiting agents, dye fixative agents, colorants, suds suppressors, and the like, and mixtures thereof. The composition is typically applied to fabπc via a, e.g., dipping, soaking and/or spraying process followed by a drying step, including the process compnsing a step of treating or spraying the fabπc with the treating composition either outside or mside an automatic clothes dryer followed by, or concurrently with, the drying step m said clothes dryer. However, the composition may be applied by spraying the fabπc with the treating composition pπor to and/or dunng ironing, if needed. Also, the composition may be applied by spraying the fabπc during dry cleaning. The application can be done industnally by large scale processes on textiles and/or finished garments and clothings, or in consumer's home by the use of commercial product.
The treating compositions herein can be made by any suitable process known m the art. Examples of such processes are descπbed in U.S. Pat. No. 5,576,282.
The treating compositions herein will preferably be formulated such that, dunng use m aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11. Techniques for controllmg pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled m the art. Non-aqueous based heavy duty laundry detergent compositions containing the polysacchande preferably compπse from about 55% to about 98.9%) by weight of the detergent composition of a structured, surfactant-containing liquid phase formed by combining: (a) from about 1% to about 80% by weight of the liquid phase of one or more non-aqueous organic diluents; and (b) from about 20% to about 99% by weight of the liquid phase of a surfactant system compπsing surfactants selected from the group consisting of anionic, noniomc, cationic surfactants and mixtures thereof. Aqueous based heavy duty laundry detergent compositions containing the polysacchaπde preferably contain a surfactant system compπsmg surfactants selected from the group consisting of noniomc detersive surfactants, anionic detersive surfactants, zwittenomc detersive surfactants, amine oxide detersive surfactants and mixtures thereof The surfactant system typically compπses from about 0 01% to about 50%, preferably from about 0.2% to about 30% by weight of the detergent composition
Another appropriate form in which the treating compositions of the present invention may be incorporated are tablets Such polysacchande-contammg treating composition tablets compnse an effective amount of one or more polysacchandes, and optionally, surfactants, builders, perfume, chlorine scavenging agents, dye transfer inhibiting agents, dye fixative agents, dispersants, detergent enzymes, heavy metal chelating agents, suds suppressors, fabπc softener actives, chemical stabilizers including antioxidants, sihcones, antimicrobial actives and/or preservatives, soil suspending agents, soil release agents, optical bnghteners, colorants, and the like, or mixtures thereof Again, the composition is preferably packaged m association with instructions for use to ensure that the consumer knows what benefits can be achieved. The tablets can be used in pre-wash and/or pretreatment procedures as well as through the wash and/or nnse cycles.
Alternatively, the treating compositions of the present invention can be incoφorated into a spray dispenser, or concentrated stick form that can create an article of manufacture that can facilitate the cleaning and/or fabnc care or conditioning of fabπc. If the spray treatment is a "pre-treat", which is followed by a wash cycle, then the spray treatment treating compositions preferably compπse from about 0.01% to about 50% of polysacchaπde by weight the of total treating composition, more preferably from about 0J%> to about 3% of polysacchande by weight of the total treating composition. If the spray treatment compositions are desired to do the cleaning, as in the case of wash, then the spray treatment compositions preferably compnse from about 2 ppm to about 10000 ppm of the polysacchaπde by weight of the total treating composition, more preferably from about 200 ppm to about 5000 ppm of the polysacchaπde by weight of the total treating composition. In the latter case, a bnef πnse, not a full wash cycle, is desirable after treatment. Such spray treatment compositions are typically packaged m a spray dispenser.
The spray-treatment compositions herein are typically packaged m spray dispensers. The spray dispensers can be any of the manually activated means for producing a spray of liquid droplets as is known in the art, e.g. tπgger-type, pump-type, non-aerosol self-pressuπzed, and aerosol-type spray means. It is preferred that at least about 70%, more preferably, at least about 80%, most preferably at least about 90% of the droplets have a particle size of smaller than about 200 microns.
The spray dispenser can be an aerosol dispenser. Said aerosol dispenser compπses a container which can be constructed of any of the conventional materials employed in fabπcatmg aerosol containers. The dispenser must be capable of withstanding internal pressure in the range of from about 20 to about 110 p.s.i.g., more preferably from about 20 to about 70 p.s l.g. The one important requirement concerning the dispenser is that it be provided with a valve member which will permit the treating compositions of the present invention contained m the dispenser to be dispensed in the form of a spray of very fine, or finely divided, particles or droplets. A more complete description of commercially available suitable aerosol spray dispensers appears m U.S. Pat. Nos.. 3,436,772, Stebbms, issued Apr.8, 1969; and 3,600,325, Kaufman et al., issued Aug. 17, 1971.
Preferably the spray dispenser is a self-pressuπzed non-aerosol container having a convoluted lmer and an elastomenc sleeve. A more complete descπption of suitable self- pressuπzed spray dispensers can be found in U.S. Pat. Nos.: 5, 111,971, Wmer, issued May 12, 1992; and 5,232,126, Wmer, issued Aug. 3, 1993. Another type of suitable aerosol spray dispenser is one wherem a barπer separates the wπnkle reducing composition from the propellant (preferably compressed air or nitrogen), as is disclosed in U.S. Pat. No. 4,260,110, issued Apr. 7, 1981, incorporated herein by reference. Such a dispenser is available from EP Spray Systems, East Hanover, NJ. More preferably, the spray dispenser is a non-aerosol, manually activated, pump-spray dispenser. A more complete disclosure of commercially available suitable dispensing devices appears in: U.S. Pat. Nos.: 4,895,279, Schultz, issued Jan. 23, 1990; 4,735,347, Schultz et al., issued Apr. 5, 1988; and 4,274,560, Carter, issued Jun. 23, 1981.
Most preferably, the spray dispenser is a manually activated tngger-spray dispenser. A more complete disclosure of commercially available suitable dispensing devices appears in U.S. Pat. Nos.: 4,082,223, Nozawa, issued Apr. 4, 1978; 4,161,288, McKmney, issued Jul. 7, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984; and 4,819,835, Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr. 19, 1994.
A broad array of tngger sprayers or finger pump sprayers are suitable for use with the compositions of this invention. These are readily available from suppliers such as Calmar, Inc., City of Industry, California; CSI (Continental Sprayers, Inc.), St. Peters, Missouπ; Berry Plastics Corp., Evansville, Indiana - a distributor of Guala ® sprayers; or Seaquest Dispensing, Cary, 111.
The preferred trigger sprayers are the blue inserted Guala ® sprayer, available from Berry Plastics Corp., the Calmar TS800-1A® sprayers, available from Calmar Inc., or the CSI T7500® available from Continental Sprayers Inc., because of the fine uniform spray charactenstics, spray volume and pattern size. Any suitable bottle or container can be used with the trigger sprayer, the preferred bottle is a 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape to the Cmch® bottle. It can be made of any mateπals such as high density polyethylene, polypropylene, polyvmyl chloπde, polystyrene, polyethylene terephthalate, glass or any other matenal that forms bottles. Preferably, it is made of high density polyethylene or polyethylene terephthalate For smaller four fl-oz size (about 1 18 ml), a finger pump can be used with canister or cylindrical bottle The preferred pump for this application is the cylmdπcal Euromist π® from Seaquest Dispensing.
It has been found that polysaccharides impart to the fabπc improved color appearance and/or pill prevention and/or abrasion resistance and/or wπnkle resistance and/or shnnkage resistance. These benefits provided by the polysacchaπde improve the appearance of the fabnc. Methods of Treating
Fabπcs, preferably finished garments, can be treated with the polysacchande-contammg treating compositions by any method known m the art that accomplishes contacting the fabnc with the polysacchande-contammg treating composition.
A preferred embodiment of the present invention is a method for treating a fabnc m need of treatment, wherem the method compπses contacting the fabπc with an effective amount of polysacchande-contammg treating composition such that the treating composition treats the fabnc. Preferably, the polysacchaπde treating composition is m contact with the fabπc for an "effective amount of time", which herein means the amount of time required for the polysacchande-contammg treating composition to adequately treat a fabπc such that the fabπc acquires improved color appearance and/or pill prevention and/or abrasion resistance and/or wπnkle resistance and/or shπnkage resistance properties. Such time can vary quite widely, however, a preferred range of time is from about 5 minutes to about 60 minutes, more preferably from about 10 minutes to about 30 minutes.
Suitable methods include, but are not limited to, washing the fabnc in a solution containing the polysacchande-contammg treating composition. The washing can be manual or automatic, such as m a washing machine. The washing machine used m the method descπbed herein can be any conventional washing machine known in the art. In addition, it can be a specially designed washing machine such as the washing machine descπbed in U.S. Patent No. 5,520,025 to Joo et al.
Other suitable methods include, but are not limited to, soaking the fabπc in a solution containing the polysacchande-contammg treating composition; spraying the fabπc with a solution containing the polysacchande-contammg treating composition; rubbing the fabnc with a solid containing the polysacchande-contammg treating composition; dipping the fabπc m a solution containing the polysacchande-contammg treating composition; rolling the polysacchande-contammg treating composition onto the fabπc, spreading the polysacchande- contammg treating composition onto the fabnc and brushing the polysacchande-contammg treating composition onto the fabπc In addition to the methods for treating fabrics m need of treatment and other surfaces, descπbed herein, the invention herein also encompasses a laundering pretreatment process for fabrics which have been soiled or stained comprising directly contacting said stains and/or soils with a highly concentrated form of the polysacchande-contammg treating composition, in any form, preferably a concentrated liquid (preferably in a spray dispenser or roll-on device), stick or bar, set forth above pπor to washing such fabncs usmg conventional aqueous washing solutions. Preferably, the cleanmg composition remains m contact with the soil/stam for a penod of from about 30 seconds to 24 hours pπor to washing the pretreated soiled/stamed substrate m conventional manner. More preferably, pretreatment times will range from about 1 to 180 minutes.
Such methods can be used m industrial applications, such as in the textile industry, or in residential (domestic) applications, preferably, the methods are used m the residential (domestic) applications.
Further, these methods can be used independently of one another, or can be combined, concurrently or sequentially.
The use of the treating compositions of the present invention in accordance with these methods maintains the color appearance and/or pill prevention and/or abrasion resistance and/or wnnkle resistance and/or shrinkage resistance of a fabπc in need of treatment through multiple wash cycles. Product/Instructions
The present invention also encompasses the inclusion of instructions on the use of the polysacchande-contammg treating compositions with the packages containing the treating compositions herein or with other forms of advertising associated with the sale or use of the treating compositions. The instructions may be mcluded m any manner typically used by consumer product manufactuπng or supply companies. Examples include providing instructions on a label attached to the container holding the composition; on a sheet either attached to the container or accompanying it when purchased; or in advertisements, demonstrations, and/or other wntten or oral instructions which may be connected to the purchase of the treating compositions.
The instructions, for instance, may include information relating to the temperature of the wash water; washing time; recommended settings on the washing machine; recommended amount of the treating composition to use; pre-soakmg procedures; and spray-treatment procedures.
A product compπsmg a polysacchande-contammg treating composition, the product further including instructions for using the treating composition to treat a fabπc in need of treatment, the instructions including the step of: contacting said fabric with an effective amount of said treating composition for an effective amount of time such that said composition treats said fabπc. The product may be a laundry detergent composition, a fabric care composition or fabπc conditioner. Furthermore, the product may be contained m a spray dispenser. Polysaccharides
"Polysacchaπdes" herein is meant natural polysacchaπdes, and does not include polysacchaπde denvatives or modified polysacchaπdes. Suitable polysacchandes for use in the treating compositions of the present invention include, but are not limited to, gums, arabmans, galactans, seeds and mixtures thereof.
Suitable polysacchandes that are useful in the present invention include polysacchaπdes with a degree of polymenzation (DP) over 40, preferably from about 50 to about 100,000, more preferably from about 500 to about 50,000, constituting sacchandes preferably include, but are not limited to, one or more of the following saccharides: isomaltose, isomaltotnose, isomaltotetraose, isomaltooligosacchaπde, fructoohgosacchande, levoohgosacchandes, galactoohgosacchaπde, xyloohgosacchande, gentioohgosacchaπdes, disacchaπdes, glucose, fructose, galactose, xylose, mannose, sorbose, arabmose, rhamnose, fucose, maltose, sucrose, lactose, maltulose, nbose, lyxose, allose, altrose, gulose, idose, talose, trehalose, mgerose, kojibiose, lactulose, ohgosacchaπdes, maltooligosaccharides, tπsacchandes, tetrasacchandes, pentasacchandes, hexasacchaπdes, ohgosacchandes from partial hydrolysates of natural polysacchaπde sources and mixtures thereof.
The polysacchandes can be extracted from plants, produced by organisms, such as bactena, fungi, prokaryotes, eukaryotes, extracted from animals and/or humans. For example, xanthan gum can be produced by Xanthomonas campestris, gellan by Sphingomonas paucimobilis, xyloglucan can be extracted from tamannd seed.
The polysacchaπdes can be linear, or branched in a vanety of ways, such as 1-2, 1-3, 104, 1-6, 2-3 and mixtures thereof. It is desirable that the polysacchaπdes of the present invention have a molecular weight m the range of from about 10,000 to about 10,000,000, more preferably from about 50,000 to about 1,000,000, most preferably from about 50,000 to about 500,000.
Preferably, the polysacchaπde is selected from the group consisting of: tamannd gum (preferably consisting of xyloglucan polymers), guar gum, locust bean gum (preferably consisting of galactomannan polymers), and other mdustnal gums and polymers, which include, but are not limited to, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psylhum seed, qumce seed, xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, schizophyllan, chitm, hydroxyalkyl cellulose, arabman (preferably from sugar beets), de-branched arabman (preferably from sugar beets), arabmoxylan (preferably from rye and wheat flour), galactan (preferably from lupin and potatoes), pectic galactan (preferably from potatoes), galactomannan (preferably from carob, and including both low and high viscosities), glucomannan, hchenan (preferably from Icelandic moss), mannan (preferably from ivory nuts), pachyman. rhamnogalacturonan, acacia gum, agar, alginates, carrageenan, chitosan, clavan, hyaluronic acid, hepaπn, inulin, cellodextπns, and mixtures thereof These polysaccharides can also be treated (preferably enzymatically) so that the best fractions of the polysacchaπdes are isolated. More preferred polysaccharides have a β-lmked backbone.
Xyloglucan polymer is a highly preferred polysacchande for use in the laundry and/or fabric care compositions of the present invention. Xyloglucan polymer is preferably obtained from tamannd seed polysacchaπdes. The preferred range of molecular weights for the xyloglucan polymer is from about 10,000 to about 1,000,000, more preferably from about 50,000 to about 200,000.
Polysacchandes, when present, are normally incorporated in the treating composition of the present invention at levels from about 0.1% to about 25%, preferably from about 0J%> to about 10% by weight of the treating composition.
Polysacchaπdes have a high affinity for binding with cellulose. Without wishing to be bound by theory, it is believed that the binding efficacy of the polysacchandes to cellulose depends on the type of linkage, extent of branching and molecular weight. The extent of binding also depends on the nature of the cellulose (i.e., the ratio of crystalline to amorphous regions in cotton, rayon, linen, etc.).
The natural polysacchandes can be modified with amines (pnmary, secondary, tertiary), amides, esters, ethers, alcohols, carboxylic acids, tosylates, sulfonates, sulfates, nitrates, phosphates and mixtures thereof. Such a modification can take place in position 2, 3 and/or 6 of the glucose unit. Such modified or deπvatized polysacchandes can be included in the compositions of the present invention m addition to the natural polysacchandes.
