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WO2000024856A1 - Composition d'entretien des textiles et procede correspondant - Google Patents

Composition d'entretien des textiles et procede correspondant Download PDF

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Publication number
WO2000024856A1
WO2000024856A1 PCT/US1999/024942 US9924942W WO0024856A1 WO 2000024856 A1 WO2000024856 A1 WO 2000024856A1 US 9924942 W US9924942 W US 9924942W WO 0024856 A1 WO0024856 A1 WO 0024856A1
Authority
WO
WIPO (PCT)
Prior art keywords
fabric
composition
fabric care
mixtures
weight
Prior art date
Application number
PCT/US1999/024942
Other languages
English (en)
Inventor
Mary Vijayarani Barnabas
Toan Trinh
Freddy Arthur Barnabas
Michael Stanford Showell
Mark Richard Sine
Johan Smets
Helen Bernardo Tordil
Todd Michael Wernicke
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 EP99956654A priority Critical patent/EP1123374B1/fr
Priority to US09/807,367 priority patent/US7012053B1/en
Priority to DE69929233T priority patent/DE69929233T2/de
Priority to JP2000578411A priority patent/JP4873781B2/ja
Priority to AT99956654T priority patent/ATE314451T1/de
Priority to BR9915536-2A priority patent/BR9915536A/pt
Priority to AU13211/00A priority patent/AU1321100A/en
Priority to CA2346771A priority patent/CA2346771C/fr
Publication of WO2000024856A1 publication Critical patent/WO2000024856A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/162—Organic compounds containing Si
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/362—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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

Definitions

  • the present invention relates to fabric care compositions, methods, and articles of manufacture for treating fabrics in order to improve various properties of fabrics, in particular, reduction and/or removal of unwanted wrinkles; fabric wear reduction; fabric pill prevention and/or reduction; and/or fabric color maintenance and/or fading reduction.
  • Other benefits that consumers value include fabric longevity, e.g., fabric wear prevention or reduction, shrinkage prevention or reduction, and the like.
  • These benefits can be more or less provided via textile finishing compositions that are applied to fabrics in textile mills and/or garment manufacturing facilities, but it is preferable that these benefits are provided via simple and convenient consumer compositions, methods and products, to be applied in the consumer's home.
  • These consumer compositions and products are preferably safe, and do not involve complicated and/or unsafe treatments and/or applications. Desirably they comprise treatments that are familiar to the consumers, such as spraying, soaking, adding to the wash cycle, adding to the rinse cycle, and/or adding to the drying cycle.
  • the present invention relates to compositions, methods, and articles of manufacture that provide some important fabric care benefits, including at least one of the following: wrinkle removal and/or reduction, fabric strengthening, fabric wear resistance and/or reduction, fabric pilling prevention and/or reduction, fabric color maintenance and/or fading reduction, color restoration, fabric soiling reduction, fabric shape retention, and/or fabric shrinkage reduction.
  • the present invention relates to fabric care compositions, fabric care methods, and articles of manufacture that contain such fabric care composition.
  • the fabric care composition comprises:
  • said fabric care polysaccharide comprises polysaccharides with globular structure and with molecular weight of from about 5,000 to about 500,000; branched versions of said polysaccharides; derivatised versions of said polysaccharides; substituted versions of said polysaccharides; and mixtures thereof;
  • adjunct fabric care oligosaccharide selected from the group consisting of oligosaccharides, oligosaccharide mixtures, substituted versions of said oligosaccharides and/or mixtures, derivatised versions of said oligosaccharides and/or mixtures, and mixtures thereof;
  • adjunct wrinkle control agent preferably selected from the group consisting of fiber lubricant, fabric shape retention polymer, lithium salts, and mixtures thereof;
  • (E) optionally, an effective amount to absorb malodor, of odor control agent
  • (G) optionally, an effective amount, to kill, or reduce the growth of microbes, of antimicrobial active
  • composition optionally, an effective amount to provide improved antimicrobial action of aminocarboxylate chelator; (I) optionally, an effective amount of antimicrobial preservative, in addition to, or in place of said antimicrobial active; and (J) optionally, an aqueous carrier; said composition optionally being essentially free of any material that would soil or stain fabric under usage conditions.
  • a preferred fabric care composition for treating fabric comprises an effective amount of said fabric care polysaccharide with a globular structure and is applied to fabric and/or an entire fabric garment via, e.g., dipping, soaking, misting and/or spraying processes followed by a drying step.