Nonhmitmg examples of such modified polysacchaπdes include: carboxyl and hydroxymethyl substitutions (e.g., glucuromc acid instead of glucose); ammo polysacchandes (amine substitution, e.g., glucosamme instead of glucose); Cι-C6 alkylated polysacchandes; acetylated polysacchande ethers; polysacchaπdes having ammo acid residues attached (small fragments of glycoprotein); polysacchaπdes containing silicone moieties. Suitable examples of such modified polysacchaπdes are commercially available from Carbomer and include, but are not limited to, ammo alginates, such as hexanediamme alginate, amine functionahzed celluloselike 0-methyl-(N-lJ2-dodecanedιamme) cellulose, biotm hepaπn, carboxymethylated dextran, guar polycarboxyhc acid, carboxymethylated locust bean gum, caroxymethylated xanthan. chitosan phosphate, chitosan phosphate sulfate, diethylammoethyl dextran, dodecylamide alginate, sialic acid, glucuromc acid, galacturonic acid, mannuronic acid, guluromc acid, N-acetylglucosamme, N-acetylgalactosamine, and mixtures thereof. The polysacchaπde polymers can be linear, like m hydroxyalkylcellulose, the polymer can have an alternating repeat like in carrageenan, the polymer can have an interrupted repeat like in pectin, the polymer can be a block copolymer like in algmate, the polymer can be branched like in dextran, the polymer can have a complex repeat like in xanthan. Descπptions of the polymer definitions are give in "An introduction to Polysacchaπde Biotechnology", by M> Tombs and S.E. Harding, TJ.Press 1998. Oligosaccharides
The compositions of the present invention may include ohgosacchandes. Suitable ohgosacchandes that are useful m the present invention include ohgosacchandes with a degree of polymenzation (DP) of less than 20, preferably from about 1 to about 15, more preferably from about 2 to about 10, constituting monosacchandes preferably include, but are not limited to, one or more of the following monosacchandes: glucose, fructose, galactose, xylose, mannose, arabmose, rhamnose, nbose, lyxose, allose, altrose, gulose, idose, talose, and/or their denvatives Preferred ohgosacchandes have a molecular weight in the range of from about 300 to about 8000. Branched ohgosacchandes are preferred over linear ohgosacchandes.
Nonhmiting examples of suitable ohgosacchandes can be obtained commercially from any of the suppliers - Carbomer (fructo-ohgosacchaπdes, levo-ohgosacchandes, mulm, dextra 5000, cellosacchandes, etc.,), Gram Processing Corporation (maltodextnn), Pharmacica Biotech (Dextran senes), Palatinit (isomalt) and Showa Sangyo (Isomalto-500). Ohgosacchandes, when present, are normally incorporated in the cleaning composition at levels from about 1% to about 25%, preferably from about 2% to about 10% by weight of the laundry and/or fabπc care composition. Cleaning Adjunct Materials
The treating compositions of the present invention compπse an effective amount of the polysacchande, and preferably one or more of the above-descπbed preferred ingredients, and optionally one or more of the following conventional cleaning adjunct mateπals either to improve the performance of the polysacchande, e.g., in the areas of wπnkle control, anti-wear, soil release, tensile strength and the like, or to provide additional benefits, such as odor control, antimicrobial, and the like. The useful optional cleaning adjunct matenals are those that are compatible with the polysacchaπde, m that they do not interfere and/or substantially or significantly dimmish the benefits provided by the polysacchande. The precise nature of these optional cleanmg adjunct mateπals, and levels of incorporation thereof will depend on the physical form of the treating compositions, and the nature of the cleaning operation for which it is to be used. Examples of such cleaning adjunct mateπals include, but are not limited to, the following. Surfactant System - Detersive surfactants can be, and preferably are included m the treating compositions of the present invention. When present, surfactants compπse at least 0.01%, preferably at least about 0.1%, more preferably at least about 0.5%, most preferably at least about 1% to about 60%., more preferably to about 35%, most preferably to about 30% by weight of the treating composition depending upon the particular surfactants used and the desired effects.
The detersive surfactant can be noniomc, anionic, ampholytic, zwitteπomc, cationic, semi-polar noniomc, and mixtures thereof, nonhmitmg examples of which are disclosed in U.S.
Patent Nos. 5,707,950 and 5,576,282. Preferred treating compositions compπse anionic detersive surfactants or mixtures of anionic surfactants with other surfactants, especially noniomc surfactants.
Anionic surfactants are highly preferred for use with the treating compositions of the present invention.
Nonhmitmg examples of surfactants useful herein include the conventional Cn-Cj alkyl benzene sulfonates and pnmary, secondary and random alkyl sulfates, the CjQ-Cig alkyl alkoxy sulfates, the Cjo- ig alkyl polyglycosides and their corresponding sulfated polyglycosides, Cj2-Cιg alpha-sulfonated fatty acid esters, C^-Cj alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C^-Cj betames and sulfobetames ("sul- taines"), CjQ- i amine oxides, and the like. Other conventional useful surfactants are listed in standard texts. The surfactant is preferably formulated to be compatible with enzyme and bleaching components, if any, present in the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
Noniomc Surfactants - Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the noniomc surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. Commercially available noniomc surfactants of this type include Igepal^M CO-630, marketed by the GAP Corporation; and Tπton™ X-45, X-l 14, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
The condensation products of pπmary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the noniomc surfactant of the noniomc surfactant systems of the present invention. Examples of commercially available noniomc surfactants of this type include TergitolTM 15-S-9 (the condensation product of C\ \- C*i5 l ear alcohol with 9 moles ethylene oxide),
Figure imgf000015_0001
24-L-6 NMW (the condensation product of Cj2-Ci4 pnmary alcohol with 6 moles ethylene oxide with a narrow molecular weight distπbution), both marketed by Union Carbide Corporation; Neodolτ^ 45-9 (the condensation product of C-[4-Ci5 linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodo.TM 45.5 ^he condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro *M EOB (the condensation product of C13- Cj5 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA O3O or O50 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB m these products is from 8-11 and most preferred from 8-10.
Also useful as the noniomc surfactant of the surfactant systems of the present invention are the alkylpolysacchaπdes disclosed in U.S. Patent No. 4,565,647.
Preferred alkylpolyglycosides have the formula:
Figure imgf000016_0001
wherein R-2 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 1J to about 10, preferably from about 1J to about 3, most preferably from about 1.3 to about 2J.
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 noniomc surfactant systems of the present invention. Examples of compounds of this type include certain of the commercially-available Plurafac *M LF404 and Pluromc * M surfactants, marketed by BASF.
Also suitable for use as the noniomc surfactant of the noniomc surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme. Examples of this type of noniomc surfactant include certain of the commercially available TetromcTM compounds, marketed by BASF.
Preferred for use as the noniomc surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of pπmary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysacchaπdes, and mixtures thereof. Most preferred are C -Ci 4 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-Cj alcohol ethoxylates (preferably C\Q avg.) having from 2 to 10 ethoxy groups, and mixtures thereof. Highly preferred noniomc surfactants are polyhydroxy fatty acid amide surfactants of the formula- R2 - C(O) - NCR1) - Z wherem R1 is H, or R1 is C*ι_4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl or a mixture thereof, R2 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 Preferably, R* is methyl, R2 is a straight C*j j_i5 alkyl or C*[6_ι alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive animation reaction.
Anionic Surfactants - Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C -C2fj carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting mateπals would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, compnse alkyl ester sulfonate surfactants of the structural formula :
O
R3 - CH - C - OR4
SO3M wherem R3 is a C -C2fj hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a Ci -Cg hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamme, diethanolamme, and tπethanolamme. Preferably, R3 is Cjø-Cig alkyl, and
R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 ιs C*ιo-Ci6 -alkyl.
Other suitable anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherem R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-
Cj alkyl or hydroxyalkyl, and M is H or a cation. Typically, alkyl chains of C12-C16 are preferred for lower wash temperatures (e.g. below about 50°C) and Cj^-i alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).
Other anionic surfactants useful for detersive purposes include salts of soap, C -C22 pπmary of secondary alkanesulfonates, C -C24 olefmsulfonates, sulfonated polycarboxyhc acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as descπbed m Bntish patent specification No 1,082,179, Cg-C24 alkylpolyglycolethersulfates
(containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, lsethionates such as the acyl lsethionates, N-acyl taurates, alkyl succinamates and sulfosuccmates, monoesters of sulfosuccinates (especially saturated and unsaturated C-^-Cj monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C -C\2 diesters), acyl sarcosmates, sulfates of alkylpolysacchandes such as the sulfates of alkylpolyglucoside (the noniomc nonsulfated compounds being descπbed below), branched pnmary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH20)ι{-CH2COO-M+ wherem R is a Cg-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resm acids and hydrogenated resin acids are also suitable, such as rosm, hydrogenated rosin, and resm acids and hydrogenated resin acids present in or denved
Further examples are descnbed m "Surface Active Agents and Detergents" (Vol. I and π by Schwartz, Perry and Berch). A vaπety of such surfactants are also generally disclosed in U.S.
Patent 3,929,678, issued December 30, 1975 to Laughlm, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted C\Q-
C24 alkyl or hydroxyalkyl group having a C1 -C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C^-C^ 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-ammomum cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, tπmethyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdmium cations and those denved from alkylammes such as ethylamme, diethylamine, tπethylamine, mixtures thereof, and the like. Exemplary surfactants are C^-C-j alkyl polyethoxylate (1.0) sulfate (Ci2-C*ιgE(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (C12-C18E(2J5)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (C12-C18E(3.0)M), and C*i2-C* alkyl polyethoxylate (4.0) sulfate (Cj2-Cι E(4.0)M), wherem M is conveniently selected from sodium and potassium.
When included therein, the treating compositions of the present invention typically compnse from about 1%, preferably from about 3% to about 40%, preferably about 20% by weight of such anionic surfactants Cationic Surfactants - Cationic detersive surfactants suitable for use in the treating compositions of the present invention are those having one long-chain hydrocarbyl group Examples of such cationic surfactants include the ammonium surfactants such as alkyltπmethylammonium halogemdes, and those surfactants having the formula [R2(OR3)y][R4(OR3)y]2R5N+X- wherem R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each
R4 IS selected from the group consisting of C1 -C4 alkyl, C1-C4 hydroxyalkyl, benzyl nng structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH2OH wherein R" is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R-^ is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R? is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula (1): R1 R2R3R4N+X" wherem R is Cg-C-jg alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4ø)xH where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl. The preferred alkyl chain length for R\ is Cj2" C15 particularly where the alkyl group is a mixture of chain lengths deπved from coconut or palm kernel fat or is deπved synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulfate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (1) for use herein are include, but are not limited to: coconut tπmethyl ammonium chloπde or bromide; coconut methyl dihydroxyethyl ammonium chloπde or bromide; decyl tπethyl ammonium chlonde; decyl dimethyl hydroxyethyl ammonium chloπde or bromide; C12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloπde or bromide; mynstyl tπmethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloπde or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloπde or bromide; chohne esters
(compounds of formula (1) wherem R\ is
CH2-CH2-O-C-C12-14 alkyl and R2R3R4 are methyl);
O and di-alkyl lmidazolmes [(1)].
Other cationic surfactants useful herein are also descπbed in U.S. Patent 4,228,044, Cambre, issued October 14, 1980 and m European Patent Application EP 000,224. When included therein, the treating compositions of the present invention typically compπse from about 0.2%, preferably from about 1% to about 25%, preferably to about 8%. by weight of such cationic surfactants.
Ampholytic Surfactants - Ampholytic surfactants, examples of which are descπbed in U.S. Patent No 3,929,678, are also suitable for use in the treating compositions of the present invention.
When included therein, the treating compositions of the present invention typically compπse from about 0J%>, preferably from about 1% to about 15%., preferably to about 10% by weight of such ampholytic surfactants. Zwittenonic Surfactants - Zwitteπonic surfactants, examples of which are descnbed in
U.S. Patent No. 3,929,678, are also suitable for use m the treating compositions of the present invention.
When included therein, the treating compositions of the present invention typically compπse from about 0J%>, preferably from about 1% to about 15%), preferably to about 10% by weight of such zwittenonic surfactants.
Semi-polar Noniomc Surfactants - Semi-polar noniomc surfactants are a special category of noniomc surfactants which include water-soluble amine oxides having the formula:
O
R3(OR4)xN(R5)2 wherem R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R-> is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group contammg from about 1 to about 3 ethylene oxide groups (the R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a nng structure); water- soluble phosphine oxides contammg one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
The amine oxide surfactants m particular include Cjo-Cjg alkyl dimethyl amine oxides and Cg-C*i2 alkoxy ethyl dihydroxy ethyl amine oxides
When included therein, the treating compositions of the present invention typically compπse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such semi-polar noniomc surfactants. Cosurfactants - The treating compositions of the present invention may further compπse a cosurfactant selected from the group of pnmary or tertiary amines. Suitable pπmary amines for use herein include amines according to the formula R]NH2 wherem R\ is a Cg-C^ preferably
Co-Cjo alkyl chain or R X(CH2)n, X is -0-,-C(0)NH- or -NH-; R is a Cg-C^ alkyl chain n is between 1 to 5, preferably 3. R\ alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
Preferred amines according to the formula herein above are n-alkyl amines. Suitable amines for use herein may be selected from 1-hexylamιne, 1-octylamιne, 1-decylamme and laurylamme. Other preferred pπmary amines include C8-C10 oxypropylamine, octyloxypropylamme, 2-ethylhexyl-oxypropylamme, lauryl amido propylamme and amido propylamme. The most preferred amines for use in the compositions herein are 1-hexylamme, 1- octylamme, 1-decylamιne, 1-dodecylamme. Especially desirable are n-dodecyldimethylamme and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamme and cocoamido propylamme. LFNIs - Low foaming noniomc surfactants (LFNT) which are descnbed in U.S. Patent
Nos. 5,705,464 and 5,710,115 can be included m the treating compositions of the present invention. LFNI may be present in amounts from 0.01% to about 10% by weight, preferably from about 0.1% to about 10%, and most preferably from about 0.25% to about 4%. LFNIs are most typically used in automatic dishwashing detergent compositions (ADDs) on account of the improved water-sheetmg action (especially from glass) which they confer to the ADD product. They also encompass non-sihcone, nonphosphate polymeπc matenals further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.
Preferred LFNIs include noniomc alkoxylated surfactants, especially ethoxylates deπved from pπmary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers as descnbed in U.S. Patent Nos. 5,705,464 and 5,710,115.
LFNIs which may also be used include those POLY-TERGENT® SLF-18 noniomc surfactants from Ohn Corp., and any biodegradable LFNI having the melting point properties discussed heremabove. These and other noniomc surfactants are well known in the art, being descnbed m more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference herein.
Bleaching System - The treating compositions of the present invention may compπse a bleaching system. Bleaching systems typically compπse a "bleaching agent" (source of hydrogen peroxide) and an "initiator" or "catalyst" When present, bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%>, preferably to about 20%> by weight of the composition If present, the amount of bleach activator will typically be from about 0.1%, preferably from about 0 5% to about 60%, preferably to about 40% by weight, of the treating composition comprising the bleaching agent-plus-bleach activator.
Bleaching Agents - Hydrogen peroxide sources are described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol 4, pp. 271-300 "Bleaching Agents (Survey)", and include the vanous forms of sodium perborate and sodium percarbonate, including vanous coated and modified forms.
The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Also useful are sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
A preferred percarbonate bleach compπses dry particles having an average particle size m 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. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants. Percarbonate is available from vanous commercial sources such as FMC, Solvay and Tokai Denka.
Compositions of the present invention may also compnse as the bleaching agent a chlonne-type bleaching matenal. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlonne-type bleaches are less preferred for compositions which compπse enzymes.
If peroxygen bleaching agents are used as all or part of the particulate matenal, they will generally compnse from about 0.1% to 30%> by weight of the composition. More preferably, peroxygen bleaching agent will compnse from about 1% to 20% by weight of the composition. Most preferably, peroxygen bleaching agent will be present to the extent of from about 5% to 20% by weight of the composition
(a) Bleach Activators - Preferably, the peroxygen bleach component in the composition is formulated with an activator (peracid precursor). The activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1%>, most preferably from about 3% to about 20%, preferably to about 15%, more preferably to about 10%), most preferably to about 8%, by weight of the composition. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1: 1 to 10: 1, more preferably from about 1.5: 1 to 5J. In addition, it has been found that bleach activators, when agglomerated with certain acids such as citπc acid, are more chemically stable.
Preferred activators are selected from the group consisting of tetraacetyl ethylene diamme (TAED), benzoylcaprolactam (BzCL), 4-nιtrobenzoylcaprolactam, 3-chlorobenzoyl- caprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C*[Q-OBS), benzoylvalerolactam
(BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) ammo hexanoyloxy] -benzene sulfonate sodium salt (NACA-OBS) an example of which is descπbed m U.S. Patent No. 5,523,434, dodecanoyloxybenzenesulphonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or C^-OBS with unsaturation in the 10 position), and decanoyloxybenzoic acid
(DOBA).
Preferred bleach activators are those descπbed in U.S. 5,698,504 Christie et al., issued December 16, 1997; U.S. 5,695,679 Chnstie et al. issued December 9, 1997; U.S. 5,686,401 Willey et al., issued November 11, 1997; U.S. 5,686,014 Hartshorn et al., issued November 11, 1997; U.S. 5,405,412 Willey et al., issued Apnl 11, 1995; U.S. 5,405,413 Willey et al., issued Apnl 11, 1995; U.S. 5,130,045 Mitchel et al., issued July 14, 1992; and U.S. 4,412,934 Chung et al., issued November 1, 1983, and copendmg patent applications U. S. Senal Nos. 08/709,072, 08/064,564, all of which are incorporated herein by reference.
The mole ratio of peroxygen bleaching compound (as AvO) to bleach activator m the present invention generally ranges from at least 1 : 1, preferably from about 20: 1, more preferably from about 10: 1 to about 1:1, preferably to about 3:1.
Quaternary substituted bleach activators may also be included. The present cleaning compositions preferably compπse a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former. Preferred QSBA structures are further described in U.S. 5,686,015 Willey et al, issued November 11, 1997; U.S. 5,654,421 Taylor et al., issued August 5, 1997; U.S. 5,460,747 Gosselmk et al., issued October 24, 1995, U.S. 5,584,888 Miracle et al., issued December 17, 1996; and U.S. 5,578,136 Taylor et al, issued November 26, 1996; all of which are incorporated herein by reference.
Highly preferred bleach activators useful herein are amide-substituted as descnbed m U.S. 5,698,504, U.S. 5,695,679, and U.S. 5,686,014 each of which are cited herein above. Preferred examples of such bleach activators include: (6-octanamιdocaproyl) oxybenzenesulfonate, (6-nonanamιdocaproyl)oxybenzenesulfonate, (6-decanamιdocaproyl)oxybenzenesulfonate and mixtures thereof.
Other useful activators, disclosed in U S. 5,698,504, U.S. 5,695,679, U.S. 5,686,014 each of which is cited herein above and U.S. 4,966,723 Hodge et al., issued October 30, 1990, include benzoxazm-type activators, such as a C6H4 nng to which is fused in the 1 J-positions a moiety -C(0)OC(R1)=N-.
Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems having with m-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, for example, activators with electron- withdrawing moieties are used for near-neutral or sub-neutral pH ranges. Alkalis and buffeπng agents can be used to secure such pH.
Acyl lactam activators, as descπbed in U.S. 5,698,504, U.S. 5,695,679 and U.S. 5,686,014, each of which is cited herein above, are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639 Willey et al., issued Apnl 2, 1996 incorporated herein by reference). Cyclic lmido bleach activators are represented by the formula:
Figure imgf000024_0001
wherein X is selected from substituted or unsubstituted, branched or linear C\ -C20 alkyl, substituted or unsubstituted, branched or linear C2-C20 alkylene. Preferably, X is branched or linear C\ -C12 alkyl, branched or linear C2 -C12 alkylene, more preferably branched or linear C* [-Cg alkyl, branched or linear C2-C alkylene, most preferably linear C^-Cg alkyl. A is selected from:
Figure imgf000024_0002
and preferably is:
Figure imgf000024_0003
where n is selected from the numbers 0, 1, 2, 3 or 4. Preferably, n is 0,1,2 or 3 and more preferably, OJ, or 2. R1 and R2 are independently selected from the group consisting of hydrogen, chloπde, bromide, iodide, substituted or unsubstituted branched or linear Cj-C2o alkyl, substituted or unsubstituted branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl. Preferably R1 and R2 are independently hydrogen, chlonde, substituted or unsubstituted branched or linear Ci -Cjg alkyl, substituted or unsubstituted branched or linear C2-Cι g alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl. More preferably, R1 and R2 are independently hydrogen, unsubstituted branched or linear Cj-Cig alkyl, unsubstituted branched or linear C2-C1 g alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted alkylphenyl substituted or unsubstituted alkylnapthyl. It is further preferred that one of R! and R2 is hydrogen or unsubstituted branched or linear Cj-Cg alkyl and the other is either an unsubstituted branched or linear C1 -C16 alkyl or an unsubstituted branched or linear C2-C16 alkenyl. L is a modified or unmodified lactam leaving group. The lactams which are suitable as leaving groups in the present application have the genenc structure:
R N — where R represents an optionally substituted alkenyl chain with at least two carbon atoms m the alkenyl chain. This alkenyl chain forms a cyclic structure with the -N- and -C(O)-. The term modified means that the alkenyl can be substituted at least once or that one or more of the alkenyl carbon atoms can be substituted by a suitable heterocycle or any combination of both. Suitable heterocyclic chain substitutes are O, N, and S, with O being preferred. Suitable substituents include, but are not limited to, C\-C alkyl, Cj-Cg alkenyl, Cj-Cg alkoxy, chloπde, bromide, iodide. The preferred substituents are Cj-Cg alkyl, Cj-Cg alkoxy and chloπde. The most preferred modified lactam leaving groups are: alpha-chlorocaprolactam, alpha-chloro- valerolactam, alpha,alpha-dιchlorolactam, alpha,alpha-dιchlorovalerolactam, alpha- methoxycaprolactam, alpha-methoxy-valerolactam,
Figure imgf000025_0001
Figure imgf000026_0001
and mixtures thereof.
When the lactams are unmodified, it means that they are contain no substituents other that hydrogen and have no heterocyclic substitution of the alkenyl chain of R. R is preferably an alkenyl chain of two to seven carbon atoms. It is preferred that the lactam leaving group will be unmodified. It is more preferred that the unsubstituted lactam leaving group will be either caprolactam or valerolactam. That is:
Figure imgf000026_0002
(b) Organic Peroxides, especially Diacyl Peroxides - These are extensively illustrated m
Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages 63-72, all incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one which exerts minimal adverse impact on spotting/filming. (c) Metal-contaming Bleach Catalysts - The present invention compositions and methods may utilize metal-containmg bleach catalysts that are effective for use in bleaching compositions. Preferred are manganese and cobalt-containing bleach catalysts.
One type of metal-contaming bleach catalyst is a catalyst system compnsmg a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediammetetraacetic acid, ethylenediammetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed m U.S. 4,430,243 Bragg, issued February 2, 1982. Manganese Metal Complexes - If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed m U.S. Patent Nos. 5,576,282; 5,246.621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub. Nos. 549,271 Al, 549,272 Al, 544,440 A2, and 544,490 Al , Preferred examples of these catalysts include MnIV2(u-0)3(l,4J-tπmethyl-l,4J-tπazacyclononane)2(PF6)2, Mnm2(u-0)l(u-OAc)2(1.4J- tπmethyl-l,4J-tnazacyclononane)2(Clθ4)2, Mn*^V4(u-0)6( 1 ,4J-tnazacyclononane)4(Clθ4)4, MnιπMnr 4(u-0)1(u-OAc)2Jl,4J-tnmethyl-l,4J-tnazacyclononane)2(Clθ4)3, MnIV(l,4J- trimethyl- 1,4,7-tπazacyclononane)- (OC^^PFg), and mixtures thereof Other metal-based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and U.S. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported m the following: U.S. Patent Nos 4,728,455, 5,284,944; 5,246,612; 5,256,119; 5,280,117; 5,274,147;
5,153,161; and 5,227,084. Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are descnbed, for example, m U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L.
Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Biomorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt pentaarmne acetate salts having the formula [Co(NH3)5θAc] Ty, wherem "OAc" represents an acetate moiety and "Ty" is an anion, and especially cobalt pentaarmne acetate chloπde, [Co(NH3)5θAc]Cl2; as well as [Co(NH3)5OAc](OAc)2; [Co(NH3)5OAc](PF6)2; [Co(NH3)5OAc](S04); [Co-
(NH3)5OAc](BF4)2; and [Co( H3)5OAc](Nθ3)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; in the Tobe article and the references cited therein; and m U.S. Patent 4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characteπzation of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem.. 18, 1497-1502 (1979); Inorg. Chem.. 21, 2881-2885 (1982); Inorg Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry. 56, 22-25 (1952). Transition Metal Complexes of Macropolvcvchc Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycychc ngid ligand. The phrase "macropolycychc πgid ligand" is sometimes abbreviated as "MRL" in discussion below. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherem "ppb" denotes parts per billion by weight and "ppm" denotes parts per million by weight).
Suitable transition metals e g., Mn are illustrated hereinafter. "Macropolycychc" means a MRL is both a macrocycle and is polycychc "Polycychc" means at least bicychc. The term "ngid" as used herein includes "having a superstructure" and "cross-bπdged". "Rigid" has been defined as the constrained converse of flexibility: see D H. Busch., Chemical Reviews.. (1993), 93, 847-860, incorporated by reference. More particularly, "ngid" as used herein means that the MRL must be determmably more rigid than a macrocycle ("parent macrocycle") which is otherwise identical (having the same nng size and type and number of atoms m the mam πng) but lacking a superstructure (especially linking moieties or, preferably cross-bπdgmg moieties) found m the MRL's. In determining the comparative πgidity of macrocycles with and without superstructures, the practitioner will use the free form (not the metal-bound form) of the macrocycles Rigidity is well-known to be useful in compaπng macrocycles; suitable tools for determining, measuπng or companng rigidity include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al., Inorganica Chimica Acta. (1989). 164, 73-84. Preferred MRL's herein are a special type of ultra-πgid ligand which is cross-bπdged. A
"cross-bndge" is nonhmitingly illustrated in 1.11 herembelow. In 1.11, the cross-bπdge is a -
1 8
CH2CH2- moiety. It bndges N and N m the illustrative structure. By companson, a "same-
1 12 side" bndge, for example if one were to be introduced across N and N m l.l l, would not be sufficient to constitute a "cross-bndge" and accordingly would not be preferred. Suitable metals in the ngid ligand complexes include Mn(U), Mn(ITf), Mn(IV), Mn(V),
Fe(π), Fe(m), Fe(TV), Co(I), Co(U.), Co(III), Nι(I), Nι(II), Nι(HΪ), Cu(I), Cu(II), Cu(m), Cr(II), Cr(m), Cr(IV), Cr(V), Cr(VI), V(__), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(TV), W(V), W(VI), Pd(U), Ru(π), Ru(m), and Ru(IV). Preferred transition-metals m the instant transition- metal bleach catalyst include manganese, iron and chromium. More generally, the MRL's (and the corresponding transition-metal catalysts) herein suitably compπse:
(a) at least one macrocycle main πng compπsing four or more heteroatoms; and
(b) a covalently connected non-metal superstructure capable of increasing the πgidity of the macrocycle, preferably selected from (1) a bndgmg superstructure, such as a linking moiety;
(II) a cross-bπdging superstructure, such as a cross-bπdgmg linking moiety; and
(III) combinations thereof.
The term "superstructure" is used herein as defined in the literature by Busch et al., see, for example, articles by Busch in "Chemical Reviews". Preferred superstructures herein not only enhance the ngidity of the parent macrocycle, but also favor folding of the macrocycle so that it co-ordinates to a metal in a cleft. Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated m Fig. 1 and Fig. 2 below, can be used.
CH2)n Fig 1 wherein n is an integer, for example from 2 to 8, preferably less than 6, typically 2 to 4, or
Figure imgf000029_0001
Fig. 2 wherem m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, tnalkylammomum, halogen, nitro, sulfonate, or the like. The aromatic πng in 1J0 can be replaced by a saturated nng, in which the atom m Z connecting into the πng can contain N, O, S or C.
Suitable MRL's are further nonlimitingly illustrated by the following compound:
Figure imgf000029_0002
Fig. 3
This is a MRL in accordance with the invention which is a highly preferred, cross- bπdged, methyl-substituted (all nitrogen atoms tertiary) deπvative of cyclam. Formally, this ligand is named 5J2-dιmethyl-l,5,8J2-tetraazabιcyclo[6.6J]hexadecane usmg the extended von Baeyer system. See "A Guide to lUPAC Nomenclature of Organic Compounds- Recommendations 1993", R. Panico, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.
Transition-metal bleach catalysts of Macrocychc Rigid Ligands which are suitable for use in the invention compositions can m general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or cleaning uses, and non-limitingly illustrated by any of the following:
Dιchloro-5J2-dιmethyl-l,5,8J2-tetraazabιcyclo[6.6J]hexadecane Manganese(II) Dιaquo-5J2-dιmethyl-l,5,8J2-tetraazabιcyclo[6.6J]hexadecane Manganese(lT) Hexafluorophosphate Aquo-hydroxy-5J2-dιmethyl-l,5,8J2-tetraazabιcyclo[6.6J]hexadecane Manganese(__) Hexafluorophosphate Diaquo-5J2-dimethyl-l,5,8J2-tetraazabicyclo[6.6J]hexadecane Manganese(II) Tetrafluoroborate Dιchloro-5J2-dιmethyl-l,5,8J2-tetraazabιcyclo[6.6J]hexadecane Manganese(πi)
Hexafluorophosphate Dιchloro-5J2-dι-n-butyl-l,5,8J2-tetraaza bιcyclo[6.6J]hexadecane Manganese(II) Dιchloro-5J2-dιbenzyl-l,5,8J2-tetraazabιcyclo[6.6J]hexadecane Manganese(II) Dιchloro-5-n-butyl-12-methyl-l,5,8J2-tetraaza-bιcyclo[6.6J]hexadecane
Manganese(II) Dιchloro-5-n-octyl-12-methyl-l,5,8J2-tetraaza-bιcyclo[6.6J]hexadecane Manganese(II) Dichloro-5-n-butyl-12-methyl-l,5,8J2-tetraaza-bicyclo[6.6J]hexadecane Manganese(II).
As a practical matter, and not by way of limitation, the 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 0J ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic washing process, typical compositions herein will compnse 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 bleaching compositions.
(d) Other Bleach Catalysts - The compositions herein may compnse one or more other bleach catalysts. Preferred bleach catalysts are zwittenonic bleach catalysts, which are descnbed in U.S. Patent No. 5,576,282 (especially 3-(3,4-dιhydroιsoquιnolmιum) propane sulfonate. Other bleach catalysts include cationic bleach catalysts are descnbed m U.S. Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO 95/13351, WO 95/13352, and WO 95/13353.
As a practical matter, and not by way of limitation, the 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 m 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 0J ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels m the wash liquor of an automatic washing process, typical compositions herein will compπse from about 0.0005% to about 0J%>, more preferably from about 0 004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions (e) Preformed peracids - Also suitable as bleaching agents are preformed peracids, such as phtha mido-peroxy-caproic acid ("PAP") See for example U.S. Patent Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431.
Enzymes - The treating compositions herein may also optionally contain one or more types of detergent enzymes. Such enzymes can include other proteases, amylases and hpases. They may be incoφorated into the non-aqueous liquid detergent compositions herein m the form of suspensions, "marumes" or "pπlls". Another suitable type of enzyme compnses those in the form of slurπes of enzymes in noniomc surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL" or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP." Suitable enzymes and levels of use are descπbed m U.S. Pat. No. 5,576,282, 5,705,464 and 5,710,115.