  • the present invention also relates to the fabric care compositions incorporated into a spray dispenser and/or mist generator, to create an article of manufacture that can facilitate treatment of fabric articles and/or entire fabric garments and/or surfaces with said compositions containing fabric care polysaccharide with globular structure and other optional ingredients at a level that is effective, yet is not discernible when dried on the surfaces.
  • aqueous or solid, preferably powder, fabric care compositions for treating fabric in the rinse step comprising an effective amount of fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharide, fabric softening actives, perfume, and mixtures thereof.
  • aqueous liquid, or solid, preferably powder or granular, fabric care compositions to be used in the wash cycle comprises an effective amount of said fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharide, surfactants, builders, perfume, and mixtures thereof.
  • fabric care compositions for treating fabric in the drying step comprising an effective amount of said fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharide, fabric softening actives, perfume, and mixtures thereof.
  • the dryer-added fabric care composition is preferably provided as part of an article of manufacture in combination with a dispensing means such as a flexible substrate or a sprayer which effectively releases the fabric care composition in an automatic tumble clothes dryer.
  • the fabric care polysaccharides with globular structure can provide at least some fabric care benefits to all types of fabrics, including fabrics made of natural fibers, synthetic fibers, and mixtures thereof.
  • the present invention relates to solid or stable, preferably translucent, more preferably clear, aqueous fabric care compositions, fabric care methods, and articles of manufacture that use such fabric care composition. It also relates to the use of fabric care polysaccharide in a fabric care composition for providing a fabric with at least one of the following fabric care benefits: wrinkle removal, wrinkle reduction, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric soiling reduction, fabric soil release, fabric shape retention, and/or fabric shrinkage reduction, said fabric care polysaccharide comprising polysaccharides with globular structure and with molecular weight of from about 5,000 to about 500,000; branched versions of said polysaccharides; derivatised versions of said polysaccharides; substituted versions of said polysaccharides; and mixtures thereof.
  • Said polysaccharides are preferably selected from the group consisting of arabinogalactan, pachyman, curdlan, callose, paramylon, sceleroglucan, lentinan, lichenan, laminarin, szhizophyllan, grifolan, sclerotinia sclerotiorum glucan (SSG), Ompharia lapidescence glucan (OL-2), pustulan, dextran, pullulan and mixtures thereof, branched versions thereof, substituted versions thereof, derivatised versions thereof, and mixtures thereof.
  • One class of preferred fabric care polysaccharides are those having 1,3- ⁇ -linked backbone, such as, arabinogalactan, pachyman, curdlan, callose, paramylon, sceleroglucan, lentinan, lichenan, laminarin, szhizophyllan, grifolan, sclerotinia sclerotiorum glucan (SSG), Ompharia lapidescence glucan (OL-2), , and mixtures thereof, branched versions thereof, substituted versions thereof, derivatised versions thereof, and mixtures thereof, more preferably arabinogalactan, its derivatised versions, its substituted versions, and mixtures thereof, typically from about 0.001% to about 20%, preferably from about 0.01 % to about 10%, more preferably from about 0.1% to about 5%, and even more preferably from about 0.1 % to about 2%, by weight of the composition.
  • 1,3- ⁇ -linked backbone such as, arabinogalactan
  • the fabric care compositions of the present invention can be in solid (powder, granules, bars, tablets), dimple tablets, liquid, paste, gel, spray, stick or foam forms.
  • a preferred fabric care composition for treating fabric comprises an effective amount of said fabric care polysaccharides with globular structure, and, optionally, one, or more ingredients selected from the group consisting of : adjunct fabric care oligosaccharides, perfume, fiber lubricant, fabric shape retention polymer, lithium salt, hydrophilic plasticizer, odor control agent including cyclodextrin, antimicrobial active and/or preservative, surfactant, fabric softening active, static control agent, enzymes, antioxidant, chelating agent, e.g., aminocarboxylate chelating agent, heavy metal chelating agent, dye transfer inhibiting agent, dye fixative agent, soil release agent, colorant, suds suppressor, insect repelling agent and/or moth repelling agent, and mixtures thereof.
  • adjunct fabric care oligosaccharides perfume, fiber lubricant, fabric shape retention polymer, lithium salt, hydrophilic plasticizer, odor control agent including cyclodextrin, antimicrobial active and/or preservative, surfactant
  • the composition is typically applied to fabric and/or an entire fabric garment via a, e.g., dipping, soaking, misting and/or spraying process, followed by a drying step, including the process comprising a step of treating and/or spraying and/or misting the fabric and/or entire fabric garment with the fabric care composition either outside or inside an automatic clothes dryer followed by, or concurrently with, the drying step in said clothes dryer.