Enzymes added to the compositions herein in the form of conventional enzyme pπlls are especially preferred for use herein. Such pnlls will generally range m size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. Pπlls in the compositions of the present invention have been found, m compaπson with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time. Thus, compositions which utilize enzyme pnlls need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents. However, enzymes added to the compositions herein may be in the form of granulates, preferably T-granulates.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stam removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and hpases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, hpases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, xylanases, hpases, phosphohpases, esterases, cutmases, pectmases, keratanases, reductases, oxidases, phenoloxidases, hpoxygenases, hgnmases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabmosidases, hyaluromdase, chondroitmase, laccase, mannanases, xyloglucanases and known amylases, or mixtures thereof Examples of such suitable enzymes are disclosed in U.S. Patent Nos. 5,705,464,
5,710,115, 5,576,282, 5,728,671 and 5,707,950 Peroxidase enzymes are used m combination with oxygen sources, e.g percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates m the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, hgninase and haloperoxidase such as chloro- and bromo-peroxidase. Suitable peroxidases and peroxidase-containmg detergent compositions are disclosed, for example, in U.S. Patent Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950, PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
Enhancers are generally compπsed at a level of from 0.1% to 5% by weight of total composition. Preferred enhancers are substituted phenthiazme and phenoxasme 10- Phenothiazmepropiomcacid (PPT), 10-ethylphenothiazine-4-carboxyhc acid (EPC), 10- phenoxazmepropionic acid (POP) and 10-methylphenoxazine (descπbed in WO 94/12621) and substitued synngates (C3-C5 substitued alkyl syπngates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
Said peroxidases are normally incorporated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition. Enzymatic systems may be used as bleaching agents. The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or dunng the washing and/or nnsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991. Other preferred enzymes that can be included m the cleanmg compositions of the present invention include hpases. Suitable hpase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzen ATCC 19.154, as disclosed in Bntish Patent 1,372,034. Suitable hpases include those which show a positive immunological cross-reaction with the antibody of the hpase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This hpase is available from Amano Pharmaceutical Co Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano- P". Other suitable commercial hpases include Amano-CES, hpases ex Chromobacter viscosum, e g. Chromobacter viscosum var Iψolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum hpases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and hpases ex Pseudomonas gladioli. Especially suitable hpases are hpases such as Ml LιpaseR anci LιpomaxR (Gist-Brocades) and LιpolaseR and Lipolase Ultra-R Novo) which have found to be very effective when used in combination with the compositions of the present invention Also suitable are the hpolytic enzymes descπbed in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever Also suitable are cutinases [EC 3.L 50] which can be considered as a special kind of hpase, namely hpases which do not require mterfacial activation. Addition of cutinases to cleaning compositions have been described m e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
Lipases and/or cutinases, when present, are normally incorporated in the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
In addition to the above referenced lipases, phosphohpases may be incorporated into the cleaning compositions of the present invention. Nonhmitmg examples of suitable phosphohpases included: EC 3JJJ2 Phosphohpase Al; EC 3J.L4 Phosphohpase A2; EC 3.LL5 Lysophohpase; EC 3.1.4.3 Phosphohpase C; EC 3. 4.4. Phospohpase D. Commercially available phosphohpases include LECITASE® from Novo Nordisk A/S of Denmark and Phosphohpase A2 from Sigma. When phospohpases are mcluded m the compositions of the present invention, it is preferred that amylases are also included. Without desiπng to be bound by theory, it is believed that the combined action of the phosphohpase and amylase provide substantive stam removal, especially on greasy/oily, starchy and highly colored stams and soils. Preferably, the phosphohpase and amylase, when present, are incorporated into the compositions of the present invention at a pure enzyme weight ratio between 4500:1 and 1:5, more preferably between 50: 1 and 1 :1.
Suitable proteases are the subtihsms which are obtained from particular strains of B subtilis and B. licheniformis (subtihsm BPN and BPN') 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 Industπes A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is descπbed in GB 1,243,784 to Novo. Proteolytic enzymes also encompass modified bacteπal senne proteases, such as those descπbed in European Patent Application Senal Number 87 303761.8, filed Apnl 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bactenal senne protealytic enzyme which is called "Protease A" herein. Suitable is the protease called herein "Protease C", which is a vanant of an alkaline senne protease from Bacillus in which Lysme replaced argimne at position 27, tyrosine replaced valme at position 104, senne replaced asparagme at position 123, and alanine replaced threonme at position 274. Protease C is described in EP 90915958 4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
A preferred protease referred to as "Protease D" is a carbonyl hydrolase as described in U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase variant of the protease described in WO95/10591, having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin (co-pending patent application US Serial No. 60/048,550, filed June 04, 1997 and PCT International Application Serial No. PCT/TB98/00853).
Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.
See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsoφtion and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.
Particularly useful proteases are described in PCT publications: WO 95/30010; WO 95/30011; and WO 95/29979. Suitable proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands).
Other particularly useful proteases are multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amyloliquefaciens subtilisin; wherein when said protease variant includes a substitution of amino acid residues at positions corresponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than amino acid residue positions corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefaciens subtilisin and or multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amyloliquefaciens subtilisin as described in PCT Application Nos. PCT US98/22588, PCT/US98/22482 and PCT/US98/22486 all filed on October 23, 1998 from The Procter & Gamble Company (P&G Cases 7280&, 7281& and 7282L, respectively). More preferably the protease variant includes a substitution set selected from the group consisting of:
12/76/ 103/ 104/ 130/222/245/261 ; 62/103/104/159/232/236/245/248/252; 62/103/104/159/213/232/236/245/248/252;
62/101/103/104/159/212/213/232/236/245/248/252;
68/103/104/159/232/236/245;
68/103/104/159/230/232/236/245;
68/103/104/159/209/232/236/245; 68/103/104/159/232/236/245/257;
68/76/103/104/159/213/232/236/245/260; 68/103/104/159/213/232/236/245/248/252; 68/103/104/159/183/232/236/245/248/252; 68/103/104/159/185/232/236/245/248/252; 68/103/104/159/185/210/232/236/245/248/252;
68/103/104/159/210/232/236/245/248/252;
68/103/104/159/213/232/236/245;
98/103/104/159/232/236/245/248/252;
98/102/103/104/159/212/232/236/245/248/252; 101/103/104/159/232/236/245/248/252;
102/103/104/159/232/236/245/248/252; 103/104/159/230/236/245;
103/104/159/232/236/245/248/252;
103/104/159/217/232/236/245/248/252;
103/104/130/159/232/236/245/248/252; 103/104/131/159/232/236/245/248/252;
103/104/159/213/232/236/245/248/252; and 103/104/159/232/236/245.
Still even more preferably the protease variant includes a substitution set selected from the group consisting of:
12R76D/103A/104T/130T/222S/245R261D; 62D/103A/104I/159D/232V/236H/245R248D/252K; 62D/103A/104I/159D/213R/232V/236H/245R/248D/252K; 68A/103A/104I159D/209W/232V/236H/245R;
68A/76D/103A/104I/159D/213R232V/236H245R260A;
68A103A/104I/159D/213E/232V/236H/245R248D/252K;
68A/103A/104I/159D/183D/232V/236H/245R248D/252K;
68A/103A/104I/159D/232V/236H245R; 68A103A/104I/159D/230V/232V/236H/245R;
68A/103A104I/159D/232V/236H/245R257V;
68A/103A/104I/159D/213G/232V/236H/245R/248D/252K;
68A103A/104I/159D/185D/232V/236H245R/248D/252K;
68A/103A/104I/159D/185D/210L/232V/236H/245R248D/252K; 68A103A/104I/159D/210L/232V/236H245R/248D/252K;
68A/103A104I/159D/213G/232V/236H/245R;
98L/103A104I/159D/232V/236H/245R/248D/252K;
98L/102A103A104I/159D/212G/232V/236H/245R/248D/252K;
101G/103A104I/159D/232V/236H245R/248D/252K; 102A/103A104I/159D/232V/236H/245R/248D/252K;
103A/104I/159D/230V/236H/245R;
103A104I/159D/232V/236H245R248D/252K;
103A104I159D/217E/232V/236H/245R248D/252K;
103A104I130G/159D/232V/236H/245R/248D/252K; 103A104I131V/159D/232V/236H/245R248D/252K;
103A/104I159D/213R/232V/236H245R/248D/252K;and
PAGE MISSING AT TIME OF PUBLICATION
Such amylolytic enzymes, when present, are incoφorated in the cleaning compositions of the present invention a level of from 0 0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0 00024%) to 0.048% pure enzyme by weight of the composition.
The compositions of the present invention may also compπse a mannanase enzyme. Preferably, the mannanase is selected from the group consisting of: three mannans-degrading enzymes : EC 3.2.1.25 : β-mannosidase, EC 3.2.1 78 : Endo-l,4-β-mannosιdase, referred therein after as "mannanase" and EC 3.2.1.100 : 1 ,4-β-mannobιosιdase and mixtures thereof. (RJPAC
Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press).
More preferably, the treating compositions of the present invention, when a mannanase is present, compπse a β-l,4-Mannosιdase (E.C. 3.2.1.78) referred to as Mannanase. The term "mannanase" or "galactomannanase" denotes a mannanase enzyme defined according to the art as officially being named mannan endo-l,4-beta-mannosιdase and having the alternative names beta-mannanase and endo-l,4-mannanase and catalyzing the reaction: random hydrolysis of 1,4- beta-D- mannosidic linkages in mannans, galactomannans, glucomannans, and galactoglucomannans.
In particular, Mannanases (EC 3.2.1.78) constitute a group of polysaccharases which degrade mannans and denote enzymes which are capable of cleaving polyose chains containing mannose units, i.e. are capable of cleaving glycosidic bonds in mannans, glucomannans, galactomannans and galactogluco-mannans. Mannans are polysacchandes having a backbone composed of β-1,4- linked mannose; glucomannans are polysacchandes having a backbone or more or less regularly alternating β-1,4 linked mannose and glucose; galactomannans and galactoglucomannans are mannans and glucomannans with α-1,6 linked galactose sidebranches. These compounds may be acetylated.
The degradation of galactomannans and galactoglucomannans is facilitated by full or partial removal of the galactose sidebranches. Further the degradation of the acetylated mannans, glucomannans, galactomannans and galactogluco-mannans is facilitated by full or partial deacetylation. Acetyl groups can be removed by alkali or by mannan acetylesterases. The oligomers which are released from the mannanases or by a combination of mannanases and α- galactosidase and/or mannan acetyl esterases can be further degraded to release free maltose by β-mannosidase and/or β-glucosidase.
Mannanases have been identified in several Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp. 3505-3510 (1990) descπbes a beta-mannanase deπved from Bacillus stearothermophilus in dimer form having molecular weight of 162 kDa and an optimum pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551- 555 (1994) descnbes a beta-mannanase deπved from Bacillus subtilis having a molecular weight of 38 kDa, an optimum activity at pH 5 0 and 55C and a pi of 4.8. JP-03047076 discloses a beta- mannanase deπved from Bacillus sp., having a molecular weight of 373 kDa measured by gel filtration, an optimum pH of 8-10 and a pi of 5J-5 4. JP-63056289 descπbes the production of an alkaline, thermostable beta-mannanase which hydrolyses beta-l,4-D-mannopyranosιde bonds of e.g. mannans and produces manno-oligosacchandes. JP-63036774 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase at an alkaline pH. JP-08051975 discloses alkaline beta-mannanases from alkalophihc Bacillus sp. AM- 001. A purified mannanase from Bacillus amyloliquefaciens useful in the bleaching of pulp and paper and a method of preparation thereof is disclosed in WO 97/11164. WO 91/18974 descπbes a hemicellulase such as a glucanase, xylanase or mannanase active at an extreme pH and temperature. WO 94/25576 discloses an enzyme from Aspergillus aculeatus, CBS 101.43, exhibiting mannanase activity which may be useful for degradation or modification of plant or algae cell wall matenal. WO 93/24622 discloses a mannanase isolated from Trichoderma reseei useful for bleaching hgnocellulosic pulps. An hemicellulase capable of degrading mannan- contammg hemicellulose is descnbed in W091/18974 and a puπfϊed mannanase from Bacillus amyloliquefaciens is descπbed in W097/11164.
Preferably, the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase originating from a bacteπal source. Especially, the laundry detergent composition of the present invention will compnse an alkaline mannanase selected from the mannanase from the strain Bacillus agaradhaerens NICMB 40482; the mannanase from Bacillus subtilis strain 168, gene yght; the mannanase from Bacillus sp. 1633 and/or the mannanase from Bacillus sp. AAI12. Most preferred mannanase for the inclusion in the detergent compositions of the present invention is the mannanase enzyme oπgmatmg from Bacillus sp. 1633 as descnbed m the co-pending Danish patent application No. PA 1998 01340.
The terms "alkaline mannanase enzyme" is meant to encompass an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5.
The alkaline mannanase from Bacillus agaradhaerens NICMB 40482 is descπbed in the co-pendmg U.S. patent application seπal No. 09/111,256. More specifically, this mannanase is: l) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or n) a polypeptide compπsing an amino acid sequence as shown m positions 32-343 of SEQ ED NO:2 as shown in U.S. patent application seπal No. 09/111,256; or in) an analogue of the polypeptide defined m I) or n) which is at least 70% homologous with said polypeptide, or is deπved from said polypeptide by substitution, deletion or addition of one or several ammo acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in punfied form. Also encompassed is the corresponding isolated polypeptide having mannanase activity selected from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase activity and compπsing a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 97 to nucleotide 1029 as shown in U.S. patent application seπal No.
09/111,256;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the ammo acid sequence of SEQ ID NO: 2 from ammo acid residue 32 to ammo acid residue 343 as shown in U.S. patent application senal No. 09/111,256;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pSJ1678 compπsing the polynucleotide molecule (the DNA sequence) encoding said mannanase has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Pmposes of Patent Procedure at the Deutsche Sammlung von Mikroorgamsmen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 18 May 1998 under the deposition number DSM 12180. A second more preferred enzyme is the mannanase from the Bacillus subtilis strain 168, which is descπbed m the co-pendmg U.S. patent application seπal No. 09/095,163. More specifically, this mannanase is:
0 is encoded by the coding part of the DNA sequence shown m SED ID No. 5 shown in the U.S. patent application seπal No. 09/095,163 or an analogue of said sequence; and/or u) a polypeptide compπsing an ammo acid sequence as shown SEQ DD NO: 6 shown in the U.S. patent application senal No. 09/095,163; or in) an analogue of the polypeptide defined in n) which is at least 70%> homologous with said polypeptide, or is deπved from said polypeptide by substitution, deletion or addition of one or several am o acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in punfied form. Also encompassed m the corresponding isolated polypeptide having mannanase activity selected from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase activity and compπsing a sequence of nucleotides as shown in SEQ ID NO:5 as shown m the U.S. patent application serial No. 09/095,163 (b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70%> identical to the ammo acid sequence of SEQ ED NO: 6 as shown in the U.S. patent application senal No. 09/095,163; (d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d). A third more preferred mannanase is descnbed in the co-pendmg Danish patent application No. PA 1998 01340. More specifically, this mannanase is: l) a polypeptide produced by Bacillus sp. 1633; n) a polypeptide compπsing an ammo acid sequence as shown in positions
33-340 of SEQ ID NO:2 as shown in the Danish application No. PA 1998 01340; or in) an analogue of the polypeptide defined in I) or n) which is at least 65% homologous with said polypeptide, is deπved from said polypeptide by substitution, deletion or addition of one or several ammo acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in puπfied form. Also encompassed is the corresponding isolated polynucleotide molecule selected from the group consisting of: (a) polynucleotide molecules encoding a polypeptide having mannanase activity and compnsmg a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 317 to nucleotide 1243 the Danish application No. PA 1998 01340;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO:
2 from ammo acid residue 33 to amino acid residue 340 the Danish application No. PA 1998 01340;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d). The plasmid pBXM3 compnsmg the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Puφoses of Patent Procedure at the Deutsche Sammlung von Mikroorgamsmen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 29 May 1998 under the deposition number DSM 12197. A fourth more preferred mannanase is descπbed in the Danish co-pend g patent application No. PA 1998 01341 More specifically, this mannanase is: l) a polypeptide produced by Bacillus sp AAI 12, n) a polypeptide compπsing an ammo acid sequence as shown in positions 25-362 of SEQ ID NOJas shown in the Danish application No. PA 1998 01341; or in) an analogue of the polypeptide defined in l) or n) which is at least 65% homologous with said polypeptide, is denved from said polypeptide by substitution, deletion or addition of one or several ammo acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in puπfied form. Also encompassed is the corresponding isolated polynucleotide molecule selected from the group consisting of
(a) polynucleotide molecules encoding a polypeptide having mannanase activity and compπsing a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 225 to nucleotide 1236 as shown m the Danish application No. PA 1998 01341;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the ammo acid sequence of SEQ ID NO:
2 from amino acid residue 25 to ammo acid residue 362 as shown m the Danish application No. PA 1998 01341;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d). The plasmid pBXMl compnsmg the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Puφoses of Patent Procedure at the Deutsche Sammlung von Mikroorgamsmen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under the deposition number DSM 12433.