  • a drying step including the process comprising a step of treating and/or spraying and/or misting the fabric and/or entire fabric garment with the fabric care composition either outside or inside an automatic clothes dryer followed by, or concurrently with, the drying step in said clothes dryer.
  • the application can be done industrially by large scale processes on textiles and/or finished garments and clothing, or in a consumer's home by the use of commercial product.
  • the fabric care composition of present invention can also be applied directly on an entire garment via an applicator, preferably a spray mechanism and/or mist mechanism.
  • an applicator preferably a spray mechanism and/or mist mechanism.
  • the spraying and/or misting of the entire garment occurs in a manner such that excessive amounts of the fabric/garment care composition are prevented from being released to the open environment.
  • the spraying and/or misting of the entire garment can occur within a bag or other article suitable for containing the garment.
  • the present invention also relates to concentrated liquid or solid fabric care compositions, which are diluted to form compositions with the usage concentrations, as given hereinabove and/or hereinbelow, for use in the "usage conditions".
  • Concentrated compositions for use in the laundry process such as pre-wash treatment compositions, wash-added compositions, and rinse-added compositions, comprise a higher level of fabric care polysaccharide with globular structure, 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 fabric care composition.
  • Concentrated compositions for use to apply directly to fabric and/or entire garment, such as in the spraying process and/or misting process and/or dipping/soaking process comprise a lower level; of fabric care polysaccharide with globular structure, typically from about 1% to about 40%, preferably from about 1% to about 25%, more preferably from about 2% to about 15%, by weight of the concentrated fabric care composition.
  • the concentrated compositions optionally comprise at least one ingredient selected from the group consisting of: perfume, fiber lubricant, shape retention polymer, lithium salt, odor control agent including cyclodextrin, hydrophilic plasticizer, surfactant, antimicrobial active and/or antibacterial preservative, aminocarboxylate chelating agent, fabric softening active, static control agent, enzyme, antioxidant, suds suppressor, dye transfer inhibiting agent, dye fixing agent, insect repelling agent including moth repelling agent, and/or liquid carrier, and mixtures thereof.
  • Concentrated compositions are used in order to provide a less expensive product per use.
  • the concentrated fabric care is diluted with about 50% to about 10,000%), more preferably from about 50% to about 8,000%>, and even more preferably from about 50% to about 5,000%, by weight of the composition, of water.
  • the concentrated compositions should also comprise proportionally higher levels of the desired optional ingredients to be diluted to be the usage compositions.
  • the present invention also relates to aqueous fabric care compositions inco ⁇ orated into a spray dispenser and/or mist generator to create an article of manufacture that can facilitate treatment of fabric articles and/or entire fabric garments and/or surfaces with said compositions containing said fabric care polysaccharide with globular structure and other optional ingredients at a level that is effective, yet is not discernible when dried on the surfaces.
  • the spray dispenser comprises manually activated and non-manual powered (operated) spray means and a container containing the fabric care composition.
  • the articles of manufacture preferably are in association with instructions for use to direct the consumer to apply at least an effective amount of the fabric care composition and/or fabric care polysaccharide with globular structure to the fabric to provide the desired benefit.
  • the present invention also relates to an article of manufacture comprising the above aqueous fabric care compositions, to be applied directly via an applicator, preferably a spray mechanism and/or mist mechanism, more preferably via misting mechanism, on said fabric and/or entire garment in a manner such that excessive amounts of the fabric/garment care composition are prevented from being released to the open environment, preferably in association with instructions for use which direct the consumer to apply at least an effective amount of said fabric care polysaccharide with globular structure and/or said composition to said fabric and/or entire garment is this manner.
  • an applicator preferably a spray mechanism and/or mist mechanism, more preferably via misting mechanism
  • compositions of the present invention can also be used as ironing aids.
  • An effective amount of the composition can be sprayed onto fabric and the fabric is ironed at the normal temperature at which it should be ironed.
  • the fabric can either be sprayed with an effective amount of the composition, allowed to dry and then ironed, or sprayed and ironed immediately.
  • the fabric care polysaccharides of the current invention have a molecular weight range that is high enough so that they are easily damaged by the hot temperature of the ironing process, as is the case of lower molecular weight oligosaccharides and monosaccharides.
  • a liquid, preferably aqueous, or solid, preferably powder, fabric care composition for treating fabric in the rinse step comprising an effective amount of said fabric care polysaccharide with globular structure, typically from about 0.05% to about 50%), preferably from about 1% to about 35%, more preferably from about 2% to about 18%), and even more preferably from about 3% to about 10%, by weight of the fabric care composition.