The mannanase, when present, is incoφorated into the treating compositions of the present invention preferably at a level of from 0 0001% to 2%, more preferably from 0.0005% to 0 1%, most preferred from 0.001% to 0.02% pure enzyme by weight of the composition. The compositions of the present invention may also compπse a xyloglucanase enzyme
Suitable xyloglucanases for the puφose of the present invention are enzymes exhibiting endoglucanase activity specific for xyloglucan, preferably at a level of from about 0.001% to about 1%, more preferably from about 0.01% to about 0.5%, by weight of the composition. As used herein, the term "endoglucanase activity" means the capability of the enzyme to hydrolyze 1,4-β-D-glycosιdιc linkages present in any cellulosic matenal, such as cellulose, cellulose derivatives, lichenm, β-D-glucan, or xyloglucan. The endoglucanase activity may be determined in accordance with methods known in the art, examples of which are descnbed m WO 94/14953 and hereinafter. One unit of endoglucanase activity (e.g. CMCU, AVIU, XGU or BGU) is defined as the production of 1 μmol reducing sugar/mm from a glucan substrate, the glucan substrate being, e.g., CMC (CMCU), acid swollen Avicell (AVIU), xyloglucan (XGU) or cereal β-glucan (BGU). The reducing sugars are determined as descnbed in WO 94/14953 and hereinafter. The specific activity of an endoglucanase towards a substrate is defined as umts/mg of protein.
Suitable are enzymes exhibiting as its highest activity XGU endoglucanase activity (hereinafter "specific for xyloglucan"), which enzyme: I) is encoded by a DNA sequence compπsing or included in at least one of the following partial sequences
(a) ATTCATTTGT GGACAGTGGA C (SEQ ID No: 1)
(b) GTTGATCGCA CATTGAACCA (SEQ ID NO: 2)
(c) ACCCCAGCCG ACCGATTGTC (SEQ ID NO: 3) (d) CTTCCTTACC TCACCATCAT (SEQ ID NO: 4)
(e) TTAACATCTT TTCACCATGA (SEQ ID NO: 5)
(f) AGCTTTCCCT TCTCTCCCTT (SEQ ID NO: 6)
(g) GCCACCCTGG CTTCCGCTGC CAGCCTCC (SEQ ID NO: 7) (h) GACAGTAGCA ATCCAGCATT (SEQ ID NO: 8) (I) AGCATCAGCC GCTTTGTACA (SEQ ID NO: 9)
0) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10)
(k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO: 11)
(1) GTGGGCGGCC CCTCAGGCAA (SEQ ID NO: 12)
(m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13) (n) GGCTGGTAG TAATGAGTCT (SEQ ID NO: 14)
(o) GGCGCAGAGT TTGGCCAGGC (SEQ ID NO: 15)
(p) CAACATCCCC GGTGTTCTGG G (SEQ ID NO: 16)
(q) AAAGATTCAT TTGTGGACAG TGGACGTTGA TCGCACATTG AACCAACCCC
AGCCGACCGA TTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT
TCCCTTCTCT CCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG
CGGTCAGTGG
GATACCGCCA CCGCCGGTGA CTTCACCCTG TACAACGACC TTTGGGGCGA
GACGGCCGGC ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC
TTGTCACACC
AGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG (SEQ ID
NO: 17) or
(r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAG
GCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG
TGTTTCAGTC
CCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA
GGAGACGCTG TATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT
CCTGTACATA
CAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA AAAA
(SEQ ID NO:18) or a sequence homologous thereto encoding a polypeptide specific for xyloglucan with endoglucanase activity, ii) is immunologically reactive with an antibody raised against a highly purified endoglucanase encoded by the DNA sequence defined in i) and derived from Aspergillus aculeatus, CBS 101.43, and is specific for xyloglucan.
More specifically, as used herein the term "specific for xyloglucan" means that the endoglucanase enzyme exhibits its highest endoglucanase activity on a xyloglucan substrate, and preferably less than 75%) activity, more preferably less than 50%> activity, most preferably less than about 25% activity, on other cellulose-containing substrates such as carboxymethyl cellulose, cellulose, or other glucans.
Preferably, the specificity of an endoglucanase towards xyloglucan is further defined as a relative activity determined as the release of reducing sugars at optimal conditions obtained by incubation of the enzyme with xyloglucan and the other substrate to be tested, respectively. For instance, the specificity may be defined as the xyloglucan to β-glucan activity (XGU BGU), xyloglucan to carboxy methyl cellulose activity (XGU/CMCU), or xyloglucan to acid swollen
Avicell activity (XGU/ AVIU), which is preferably greater than about 50, such as 75, 90 or 100. The term "derived from" as used herein refers not only to an endoglucanase produced by strain CBS 101.43, but also an endoglucanase encoded by a DNA sequence isolated from strain CBS 101.43 and produced m a host organism transformed with said DNA sequence. The term "homologue" as used herein indicates a polypeptide encoded by DNA which hybπdizes to the same probe as the DNA coding for an endoglucanase enzyme specific for xyloglucan under certain specified conditions (such as presoakmg in 5xSSC and prehybπdizmg for 1 h at -40°C m a solution of 5xSSC, 5xDenhardt's solution, and 50 μg of denatured sonicated calf thymus DNA, followed by hybπdization in the same solution supplemented with 50 μCi 32-P-dCTP labelled probe for 18 h at -40°C and washing three times in 2xSSC, 0.2% SDS at 40°C for 30 minutes). More specifically, the term is intended to refer to a DNA sequence which is at least 70% homologous to any of the sequences shown above encoding an endoglucanase specific for xyloglucan, including at least 75%, at least 80%, at least 85%, at least 90% or even at least 95% with any of the sequences shown above. The term is intended to include modifications of any of the DNA sequences shown above, such as nucleotide substitutions which do not give nse to another ammo acid sequence of the polypeptide encoded by the sequence, but which correspond to the codon usage of the host organism into which a DNA construct compnsmg any of the DNA sequences is introduced or nucleotide substitutions which do give nse to a different amino acid sequence and therefore, possibly, a different amino acid sequence and therefore, possibly, a different protein structure which might give nse to an endoglucanase mutant with different properties than the native enzyme. Other examples of possible modifications are insertion of one or more nucleotides into the sequence, addition of one or more nucleotides at either end of the sequence, or deletion of one or more nucleotides at either end or within the sequence.
Endoglucanase specific for xyloglucan useful in the present invention preferably is one which has a XGU BGU, XGU/CMU and/or XGU/AVIU ratio (as defined above) of more than 50, such as 75, 90 or 100.
Furthermore, the endoglucanase specific for xyloglucan is preferably substantially devoid of activity towards β-glucan and/or exhibits at the most 25% such as at the most 10% or about 5%, activity towards carboxymethyl cellulose and/or Avicell when the activity towards xyloglucan is 100%. In addition, endoglucanase specific for xyloglucan of the invention is preferably substantially devoid of transferase activity, an activity which has been observed for most endoglucanases specific for xyloglucan of plant origin. Endoglucanase specific for xyloglucan may be obtained from the fungal species A aculeatus, as descπbed in WO 94/14953. Microbial endoglucanases specific for xyloglucan has also been descπbed in WO 94/14953. Endoglucanases specific for xyloglucan from plants have been descπbed, but these enzymes have transferase activity and therefore must be considered mfeπor to microbial endoglucanases specific for xyloglucan whenever extensive degradation of xyloglucan is desirable. An additional advantage of a microbial enzyme is that it, in general, may be produced in higher amounts m a microbial host, than enzymes of other ongms. The xyloglucanase, when present, is incoφorated into the treating compositions of the invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0 001% to 0.02% pure enzyme by weight of the composition.
The above-mentioned enzymes may be of any suitable oπgm, such as vegetable, animal, bactenal, fungal and yeast oπgin Ongm can further be mesophihc or extremophihc (psychrophihc, psychrotrophic, thermophihc, barophihc, alkalophihc, acidophihc, halophihc, etc.). Puπfied or non-puπfied forms of these enzymes may be used. Nowadays, it is common practice to modify wild-type enzymes via protein / genetic engineeπng techniques in order to optimize their performance efficiency m the treating compositions of the invention. For example, the vanants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased. Alternatively, the vaπant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme vaπant is tailored to suit the particular cleaning application.
In particular, attention should be focused on am o acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility. The isoelectnc point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase m isoelectnc point may help to improve compatibility with anionic surfactants. The stability of the enzymes may be further enhanced by the creation of e.g. additional salt bπdges and enforcing calcium binding sites to increase chelant stability. These optional detersive enzymes, when present, are normally incoφorated in the treating composition at levels from 0.0001% to 2% of pure enzyme by weight of the treating composition. The enzymes can be added as separate single ingredients (pπlls, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ). Other suitable cleanmg adjunct mateπals that can be added are enzyme oxidation scavengers. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyaπunes.
A range of enzyme mateπals and means for their mcoφoration into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed m U.S. 4,101,457, and m U.S. 4,507,219. Enzyme matenals useful for liquid detergent formulations, and their mcoφoration into such formulations, are disclosed in U.S. 4,261,868. Enzyme Stabilizers - Enzymes for use m treating compositions can be stabilized by vanous techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also descnbed, for example, in U S 3,519,570 A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is descπbed in WO 9401532 The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are described in U.S. Pat. Nos 5,705,464, 5,710,115 and 5,576,282. Builders - The treating compositions descnbed herein preferably compπse one or more detergent builders or builder systems. When present, the compositions will typically compπse at least about 1%) builder, preferably from about 5%, more preferably from about 10% to about 80%>, preferably to about 50%, more preferably to about 30% by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded. Preferred builders for use in the treating compositions, particularly dishwashing compositions, described herein include, but are not limited to, water-soluble builder compounds, (for example polycarboxylates) as descnbed m U.S. Patent Nos. 5,695,679, 5,705,464 and 5,710,H5. Other suitable polycarboxylates are disclosed m U.S. Patent Nos. 4,144,226,
3,308,067 and 3,723,322. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly titrates.
Inorganic or P-contaimng detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammomum salts of polyphosphates (exemplified by the tπpolyphosphates, pyrophosphates, and glassy polymeπc meta-phosphates), phosphonates (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and alummosihcates.
However, non-phosphate builders are required in some locales. Importantly, the compositions herein function suφnsmgly well even m the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.
Suitable silicates include the water-soluble sodium silicates with an Sι02:Na20 ratio of from about 1.0 to 2.8, with ratios of from about 1.6 to 2.4 being preferred, and about 2.0 ratio being most preferred. The silicates may be m the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an Sι02:Na20 ratio of 2.0 is the most preferred. Silicates, when present, are preferably present in the treating compositions descπbed herein at a level of from about 5% to about 50% by weight of the composition, more preferably from about 10% to about 40% by weight.
Partially soluble or insoluble builder compounds, which are suitable for use in the treating compositions, particularly granular detergent compositions, include, but are not limited to, crystalline layered silicates, preferably crystalline layered sodium silicates (partially water- soluble) as descπbed in U.S. Patent No. 4,664,839, and sodium alummosihcates (water- insoluble). When present in treating compositions, these builders are typically present at a level of from about 1% to 80% by weight, preferably from about 10% to 70% by weight, most preferably from about 20% to 60% by weight of the composition.
Crystalline layered sodium silicates having the general formula NaMSιxθ2x+ι-yH2θ wherem M is sodium or hydrogen, x is a number from about 1.9 to about 4, preferably from about 2 to about 4, most preferably 2, and y is a number from about 0 to about 20, preferably 0 can be used in the compositions descnbed herein. Crystalline layered sodium silicates of this type are disclosed m EP-A-0164514 and methods for their preparation are disclosed in DE-A- 3417649 and DE-A-3742043. The most preferred matenal is delta-Na2Sιθ5, available from Hoechst AG as NaSKS-6 (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-N_2Sιθ5 moφhology form of layered silicate. SKS-6 is a highly preferred layered silicate for use in the compositions descnbed herein, but other such layered silicates, such as those having the general formula NaMSιxθ2x+ι-yH2θ wherem 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 be used in the compositions descnbed herein. Vanous other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2Sιθ5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a cπspemng agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
The crystalline layered sodium silicate material is preferably present m granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble lomzable matenal. The solid, water-soluble lomzable matenal is preferably selected from organic acids, organic and inorganic acid salts and mixtures thereof. Alummosihcate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Alummosihcate builders have the empiπcal formula:
[Mz(A102)y] xH20 wherem z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264. Preferably, the alummosihcate builder is an alummosihcate zeolite having the unit cell formula:
Naz[(A102)z(Sι02)y] -xH20 wherem z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably from 10 to 264. The alummosihcate builders are preferably m hydrated form and are preferably crystalline, containing from about 10% to about
28%, more preferably from about 18%> to about 22% water in bound form. These alummosihcate ion exchange mateπals can be crystalline or amoφhous in structure and can be naturally-occurring alummosihcates or synthetically denved A method for producing alummosihcate ion exchange mateπals is disclosed in U.S. 3,985,669. Preferred synthetic crystalline alummosihcate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite AX, Zeolite MAP and Zeolite HS and mixtures thereof In an especially preferred embodiment, the crystalline alummosihcate ion exchange matenal has the formula:
Na12[(Alθ2)i2(Sιθ2)i2]-xH20 wherein x is from about 20 to about 30, especially about 27 This matenal is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the alummosihcate has a particle size of about OJ-10 microns in diameter. Zeolite X has the formula:
Na86[(Alθ2)86(Sιθ2)i06]-276H2O
Citrate builders, e.g., citnc acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions descπbed herein are the 3J-dιcarboxy-4- oxa-l,6-hexanedιoates and the related compounds disclosed in U.S. 4,566,984. Useful succimc acid builders include the C5-C20 alkyl and alkenyl succimc acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccimc acid. Specific examples of succmate builders include- laurylsuccinate, myπstylsuccmate, palmitylsucc ate, 2- dodecenylsuccmate (preferred), 2-pentadecenylsuccmate, and the like. Laurylsuccinates are the preferred builders of this group, and are descπbed m European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Fatty acids, e.g., C*i2-Cι monocarboxyhc acids, can also be incoφorated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succmate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator. Dispersants - One or more suitable polyalkyleneimine dispersants may be incoφorated into the treating compositions of the present invention. Examples of such suitable dispersants can be found in European Patent Application Nos. 111,965, 111,984, and 112,592; U.S Patent Nos 4,597,898, 4,548,744, and 5,565,145 However, any suitable clay/soil dispersent or anti- redepostion agent can be used in the treating compositions of the present invention. In addition, polymeric dispersing agents which include polymeπc polycarboxylates and polyethylene glycols, are suitable for use m the present invention Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumanc acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalo c acid. Particularly suitable polymeric polycarboxylates can be denved from acrylic acid Sucn acrylic acid-based polymers which are useful herein are the water- soluble salts of polymenzed 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 mateπals. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, m U.S. 3,308,067.
Acry c/maleic-based copolymers may also be used as a preferred component of the dispersmg/anti-redeposition agent. Such mateπals 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 mateπals which are descnbed in European Patent Application No. 66915, published December 15, 1982, as well as m EP 193,360, published September 3, 1986, which also descnbes such polymers compπsing hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acryhc/vinyl alcohol teφolymers. Such matenals are also disclosed in EP 193,360, including, for example, the 45/45/10 teφolymer of acryhc/maleic/vmyl alcohol. Another polymeπc matenal which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these puφoses 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.
Soil Release Agents - The treating compositions according to the present invention may optionally compπse one or more soil release agents. If utilized, soil release agents will generally compπse from about 0.01%, preferably from about 0.1%, more preferably from about 0.2% to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition Nonhmitmg examples of suitable soil release polymers are disclosed m U.S Patent Nos 5,728,671, 5,691,298, 5,599,782; 5,415,807; 5,182,043, 4,956,447; 4,976,879, 4,968,451, 4,925,577; 4,861,512; 4,877,896; 4,771,730; 4,711,730; 4,721,580, 4,000,093; 3,959,230; and 3,893,929; and European Patent Application 0 219 048. Further suitable soil release agents are descπbed in U.S. Patent Nos. 4,201,824;
4,240,918; 4,525,524; 4,579,681; 4,220,918; and 4,787,989; EP 279,134 A; EP 457,205 A; and DE 2,335,044.
Chelatmg Agents - The treating compositions of the present invention herein may also optionally contain a chelatmg agent which serves to chelate metal ions and metal impunties which would otherwise tend to deactivate the bleaching agent(s). Useful chelating agents can include ammo carboxylates, phosphonates, ammo phosphonates, polyfunctionally-substituted aromatic chelatmg agents and mixtures thereof. Further examples of suitable chelating agents and levels of use are descnbed in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282.
The 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.
If utilized, these chelating agents will generally compπse from about 0.1% to about 15%, more preferably from about 0.1% to about 3.0% by weight of the treating compositions herein. Suds suppressor - Another optional ingredient is a suds suppressor, exemplified by sihcones, and silica-sihcone mixtures. Examples of suitable suds suppressors are disclosed in U.S. Patent Nos. 5,707,950 and 5,728,671. These suds suppressors are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight. Softening agents - Fabπc softening agents can also be incoφorated into the treating compositions of the present invention. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in U.S. 5,019,292. Organic softening agents include the water insoluble tertiary amines as disclosed in GB-A-1 514 276 and EP-B-011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-026 527 and EP-B-026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabnc softening systems include high molecular weight polyethylene oxide matenals as disclosed in EP-A-0 299 575 and 0 313 146
Particularly suitable fabπc softening agents are disclosed in U S. Patent Nos. 5,707,950 and 5,728,673.
Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15%) by weight, with the matenal being added as a dry mixed component to the remainder of the formulation. Organic fabnc softening agents such as the water-msoluble tertiary amines or dilong chain amide materials are incoφorated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide matenals and the water soluble cationic mateπals are added at levels of from 0.1% to 2%, normally from 0.15% to 1 5% by weight. These mateπals are normally added to the spray dned portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.
Biodegradable quaternary ammonium compounds as descnbed in EP-A-040 562 and EP- A-239 910 have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chloπdes and methyl sulfates.
Non-hmitmg examples of softener-compatible amons for the quaternary ammonium compounds and amine precursors include chlonde or methyl sulfate.
Dye transfer inhibition - The treating compositions of the present invention can also include compounds for inhibiting dye transfer from one fabπc to another of solubihzed and suspended dyes encountered dunng fabnc laundeπng and conditioning operations involving colored fabπcs. Polymeric dye transfer inhibiting agents The treating compositions according to the present invention can also compπse from
0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05%> to 1% by weight of polymeπc dye transfer inhibiting agents. Said polymeπc dye transfer inhibiting agents are normally incoφorated into treating compositions in order to inhibit the transfer of dyes from colored fabrics onto fabncs washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabncs before the dyes have the opportunity to become attached to other articles in the wash.
Especially suitable polymeπc dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrohdone and N-vmyhmidazole, polyvmylpyrrohdone polymers, polyvinyloxazohdones and polyvinylimidazoles or mixtures thereof. Examples of such dye transfer inhibiting agents are disclosed m U.S. Patent Nos. 5,707,950 and 5,707,951.
Additional suitable dye transfer inhibiting agents include, but are not limited to, cross- linked polymers. Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been descπbed in the Journal of Polymer Science, volume 22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made m such a way that they form a three-dimensional ngid structure, which can entrap dyes in the pores formed by the three- dimensional structure. In another embodiment, the cross-linked polymers entrap the dyes by swelling Such cross-linked polymers are descnbed in the co-pendmg European patent application 94870213 9. Addition of such polymers also enhances the performance of the enzymes according the invention.
Hydrogen Bond Breaking Agents - Suitable hydrogen bond breaking agents including, but not limited to, plant expansin and urea can optionally be incoφorated into the treating compositions of the present invention. pH and Buffenng Vanation - Many of the treating compositions descπbed herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low buffeπng capacity, or may be substantially unbuffered. Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled m the art. Other Mateπals - Other cleaning adjunct mateπals optionally mcluded in the treating compositions of the present invention can include one or more matenals for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions. Adjuncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct matenals compnse, m total, from about 30%. to about 99.9%, preferably from about 70%> to about 95%>, by weight of the compositions), include other active ingredients such as clay soil removal/anti- redeposition agents, bnghteners, dyes, perfumes, structure elasticizmg agents, earners, hydrotropes, processing aids, fillers, germicides, alkalinity sources, solubilizing agents and/or pigments. Suitable examples of such other cleaning adjunct mateπals and levels of use are found in U.S. Patent Nos. 5,576,282, 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101.
The following examples are meant to exemplify compositions of the present invention, but are not necessaπly meant to limit or otherwise define the scope of the invention. In the treating compositions, the enzyme levels are expressed by percent of pure enzyme by weight of the total composition and unless otherwise specified, the cleaning adjunct matenals are expressed as percent of cleaning adjunct mateπals by weight of the total compositions The polysacchandes can be any suitable polysacchande disclosed heremabove. Further, in the following examples some abbreviations known to those of ordinary skill in the art are used, consistent with the disclosure set forth herein, and or are defined m below
L S Sodium linear C 12 alkyl benzene sulphonate
TAS Sodium tallow alkyl sulphate
CXYAS • Sodium C \ x - C \ y alkyl sulfate 25EY A C* 2-Ci5 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide
CXYEZ A C χ - Cjy predominantly linear primary alcohol condensed with an average of Z moles of ethylene oxide
XYEZS C* χ - CJY sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole
QAS R2.N+(CH3)2(C2H4θH) with R2 = C12-C14 Soap Sodium linear alkyl carboxylate derived from a 80/20 mixture of tallow and coconut oils.
Nonionic C13- 15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxy lation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by
BASF Gmbh.
CFAA C12-C14 alkyl N-methyl glucamide TFAA C1 g-Cjg alkyl N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids. DEQA Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.
Neodol 45-13 C14-C15 linear primary alcohol ethoxylate, sold by Shell
Chemical CO.
Silicate Amoφhous Sodium Silicate (Siθ2:Na2θ ratio = 2.0)
NaSKS-6 Crystalline layered silicate of formula δ-Na2Si2θ5
Carbonate Anhydrous sodium carbonate with a particle size between
200 μm and 900μm.
Bicarbonate Anhydrous sodium bicarbonate with a particle size between
400 μm and 1200μm.
STPP Anhydrous sodium tripolyphosphate
MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000-80,000
Zeolite A Hydrated Sodium Alummosihcate of formula Naj2(Alθ2Siθ2)i2
. 27H2O having a primary particle size in the range from
0J to 10 micrometers
Citrate Tri-sodium citrate dihydrate of activity 86,4% with a particle size distribution between 425 μm and 850 μm.
Citric Anhydrous citric acid PB1 Anhydrous sodium perborate monohydrate bleach, empirical formula NaB0 .H2θ2 PB4 Anhydrous sodium perborate tetrahydrate
Percarbonate Anhydrous sodium percarbonate bleach of empirical formula
2Na2CO3.3H2θ2
TAED Tetraacetyl ethylene diamine. NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt. Photoactivated Bleach Sulfonated zinc phtalocyanine encapsulated in dextrin soluble polymer.
Protease Proteolytic enzyme described hereinbefore.
Amylase Amylolytic enzyme described hereinbefore.
Lipase Lipolytic enzyme described hereinbefore.
Cellulase Cellulytic enzyme described hereinbefore.
CMC Sodium carboxymethyl cellulose.
HEDP lJ-hydroxyethane diphosphonic acid.
DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.
PVNO Poly(4-vinylpyridine)-N-Oxide . PVPVI Poly (4-vinylpyridine)-N-oxide/copolymer of vinyl-imidazole and vinyl-pyrrolidone.
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl. Brightener 2 Disodium 4,4'-bis(4-anilino-6-moφholino-1.3.5-triazin-2-yl) stilbene-2 : 2'-disulfonate .
Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100: 1.
Granular Suds 12% Silicone/silica, 18% stearyl alcohol,70% starch in
Suppressor granular form
SRP 1 Sulfobenzoyl or sodium isethionate end capped esters with oxyethylene oxy and terephtaloyl backbone.
SRP 2 Diethoxylated poly (1,2 propylene terephtalate) short block polymer.
Sulphate Anhydrous sodium sulphate. HMWPEO High molecular weight polyethylene oxide
Example I la lb Ic Id Ie If
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Polysaccharide 0.5 1 0.2 0.5 0.5 0.5
Volatile Perfume A(1) - — -- 0.1 — -
Substantive Perfume B(2) — — — — 0.03 —
Hydrophilic Perfume C(3) — - - - - 0.05
Polysorbate 60(4) - - — 0.2 0.1 —
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
(1) Perfume contains mainly ingredients having a boiling point of less than about 250°C.
(2) Perfume contains mainly ingredients having a boiling point of about 250°C or higher.
(3) Perfume contains mainly ingredients having a ClogP of about 3.0 or less.
(4) A mixture of stearate esters of sorbitol and sorbitol anhydride, consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide.
Example II
Da πb lie lid He πf
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% wt.%
Polysaccharide 1 2 0.5 1 1 1
Perfume A — - - - 1 —
Perfume B — - - 0.3 — —
Perfume C - - - - - 1.5
Polysorbate 60 - - - 0.5 1.5 1
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
Concentrated compositions of Examples Et are diluted with water to obtain usage compositions for, e.g., spraying, soaking, dipping, cellulosic fabrics.
Example HJ
Figure imgf000056_0001
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.%
Polysaccharide 1 2 0.5 1 1
LiBr 3 - ~ 2 2
Silicone Emulsion A(5) - 1.5 - - 2.0
D5 Volatile Silicone — - 0.5 0.5 -
Perfume A - - - - 0.03
Perfume B - - - 0.05 —
Perfume C 0.03 ~ - — -
Polysorbate 60 - - ~ 0.1 0.05
Silwet L-7602 — - - 0.5 -
Silwet L-7622 — - ~ - 0.3
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal.
(5) DC-2-5932 silicone microemulsion (25% active) from Dow Corning, with a particle size of about 24 nm, a cationic surfactant system, and a silicone with an internal phase viscosity of about 1,200 cps.
Example rv
Figure imgf000057_0001
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Polysaccharide 1 2 0.5 1 1 0.5
Copolymer A^ ' 0.4 - - — - 0.5
(7) Copolymer B ' — 0.5 - 0.3 — ~
Copolymer C^ ' — - 0.6 - 0.5 -
LiBr - - - 3 - 2
Silicone Emulsion A(5) — ~ - - 1.5 -
D5 Volatile Silicone — - - — - 0.5
Perfume A 0.06 - - — — 0.07
Perfume B ~ 0.03 - 0.03 - -
Perfume C - - 0.04 ~ 0.03 -
Polysorbate 60 0.1 0.1 0.03 0.1 0.1 0.1
Silwet L-7600 - - - 0.5 - ~
Silwet L-7602 - ~ - — - 0.7
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal. (5) DC-2-5932 silicone microemulsion (25% active) from Dow Coming, with a particle size of about 24 nm, a cationic surfactant system, and a silicone with an internal phase viscosity of about 1J00 cps.
(6) Acrylic acid/tert-butyl acrylate copolymer, with an approximate acrylic acid/tert-butyl acrylate weight ratio of about 25/75 and an average molecular weight of from about 70,000 to about 100,000.
(7) Acrylic acid/tert-butyl acrylate copolymer, with an approximate acrylic acid/tert-butyl acrylate weight ratio of about 35/65 and an average molecular weight of from about 60,000 to about 90,000.
(8) Acrylic acid tert-butyl acrylate copolymer, with an approximate acrylic acid/tert-butyl acrylate weight ratio of about 20/80 and an average molecular weight of from about 80,000 to about 110,000.
Example V
Va Vb Vc Vd Ve Vf
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Polysaccharide 1 2 0.5 1 1 0.5 Copolymer D (9) ' 0.4 ~ — - 2 0.25
Copolymer E^ ' - 0.5 — - - 0.25
Copolymer F^ ' - - 0.4 — -- —
Copolymer G - - - 0.5 - -
D5 Volatile Silicone - 0.25 — — - -
PDMS 10,000 cst - - - 0.3 — -
Silicone Emulsion B^ ' ~ -- 1 - 2 -
Perfume A 0.06 — - ~ - 0.07
Perfume B - 0.03 - 0.03 - -
Perfume C - - 0.04 — 0.5 ~
Polysorbate 60 0.1 0.1 -- 0.1 0.5 0.1
Neodol 23-3 - 0.25 - 0.2 - -
Neodol 25-3 - - 0.3 - 0.3 0.25
Silwet L-77 ~ 0.7 - 1 ~ -
Silwet L-7604 - - 0.5 - ~ 0.7
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal. (9) Acrylic acid/tert-butyl acrylate copolymer, with an approximate acrylic acid/tert-butyl acrylate weight ratio of about 23/77 and an average molecular weight of about 82,000.
(10) Sihcone-contammg copolymer having t-butyl acrylate/acryhc acid/ (polydimethylsiloxane macromer, 10,000 approximate molecular weight) monomer at an approximate 63/20/17 weight ratio, and of an average molecular weight of about 130,000.
(11) Sihcone-contammg copolymer having t-butylacrylate/acryhc acid/ (polydimethylsiloxane macromer, 10,000 approximate molecular weight) monomer at an approximate 65/25/10 weight ratio, and of average molecular weight of about 200,000.
(12) Sihcone-containmg copolymer having (N,N,N-tπmethylammonιoethyl methacrylate chloπde)/N,N-dιmethylacrylamιde/(PDMS macromer - 15,000 approximate molecular weight) at an approximate 40/40/20 weight ratio, and of average molecular weight of about 150,000.
(13) DC-1550 silicone microemulsion (25% active) from Dow Coming, with a particle size of about 50 nm, an aniomc/nomomc surfactant system, and a silicone with an internal phase viscosity of about 100,000 cps.
The composition of Example Ve is a concentrated composition, to be diluted for use.
Example VI
Via VIb Vie yjd Vie Vlf
Ingredients Wt% Wt% Wt% Wt% Wt% Wt% Polysacchande 1 2 0.5 1 1 0.5
HPBCD(14) 1 0.5 0.5 ..
RAMEB(15)
HPACDO6) 0.5 α-Cyclodextπn ~ - - - 0.5 0.5 b-Cyclodextπn - - - 0.5 - 0.5 ZnCl2 — 1.0 - 1.0 - 1
Silwet L-7657 — - - - 0.05 - Perfume C 0.1 0.07 0.05 - 0.1 0.05 Propylene glycol 0.06 - 0.05 - 0.03 - Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm HCl - to pH 4.5 - to pH 5 - to pH 4.5 Distilled water Bal. Bal. Bal. Bal. Bal. Bal
(14) Hydroxypropyl beta-cyclodextnn (15) Randomly methylated beta-cyclodextπn.
(16) Hydroxypropyl alpha-cyclodextπn.
Example VII
Vila Vllb Vπc Vlld vπe VOf
Ingredients Wt% Wt% Wt% Wt% Wt% Wt%
Polysacchaπde 1 2 0.5 1 1 0.5
HPBCD 1.0 - - — - -
RAMEB - 1.0 - - - -
Silwet L-7604 0.3 0.2 0.2 - — 0.1
Chlorhexidine 0.01 — — — — 0.005
Barquat 425θ(17) — — 0.03 — — —
Bardac 205θ(18) - - - 0.03 0.03 —
Perfume C 0.08 0.08 0.05 0.05 — ~
HCl to pH 4 — - - - -
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Distilled water Bal. Bal. Bal. Bal. Bal. Bal.
(17) Benzalkomum chloπde, 50% solution.
(18) Dioctyl dimethyl ammonium chloπde, 50% solution.
The compositions of Examples I to VII (diluted when appropπate) are sprayed onto clothing using, e.g., the TS-800 sprayer from Calmar, and allowed to evaporate off of the clothing.
The compositions of Examples I to VH (diluted when appropnate) are sprayed onto
® clothing, using a blue inserted Guala trigger sprayer, available from Berry Plastics Coφ. and a
® cylindrical Euromist π pump sprayer available from Seaquest Dispensing, respectively, and allowed to evaporate off of the clothing.
The compositions of Examples I to VH (diluted when appropπate) contained in rechargeable battery-operated Solo Spraystar sprayers are sprayed onto large surfaces of fabπc, such as several pieces of clothing, and allowed to evaporate off of these surfaces. The level of coverage is uniform and the ease and convenience of application is supeπor to conventional manually operated tπgger sprayers.