  • the fabric care composition optionally comprises of: adjunct fabric care oligosaccharide, fabric softening active, perfume, electrolyte, chlorine scavenging agent, dye transfer inhibiting agent, dye fixing agent, phase stabilizer, chemical stabilizer including antioxidant, silicone, antimicrobial actives and/or preservative, chelating agent including aminocarboxylate chelating agent, colorant, enzyme, brightener, soil release agent, or mixtures thereof.
  • Said composition is preferably packaged into an article of manufacture in association with instructions for use to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • the present invention also relates to concentrated liquid or solid compositions, which are diluted to form rinse-added fabric care compositions with the usage concentrations, as given hereinabove, for use in the "usage conditions".
  • Another preferred aqueous or solid, preferably powder or granular, fabric care composition of this invention to be used in the wash cycle comprises an effective amount of said fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharide, surfactants, builder, perfume, chlorine scavenging agent, dye transfer inhibiting agent, dye fixing agent, dispersant, detergent enzyme, heavy metal chelating agent, suds suppressor, fabric softening active, chemical stabilizers including antioxidant, silicone, antimicrobial active and/or preservative, soil suspending agent, soil release agent, optical brightener, colorant, and the like, or mixtures thereof.
  • wash- added fabric care compositions can be in the form of tablets, bar, paste, gel, spray, stick, foam, and can optionally be contained in a pouch or attached to a releasable substrate.
  • wash-added compositions which can be wash additive compositions or detergent compositions are preferably packaged into an article of manufacture in association with instructions for use to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • fabric care compositions for treating fabric in the drying step comprising an effective amount of said fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharides, fabric softening actives, distributing agent, perfume, fiber lubricants, fabric shape retention polymers, lithium salts, phase stabilizers, chlorine scavenging agents, dye transfer inhibiting agents, dye fixing agents, chemical stabilizers including antioxidants, silicones, antimicrobial actives and/or preservatives, heavy metal chelating agents, aminocarboxylate chelating agents, enzymes, brighteners, soil release agents, and mixtures thereof.
  • the fabric care composition can take a variety of physical forms including liquid, foams, gel and solid forms such as solid particulate forms.
  • the dryer-added fabric care composition of the present invention is provided as part of an article of manufacture in combination with a dispensing means such as a flexible substrate which effectively releases the fabric care composition in an automatic tumble clothes dryer.
  • a dispensing means such as a flexible substrate which effectively releases the fabric care composition in an automatic tumble clothes dryer.
  • Such dispensing means can be designed for single usage or for multiple uses.
  • the composition is applied onto a sheet substrate- to form a dryer sheet product.
  • the substrates in such products are typically non-woven fabric substrates, paper, foams, etc.
  • Typical and preferred dispensing means are described in U.S. Pat. No. 5,102,564, issued Apr. 7, 1992 to Gardlik et al., inco ⁇ orated herein by reference.
  • the fabric care compositions can be desirable to provide some of the fabric care compositions as one, or more, separate compositions, e.g., as separate areas on a substrate, as disclosed hereinafter.
  • Said composition is preferably packaged with or without a dispensing means into an article of manufacture in association with instructions for use to ensure that the consumer knows what benefits can be achieved.
  • Another preferred dispensing means is a sprayer which dispense the liquid fabric care composition at the beginning and/or during the drying cycle.
  • the present invention also relates to fabric care compositions for dipping and/or soaking pre-wash treatment containing an effective amount of fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharide, surfactants, builders, perfume, chlorine scavenging agents, dye transfer inhibiting agents, dye fixing agents, dispersants, detergent enzymes, heavy metal chelating agents, fabric softening actives, chemical stabilizers including antioxidants, silicones, antimicrobial actives and/or preservatives, soil suspending agents, soil release agents, optical brighteners, colorants, and the like, or mixtures thereof.
  • Said composition is preferably packaged in association with instructions for use to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • the present invention also relates to concentrated liquid or solid compositions, which are diluted to form pre-wash fabric care compositions with the usage concentrations, for use in the "usage conditions".
  • the present invention also relates to fabric care methods and articles of manufacture that use such fabric care compositions.
  • the present invention relates to the compositions inco ⁇ orated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabric surfaces with said fabric care compositions containing a fabric care polysaccharide with globular structure and other optional ingredients at a level that is effective, yet is not discernible when dried on the surfaces.
  • the spray dispenser comprises manually activated and non-manual powered spray means and a container containing the fabric care composition.