The compositions of Examples I to VII (diluted when appropπate) are used for soaking or dipping of fabπcs which are then optionally wrung or squeezed to remove excess liquid and subsequently dned. Followmg are Examples for πnse added fabπc care compositions in accordance with the present invention:
Example VE_
vπia vπib VIIIc vπid vπie
Ingredients Wt% Wt% Wt% Wt.% Wt%
Polysacchaπde 1 2 2 3 2
Fabπc softener A(19) 4.5 - - - -
Fabπc softener B(20) — 24 — — -
Fabnc softener C(21) — — 26 - —
Fabnc softener D(22) — — — 28 28
Fabnc softener E(23) 3.4 - — — -
1 J-Hexanediol — — 18 - -
2-Ethyl-l,3-hexanedιol - - - 6 -
Neodol 91-8 — - - 5 3
Pluromc L-350 - - - 1
Hexylene glycol - — — — 3
Hexylene glycol (from - - — 2.5 2.5 softener active)
Ethanol (from softener - 4.2 4.6 2.3 2.3 active)
Perfume B 0.3 1.3 1.3 2 1.2
Tenox 6 antioxidant 0.02 0.04 0.04 0.04 0.04
CaCl2 0.05 0.4 0.5 — 2
MgCl2 - ~ — 1.6 -
HCl to pH 6 to pH 3.5 to pH 3.5 to pH 3 to pH 3
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized water and other Bal. Bal. Bal. Bal. Bal. minor ingredients
(19) Dι(hydrogenated tallowyl) dimethyl ammonium chloπde/hydrogenated tallowyl tπmethyl ammonium chlonde blend of about 83:17 weight ratio.
(20) Dι(acyloxyethyl) dimethyl ammonium chloπde wherem the acyl group is deπved from soft tallow fatty acids and with a diester-to-monoester weight ratio of about 11: 1. (21) Dι(acyloxyethyl) dimethyl ammonium chloπde wherem the acyl group is deπved from partially hydrogenated canola fatty acids and with a diester-to-monoester weight ratio of about 11:1.
(22) Dι(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate wherem the acyl group is deπved from partially hydrogenated canola fatty acids.
(23) 1 -Tallow(amιdoethyl)-2-tallowιmιdazolme.
Example IX
IXa IXb _Xc IXd IXe IXf
Ingredients Wt% Wt% Wt% Wt.% Wt% Wt%
Polysacchaπde 1 2 2 2 3 3
Fabnc softener A(19) 4.5 - — - - —
Fabπc softener B(20) — 22 25 25 — —
Fabπc softener E 23) 3.4 — — — — —
PVP K-15(24) 1 3 — — 5 —
PVNO(25) — - 1 - — —
Cellulase(26) - - — 1 - 2
Perfume B 0.4 1.3 1.3 1.3 2 -
Perfume C - - - - - 1.5
Polysorbate 60 - - — — 5 1
HCl to pH 5 to pH to pH to pH — —
3.5 3.5 3.5
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized water and minor Bal. Bal. Bal. Bal. Bal. Bal. ingredients
(19) Dι(hydrogenated tallowyl) dimethyl ammonium chlonde/hydrogenated tallowyl tnmethyl ammonium chloπde blend of about 83:17 weight ratio.
(20) Dι(acyloxyethyl) dimethyl ammonium chloπde wherem the acyl group is denved from soft tallow fatty acids and with a diester-to-monoester weight ratio of about 11:1.
(23) 1 -Tallow(amιdoethyl)-2-tallowιmιdazolme.
(24) Polyvmylpyrrohdone with an average molecular weight of about 10,000.
(25) Poly(4-vmylpyndme-N-oxιde) with an average molecular weight of about 25,000.
(26) The cellulase consists essentially of a homogeneous endoglucanase component, which is lmmunoreactive with an antibody raised against a highly punfied 43 kD cellulase denved from Humicola insolens, DMS 1800, or which is homologous to said 43 kD endoglucanase; the cellulase solution used provides about 5,000 CEVU's per gram. Followmg are Examples for laundry detergent fabπc care compositions m accordance with the present invention:
Example X
Xa Xb
Ingredients Wt% Wt.%
LAS 8 8
C25E3 3.4 3.4
QAS - 0.8
Zeolite A 17 17
Carbonate 13 24
Silicate 1.4 3
Sulfate 25 15
PB4 9 8
TAED 1.5 1.5
DETPMP 0J5 0.25
HEDP 0.3 0.3
Polysacchande 3 5
Protease 26 ppm 26 ppm
MA/AA 0.3 0.3
CMC 0.2 0.2
Photoactivated Bleach - 10 ppm
Bnghtener 0.09 0.09
Perfume 0.3 0.3
Silicone antifoam 0.5 0.5
Moisture and Miscellaneous Balance Balance
Example XI
Nil bleach-contammg laundry detergent fabπc care compositions of particular use in the washing of colored clothing:
XIa Xib
Ingredients Wt% Wt.% Blown Powder
Zeolite A 14 14
Sodium sulfate — 13 LAS 2.8 3
DETPMP 0.4 0.5
CMC 0.4 0.4
MA/AA 3.8 4
Agglomerates
LAS 5.5 5
TAS 3 2
Silicate 4 4
Zeolite A 9 13
Carbonate 9 7
Spray On
Perfume 0J 0J
C45E7 4 4
C25E3 1.8 1.8
Dry additives
Citrate 10 -
Bicarbonate 6.5 3
Carbonate 7.5 5
PVPVI/PVNO 0.5 0.5
Polysaccharide 3 2
Protease 0.026 0.016
Lipase 0.009 0.009
Amylase 0.005 -
Cellulase 0.006 0.006
Silicone antifoam 4 3
Moisture and Miscellaneous Balance Balance
Example XII imples of liquid detergent fabric care compositions according to the present i nventic
Figure imgf000064_0001
Ingredients wt% Wt.% Wt% Wt% Wt%
LAS 9 8 22 —
C25AS 4 2 9 12
C25E3S 1 - 3 3.5
C25E7 6 12 2.5 3.5
TFAA .. 4.5 7.5 QAS ~ - — 3 —
TPKFA 2 12 2 ~ 5.5
Canola fatty acids - ~ 5 - 4
Citric 2 1 1.5 1 1
Dodecenyl/ tetradecenyl 10 - ~ 14 ~ succimc acid
Oleic acid 4 1 - 1 -
Ethanol 4 6 2 6 2
1,2 Propanediol 4 2 6 6 10
Mono Ethanol Amine - - 5 — 8
Tπ Ethanol Amine ~ 7 - - —
NaOH (pH) 8 7.5 7.5 8 8
Ethoxylated tetraethylene 0.5 0.5 0.2 - 0.3 pentamine
DETPMP 1 0.5 1 2 -
SRP 2 0.3 0.3 0.1 - 0.1
PVNO - - — ~ 0.1
Polysacchande 1 2 2 3 1
Protease 50 ppm 40 ppm 30 ppm 0.08 60 ppm
Lipase - - 2 ppm - 30 ppm
Amylase 20 ppm 50 ppm 40 ppm 20 ppm 50 ppm
Cellulase - - 1 ppm - 4 ppm
Figure imgf000065_0001
Na formate - 1 - — -
Ca chlonde - - 0.01 — -
Bentomte clay - - - 3.5 -
Suspending clay SD3 - - - 0.6 —
Water and Miscellaneous Bal. Bal. Bal. Bal. Bal.
Example X__ Examples of syndet bar fabnc detergent fabπc care compositions in accord with the present invention:
XlVa XlVb
Ingredients Wt% Wt.%
C26 AS 18 18
CFAA 5 5 LAS (Cl 1-13) 10 10
Sodium carbonate 22 25
Sodium pyrophosphate 6 6
STPP 6 6
Zeolite A 5 5
CMC 0.2 0.2
Polyacrylate (MW 1400) 0.2 0.2
Coconut monoethanolamide 5 5
Polysaccharide 5 3
Amylase — 0.02
Protease - 0.3
Perfume 0.2 0.2
Brightener 0.1 0.1
CaS04 1 1
MgS04 1 1
Water 4 4
Filler* Balance Balance
* Can be selected from convenient materials such as CaCθ3, talc, clay (Kaolinite, Smectite), silicates, and the like.
Example XIV
Examples of syndet bar fabric detergent fabric care compositions in accord with the present invention:
XlVa XlVb
Ingredients Wt% Wt.%
C26 AS 20.00 20.00
CFAA 5.0 5.0
LAS (Cl 1-13) 10.0 10.0
Sodium carbonate 25.0 25.0
Sodium pyrophosphate 7.0 7.0
STPP 7.0 7.0
Zeolite A 5.0 5.0
CMC 0.2 0.2 Polyacrylate (MW 1400) 0.2 0.2
Coconut monoethanolamide 5.0 5.0
Polysaccharide 3 5
Amylase 0.01 0.02
Protease 0.3 -
Brightener, perfume 0.2 0.2
CaS04 1.0 1.0
MgS04 1.0 1.0
Water 4.0 4.0
Filler* : balance to 100%
Example XV The following detergent formulations, according to the present invention, are prepared where XVa and XVc are phosphorus-containing detergent compositions, and XVb is a zeolite-containing detergent composition:
XVa XVb XVc
Blown Powder: STPP 24.0 - 24.0
Zeolite A - 24.0 - C45AS 9.0 6.0 13.0 MA AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 - - Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0
DETPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3
Dry additives: Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02
Polysacchaπde 1 2 1
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 -
Amylase 0.002 - 0.001
Dry mixed sodium sulfate 3.0 3.0 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/htre) 630 670 670
Example XVI
The following nil bleach-containing detergent formulations of particular use in the washing of colored clothing, according to the present invention are prepared:
XVIa XVIb XVIc
Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 5.0 LAS 3.0 3.0
DETPMP 0.4 0.5 CMC 0.4 0.4 MA/AA 4.0 4.0
Agglomerates C45AS 11.0 LAS 6.0 5.0 - TAS 3.0 2.0 - Silicate 4.0 4.0 - Zeolite A 10.0 15.0 13.0 CMC - - 0.5 MA AA - - 2.0 Carbonate 9.0 7.0 7.0
Spray On Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0
Dry additives MA AA - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Polysaccharide 2 2 3
Protease 0.026 0.016 0.047
Lipase 0.009 — 0.009
Amylase 0.005 0.005 -
Cellulase 0.006 0.006 -
Silicone antifoam 5.0 5.0 5.0
Dry additives Sodium sulfate 0.0 9.0 0.0 Balance (Moisture and 100.0 100.0 100.0
Miscellaneous) Density (g/litre) 700 700 700
Example XVII The following liquid detergent formulations, according to the present invention are prepared: xvπa xvπb xviic xvπ xvπ xvπ xvπg xvπh d e f
LAS 1 100..00 1 133..00 9 9..00 - - 25.0
C25AS 4.0 1.0 2.0 10.0 13.0 18.0 15.0
C25E3S 1.0 - - 3.0 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - 4.0 4.0
TFAA - - - 4.5 6.0 8.0 8.0
QAS - . . . 3.0 1.0 - -
TPKFA 2.0 . 13.0 2.0 15.0 7.0 7.0
Rapeseed fatty _ _ _ 5.0 _. 4.0 4.0 acids Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Dodecenyl/ 12 0 10.0 - - 15.0 - - - tetradecenyl succimc acid
Oleic acid 4.0 2.0 1.0 - 1.0 - - -
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1 ,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Mono Ethanol - - - 5.0 - - 9.0 9.0
Amine
Tπ Ethanol - - 8 - - - - -
Amine
NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3 tetraethylene pentamine
DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 -
SRP 2 0J - 0.3 0.1 - - 0.2 0.1
PVNO - - - - - - - 0.10
Polysacchande 0.01 1.0 10.0 2 3 5 5 1.0
Protease .005 .005 .004 .003 0.08 .005 .003 .006
Lipase - .002 - .0002 - - .003 .003
Amylase .002 ~ - .004 .002 .008 .005 .005
Cellulase - - - .0001 - - .0004 .0004
Bone acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0 - - - - -
Ca chlonde - 0.015 - 0.01 - - - -
Bentomte clay - - - - 4.0 4.0 - -
Suspending clay - - - - 0.6 0.3 - -
SD3
Balance 100 100 100 100 100 100 100 100
Moisture and
Miscellaneous Example XVDJ Granular Fabric Cleaning Composition
Example No.
Component A B C D Polysaccharide 0.5 0.2 1 2
Protease 0.10 0.20 0.03 0.05
C 13 linear alkyl benzene sulfonate 22.00 22.00 22.00 22.00
Phosphate (as sodium 23.00 23.00 23.00 23.00 tripolyphosphates) Sodium carbonate 23.00 23.00 23.00 23.00 Sodium silicate 14.00 14.00 14.00 14.00 Zeolite 8.20 820 8.20 8 JO
Chelant (diethylaenetriamine- 0.40 0.40 0.40 0.40 pentaacetic acid) Sodium sulfate 5.50 5.50 5.50 5.50
Water balance to 100%
Example XIX Granular Fabric Cleaning Composition
Example No.
Component A B C__ D
Polysaccharide 1 3 5 0.4
Protease 0.10 0.20 0.03 0.05
C]2 alkyl benzene sulfonate 12.00 12.00 12.00 12.00
Zeolite A (1-10 micrometer) 26.00 26.00 26.00 26.00 Cl2"Cl4 secondary (2,3) alk yl sulfate, 5.00 5.00 5.00 5.00
Na salt Sodium citrate 5.00 5.00 5.00 5.00 Optical brightener 0.10 0.10 0.10 0.10 Sodium sulfate 17.00 17.00 17.00 17.00 Fillers, water, minors balance to 100%
Example XX
Granular Fabric Cleaning Compositions Components Example No.
A B
Linear alkyl benzene sulphonate 11.4 10.70
Tallow alkyl sulphate 1.80 2.40
Cl4-15 alkyl sulphate 3.00 3.10
Cl4-15 alcohol 7 times ethoxylated 4.00 4.00
Tallow alcohol 11 times ethoxylated 1.80 1.80
Dispersant 0.07 0.1
Silicone fluid 0.80 0.80
Tnsodium citrate 14.00 15.00
Citric acid 3.00 2.50
Zeolite 32.50 32.10
Maleic acid acrylic acid ι copolymer 5.00 5.00
Diethylene tnamme penta methylene 1.00 0.20 phosphomc acid
Polysacchande 1 3
Protease 0.1 0.01
Lipase 0J6 0.40
Amylase 0.30 0.30
Sodium silicate 2.00 2.50
Sodium sulphate 3.50 5 JO
Polyvmyl pyrrolidone 0.30 0.50
Perborate 0.5 1
Phenol sulphonate 0.1 0.2
Peroxidase 0.1 0.1
Minors Up to 100 Up to 100
Example XXI
Granular Fabπc Cleaning Compositions
Example No.
Components A B
Sodium linear Cj2 alkyl benzene-sulfonate 6.5 8.0
Sodium sulfate 15.0 18.0
Zeolite A 26.0 22.0
Sodium nitπlotnacetate 5.0 5.0
Polyvmyl pyrrolidone 0.5 0.7 Tetraacetylethylene diamine 3 0 3 0
Boric acid 4.0 -
Perborate 0.5 1
Phenol sulphonate 0.1 0.2
Polysacchaπde 2 0.5
Protease 0.02 0.05
Fillers (e.g., silicates; carbonates; perfumes; water) Up to 100 Up to 100
Example XXII
Compact Granular Fabπc Cleaning Composit ion
Components Weight %
Alkyl Sulphate 8.0
Alkyl Ethoxy Sulphate 2.0
Mixture of C25 and C45 alcohol 3 and 7 times ethoxylated 6.0
Polyhydroxy fatty acid amide 2.5
Zeolite 17.0
Layered silicate/citrate 16.0
Carbonate 7.0
Maleic acid acrylic acid copolymer 5.0
Soil release polymer 0.4
Carboxymethyl cellulose 0.4
Poly (4-vmylpyndme) -N-oxide 0.1
Copolymer of vmyhmidazole and vmylpyrrohdone 0.1
PEG2000 0.2
Polysacchaπde 1
Protease 0.03
Lipase 0.2
Cellulase 0.2
Tetracetylethylene diamine 6.0
Percarbonate 22.0
Ethylene diamine disuccmic acid 0.3
Suds suppressor 3.5
Dιsodιum-4,4'-bιs (2-moφholmo -4-anιhno-s-tπazm-6- 0.25 ylamino) stιlbene-2J'-dιsulphonate
Dιsodιum-4,4'-bιs (2-sulfostyπl) biphenyl 0.05
Water, Perfume and Minors Up to 100 Example : xxm
Granular Fabric Cleaning Composition
Component Weight %
Linear alkyl benzene sulphonate 7.6
Cl6"Cl8 alkyl sulfate 1.3
Cl4-15 alcohol 7 times ethoxylated 4.0
Coco-alkyl-dimethyl hydroxyethyl ammonium chloride 1.4
Dispersant 0.07
Silicone fluid 0.8
Trisodium citrate 5.0
Zeolite 4A 15.0
Maleic acid acrylic acid copolymer 4.0
Diethylene triamine penta methylene phosphonic acid 0.4
Perborate 15.0
Tetraacetylethylene diamine 5.0
Smectite clay 10.0
Poly (oxyethylene) (MW 300,000) 0.3
Polysaccharide 0.8
Protease 0.02
Lipase 0.2
Amylase 0.3
Cellulase 0.2
Sodium silicate 3.0
Sodium carbonate 10.0
Carboxymethyl cellulose 0.2
Brighteners 0.2
Water, perfume and minors Up to 100 Example XXIV
Granular Fabric Cleaning Composition
Component Weight %
Linear alkyl benzene sulfonate 6.92
Tallow alkyl sulfate 2.05
■Cl4"15 alcohol 7 times ethoxylated 4.4
Cl2-15 -^- eth°χy sulfate - 3 times ethoxylated 0J6
Zeolite 20.2
Citrate 5.5
Carbonate 15.4
Silicate 3.0
Maleic acid acrylic acid copolymer 4.0
Carboxymethyl cellulase 0.31
Soil release polymer 0J0
Polysaccharide 0.5
Protease 0J
Lipase 0J6
Cellulase 0J3
Perborate tetrahydrate 11.64
Perborate monohydrate 8.7
Tetraacetylethylene diamine 5.0
Diethylene tramine penta methyl phospt ionic acid 0.38
Magnesium sulfate 0.40
Brightener 0.19
Perfume, silicone, suds suppressors 0.85
Minors Up to 100
Example XXV Granular Fabric Cleaning Composition Component B C
Base Granule Components
LAS/AS/AES (65/35) 9.95
LAS/AS/AES (70/30) - 12.05 7.70 Alumino silicate 14.06 15.74 17.10 Sodium carbonate 11.86 12.74 13.07 Sodium silicate 0.58 0.58 0.58 NaPAA Solids 2J6 2.26 1.47 PEG Solids 1.01 1.12 0.66 Brighteners 0.17 0.17 0.11 DTPA - - 0.70 Sulfate 5.46 6.64 4.25
DC- 1400 Deaerant 0.02 0.02 0.02 Moisture 3.73 3.98 4.33 Minors 0.31 0.49 0.31 B.O.T. Spray-on
Nonionic surfactant 0.50 0.50 0.50
Agglomerate Components LAS/AS (25/75) 11.70 9.60 10.47 Alumino silicate 13.73 11.26 12.28 Carbonate 8.11 6.66 7.26 PEG 4000 0.59 0.48 0.52 Moisture Minors 4.88 4.00 4.36 Functional Additives Sodium carbonate 7.37 6.98 7.45 Perborate 1.03 1.03 2.56 TAED - 1.00 - NOBS - - 2.40
Soil release polymer 0.41 0.41 0.31 Polysaccharide 1 0.75 3 Cellulase 0.33 0.33 0.24 Protease 0.1 0.05 0.15 AE-Flake 0.40 0.40 0.29 Liquid Spray-on Perfume 0.42 0.42 0.42
Noionic spray-on 1.00 1.00 0.50 Minors Up to 100
Example XXVI
Granular Fabric Cleaning Composition
Figure imgf000077_0001
Figure imgf000078_0001
Example XXVII Granular Fabric Cleaning Composition
Figure imgf000079_0001
Figure imgf000080_0001
Example XXVU The following granular laundry detergent compositions XXVIH A-C are of particular utility under European machine wash conditions were prepared in accord with the invention:
Figure imgf000080_0002
Figure imgf000081_0001
Figure imgf000082_0001
Example XXIX The following formulations are examples of compositions in accordance with the invention, which may be in the form of granules or in the form of a tablet.
Figure imgf000082_0002
Figure imgf000083_0001
Example XXX Granular laundry detergent compositions XXX A-E are of particular utility under Japanese machine wash conditions and are prepared in accordance with the invention:
Figure imgf000083_0002
Figure imgf000084_0001
Example XXXI Liquid Fabric Cleaning Compositions
Example No.
Component A B C D
Polysaccharide 0.5 1 2 5 1
Protease 0.05 0.03 0.30 0.03 0.10
C* 2" C*i4 alkyl sulfate, Na 20.00 20.00 20.00 20.00 20.00
2-Butyl octanoic acid 5.00 5.00 5.00 5.00 5.00
Sodium citrate 1.00 1.00 1.00 1.00 1.00
C*ιo alcohol ethoxylate (3) 13.00 13.00 13.00 13.00 13.00
Monethanolamine 2.50 2.50 2.50 2.50 2.50
Water/propylene glvcol/ethanol (100:1 : 1) balance to 100%
Examples XXXII Liquid Fabric Cleaning Compositions
Example No.
Component A B
C*i2-14 alkenyl succinic acid 3.0 8.0
Citric acid monohydrate 10.0 15.0
Sodium C 12-15 alkyl su lphate 8.0 8.0
Sodium sulfate of C12-15 alcohol 2 times ethoxylated - 3.0
Cl2-15 alcohol 7 times 1 ethoxylated - 8.0
Diethylene triamine penta (methylene phosphonic acid) 0.2 -
Oleic acid 1.8 -
Ethanol 4.0 4.0
Propanediol 2.0 2.0
Polysaccharide 1 2
Protease 0.01 0.02
Polyvinyl pyrrolidone 1.0 2.0
Suds suppressor 0J5 0J5
NaOH up to 1 pH 7.5
Perborate 0.5 1
Phenol sulphonate 0J 0J
Peroxidase 0.4 0J
Waters and minors up to 100 %
Example XXXiπ
Liquid Fabric Cleaning Compositions
Example No.
Component 40
NaLAS (100%am) 16 Neodol 21.5
Citrate 6.8
EDDS 1.2
Dispersant 1.3
Perborate 12
Phenolsulfonate ester of N- nonanoyl-6- -aminocaproic acid 6
Polysaccharide 0.5
Protease (% pure er lzyme) 0.03
Amylase 0.40
Cellulase 0.03
Solvent (BPP) 18.5
Polymer 0J
Carbonate 10
FWA 15 0.2
Ti02 0.5
PEG 8000 0.4
Perfume 1.0-1.2
Suds suppressor 0.06
Waters and minors up to 100%
Example XXXIV Liquid Fabric Cleaning Compositions
Example No.
Component A B
D1 H20 38.63 -
MEA 0.48 9.0
NaOH 4.40 1.0
Pdiol 4.00 10.0
Citric acid 2.50 2.0
Sodium sulfate 1.75 -
DTPA 0.50 1.0
FWA Premix (Br 15/MEA/Nl 23-9) 0.15 0.15
Na C25AE1.80S 23.50 -
AE3S (H) - 4.0
C11.8HLAS 3.00 14.0
Neodol 2.00 6.0
EtOH 0.50 2.0
Ca*Formate 0.10 0.1
Borax premix (Borax MEA/Pdiol/CitricAcid) 2.50 -
Boric acid - 1.0
CIO APA 1.50 -
TEPA 105 1.20 -
FA C12-18 5.00 -
Neptune LC 0.50 -
Dye 0.0040 0.0015
Polysaccharide 1 0.7
Cellulase 0.053 0.2
Amylase 0.15 0.2
Protease 0.1 0.1
DC 2-3597 0.12 0.2
Rapeseed FA 6.50 4.0
Waters and minors up to 100 % Example XXXV
Liquid Fabπc Cleaning Composition
Component XXXV
NaOH 5.50
Pdiol 6.90
Citnc acid 1.50
DTPA 1.50
FWA Premix (Br 15/MEA/Nl 23-9) 0.15
AE3S (H) 2.50
LAS (H) 13.0
Neodol 2.00
EtOH 3.50
Ca*Formate 0J0
Boric acid 1.00
Clay 4.00
Polysacchande 2
Amylase 0.15
Protease 0.02
Fatty Acid 16.50
Waters and minors up to 100 %
Example XXXVI
Liquid Fabric Cleaning Composition
Liquid fabπc cleaning composition of particular utility under Japanese machine wash conditions is prepared in accordance with the invention:
Figure imgf000089_0001
Figure imgf000090_0001
Example XXXVH Liquid Fabπc Cleaning Composition Liquid fabric cleanmg composition of particular utility under Japanese machine wash conditions and for fine fabπcs is prepared in accordance with the invention:
Figure imgf000091_0001
Example XXXVffl Bar Fabπc Cleaning Compositions
Example No.
Component A B C D
Polysaccharide 0.5 2 5 3
Protease 0.3 0.05 0.1 0.02
Cl2"Cl6 alkyl sulfate, Na 20.0 20.0 20.0 20.00
Cl2"Cl4 N-methyl glucamide 5.0 5.0 5.0 5.00
C* *[-Ci3 alkyl benzene sulfonate, Na 10.0 10.0 10.0 10.00
Sodium pyrophosphate 7.0 7.0 7.0 7.00
Sodium tπpolyphosphate 7.0 7.0 7.0 7.00
Zeolite A (OJ-JOμ) 5.0 5.0 5.0 5.00
Carboxymethylcellulose 0.2 0.2 0.2 0.20
Polyacrylate (MW 1400) 0.2 0.2 0.2 0.20
Coconut monethanolamide 5.0 5.0 5.0 5.00
Bπghtener, perfume 0.2 0.2 0.2 0.20 CaS04 1.0 1.0 1.0 1.00
MgS04 1.0 1.0 1.0 1.00
Water 4.0 4.0 4.0 4.00 Filler* balance to 100%
*Can be selected from convenient matenals such as CaCOβ, talc, clay, silicates, and the like.
The compositions of the present invention can be suitably prepared by any process chosen by the formulator, non-hmitmg examples of which are descπbed in U.S. 5,691,297 Nassano et al., issued November 11, 1997; U.S. 5,574,005 Welch et al., issued November 12, 1996; U.S. 5,569,645 Dmniwell et al., issued October 29, 1996; U.S. 5,565,422 Del Greco et al., issued October 15, 1996; U.S. 5,516,448 Capeci et al, issued May 14, 1996; U.S. 5,489,392 Capeci et al., issued February 6, 1996; U.S. 5,486,303 Capeci et al., issued January 23, 1996 all of which are mcoφorated herein by reference.
In addition to the above examples, the cotyledon extracts of the present invention can be formulated into any suitable laundry detergent composition, non-hmitmg examples of which are descπbed in U.S. 5,679,630 Baeck et al., issued October 21, 1997; U.S. 5,565,145 Watson et al, issued October 15, 1996; U.S. 5,478,489 Fredj et al, issued December 26, 1995; U.S. 5,470,507 Fredj et al., issued November 28, 1995; U.S. 5,466,802 Panandiker et al., issued November 14, 1995; U.S. 5,460,752 Fredj et al., issued October 24, 1995; U.S. 5,458,810 Fredj et al., issued October 17, 1995; U.S. 5,458,809 Fredj et al., issued October 17, 1995; U.S. 5,288,431 Huber et al., issued February 22, 1994 all of which are incoφorated herein by reference. Having described the invention in detail with reference to preferred embodiments and the examples, it will be clear to those skilled in the art that various changes and modifications may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

WHAT IS CLAIMED IS
1 A starch-free treating composition for treating a fabπc m need of treatment compnsmg a polysaccharide having a degree of polymenzation of over 40, preferably said polysacchaπde has a β-hnked backbone.
2. The composition according to Claim 1 wherem said polysacchande has a degree of polymerization m the range of from 50 to 100,000, preferrably from 500 to 50,000.
3. The composition according to Claim 1 wherem said polysacchande has a molecular weight in the range of from 10,000 to 10,000,000, preferably from 50,000 to 1,000,000, most preferably from 50,000 to 500,000.
4. The composition according to Claim 1 wherem the polysacchande is selected from the group consisting of gums, arabinans, galactans, seeds and mixtures thereof, preferably said polysacchaπde is selected from the group consisting of tamannd gum, guar gum, locust bean gum, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psylhum seed, qumce seed, xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, chitin, hydroxyalkyl cellulose, arabman, de- branched arabman, arabmoxylan, galactan, pectic galactan, galactomannan, glucomannan, hchenan, mannan, pachyman, rhamnogalacturonan, acacia gum, agar, alginates, chitosan, clavan, hyaluronic acid, hepann, lnuhn, cellodextπns, and mixtures thereof, most preferably said polysacchande is a xyloglucan polymer, wherein said xyloglucan polymer is obtained from tamarind seed polysacchaπdes.
5 The composition according to Claim 4 wherein said xyloglucan polymer has a molecular weight in the range of from 10,000 to 1,000,000, preferably from 50,000 to 200,000.
6 The composition according to Claim 1 wherem said polysacchaπde is present in said treating composition at a level of from 0.01% to 25% by weight of the treating composition, preferably at a level of from 0J%> to 10%> by weight of the treating composition.
7 The composition according to Claim 1 wherein said composition further compnses one or more ingredients selected from the group consisting of: surfactants, builders, bleaching agents, dye transfer inhibiting agents, chelants, dispersants, polysacchaπdes, softening agents, suds suppressors, earners, enzymes, enzyme stabilizing systems, polyacids, soil removal agents, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bactencides, dyes, perfumes, bπghteners, anti-encrustation agents and mixtures thereof
8. The composition according to Claim 1 wherem said composition further compnses a deπvatized polysacchaπde, wherein said deπvatized polysacchande is preferably selected from the group consisting of ammo alginates, 0-methyl-(N-lJ2-dodecanedιamme) cellulose, biotin hepaπn, carboxymethylated dextran, guar polycarboxyhc acid, carboxymethylated locust bean gum, caroxymethylated xanthan, carboxymethylated pachyman, chitosan phosphate, chitosan phosphate sulfate, diethylammoethyl dextran, dodecylamide alginate and mixtures thereof
9. The composition according to Claim 1 wherem said composition further compπses an ohgosacchande, wherein said ohgosacchande is preferably selected from the group consisting of ohgosacchandes with a degree of polymenzation (DP) of less than 20 compnsmg one or more monosacchandes selected from the group consisting of glucose, fructose, galactose, xylose, mannose, arabmose, rhamnose, nbose, lyxose, allose, altrose, gulose, idose, talose, and/or their denvatives.
10. A method for treating a fabnc in need of treatment compnsmg contacting said fabπc with an effective amount of a polysacchande-contammg treating composition, wherein the polysacchande has a degree of polymenzation over 40, such that said composition treats said fabnc, preferably said fabπc is selected from the group consisting of natural fibers, most preferably said fabnc is selected from the group consisting of cotton, rayon, ramie, jute, flax, lmen, polynosic-fibers, Lyocell, poly/cotton, other cotton blends and mixtures thereof.
11. The method according to Claim 10 wherein said fabnc is treated such that said garment is imparted color appearance and or pill prevention and/or abrasion resistance and/or wπnkle resistance and or shnnkage resistance properties.
12. The method according to Claim 10 wherem said polysacchande-contammg treating composition further includes one or more cleaning adjunct matenals selected from the group consisting of surfactants, builders, bleaching agents, dye transfer inhibiting agents, chelants, dispersants, polysacchandes, softening agents, suds suppressors, earners, enzymes, enzyme stabilizing systems, polyacids, soil removal agents, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bacteπcides, dyes, perfumes, bπghteners and mixtures thereof.
13. The method according to Claim 10 wherein said polysacchande-contammg treating composition is applied to said fabπc by a spray dispenser.
14 A treated fabπc made by the method according to Claim 10
15 A treating composition for treating a fabric m need of treatment compnsmg: a) a polysacchande having a degree of polymenzation of over 40; and b) one or more cleaning adjunct materials selected from the group consisting of builders, bleaching agents, dye transfer inhibiting agents, chelants, dispersants, polysacchandes, softening agents, suds suppressors, earners, enzymes, enzyme stabilizing systems, polyacids, soil removal agents, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bactencides, dyes, perfumes, bπghteners and mixtures thereof.
16. The composition according to Claim 15 wherem said composition further compπses a surfactant.
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