  • the article of manufacture can comprise a fabric care composition and a dispensing means to distribute said composition onto the fabrics in a automatic tumble clothes dryer.
  • the dispensing means is a flexible substrate, e.g., in sheet configuration with the fabric care composition releasably affixed onto the substrate.
  • the article of manufacture can simply comprise a liquid or granular solid fabric care composition and a suitable container.
  • the articles of manufacture are in association with instructions for how to use the composition to treat fabrics correctly, to obtain the desirable fabric care results, viz, wrinkle removal and/or reduction, wrinkle resistance, fiber strengthening/anti-wear, fabric wear reduction, fabric shrinkage prevention and/or reduction, fabric pill prevention and/or reduction, shrinkage prevention and/or reduction, fabric color maintenance, fabric color restoration, fabric color fading reduction, soiling prevention and/or reduction, soil release, and/or fabric shape retention, and mixtures thereof, including, e.g., the manner and/or amount of composition to used, and the preferred ways of stretching and/or smoothing of the fabrics. It is important that the instructions be as simple and clear as possible, so that using pictures and/or icons is desirable.
  • Suitable fabric care polysaccharides for use in the fabric care composition of the present invention are those which have a globular conformation in dilute aqueous solution, via a random coiling structure.
  • Said polysaccharides include homo- and/or hetero- polysaccharides with simple helical structure with or without branching, e.g., with 1,4- ⁇ -linked backbone structure (e.g., 1 ,4- -glucan, 1,4- ⁇ -xylan) with or without branching, 1,3- ⁇ -linked backbone with or without branching (e.g., galactan), and all 1,6- linked backbones with or without branching (e.g., dextran, pullulan, pustulan), and with a weight-average molecular weight of from about 5,000 to about 500,000, preferably from about 8,000 to about 250,000, more preferably from about 10,000 to about 150,000, typically with sizes ranging from about 2 nm to about 300 nm, preferably from about 3 nm to
  • the fabric care polysaccharide is selected from the group consisting of arabinogalactan, pachyman, curdlan, callose, paramylon, sceleroglucan, lentinan, lichenan, laminarin, szhizophyllan, grifolan, sclerotinia sclerotiorum glucan (SSG), Ompharia lapidescence glucan (OL-2), pustulan, dextran, pullulan, substituted versions thereof, derivatised versions thereof, and mixtures thereof.
  • the fabric care polysaccharide is selected from the group consisting of arabinogalactan, dextran, curdlan, substituted versions thereof, derivatised versions thereof, and mixtures thereof, and even more preferably the fabric care polysaccharide comprises arabinogalactan, substituted versions thereof, derivatised versions thereof, and mixtures thereof.
  • Substituted and/or derivatised materials of the fabric care polysaccharides listed hereinabove are also preferred in the present invention.
  • Nonlimiting examples of these materials include: carboxyl and hydroxymethyl substitutions (e.g., some uronic acid instead of neutral sugar units); amino polysaccharides (amine substitution); cationic quaternized polysaccharides; C ⁇ -C] 8 alkylated polysaccharides; acetylated polysaccharide ethers; polysaccharides having amino acid residues attached (small fragments of glycoprotein); polysaccharides containing silicone moieties, and the like. Some hydrophobic derivatives of the polysaccharides help the polysaccharides maintaining the globular conformation.
  • a preferred class of fabric care polysaccharides suitable for use in the present invention include those that have the backbone comprising at least some, but preferably almost entirely of 1,3- ⁇ -glycosidic linkages, preferably branched, preferably with either side chains attached with 1 ,6-linkages or derivatised for better water solubility and/or to maintain the globular structure.
  • the 1,6-linked branched polysaccharides with 1,3- ⁇ - linked backbone have higher water solubility and/or dispersibihty than the non-branched polysaccharides, so that branched polysaccharides can be used at higher molecular weight ranges.
  • Nonlimiting examples of useful fabric care polysaccharides with 1,3- ⁇ -linked backbone include arabinogalactan, pachyman, curdlan, callose, paramylon, sceleroglucan, lentinan, lichenan, laminarin, szhizophyllan, grifolan, sclerotinia sclerotiorum glucan (SSG), Ompharia lapidescence glucan (OL-2), and mixtures thereof.
  • Low molecular weight materials are preferred for polysaccharides with less or no branching, such as curdlan, while higher molecular weight materials for highly branched polysaccharides, such as arabinogalactan, can be used.
  • Higher molecular weight polysaccharides with mixed 1,3- ⁇ and 1 ,4- ⁇ linkages, such as lichenan, can also be used.
  • a preferred fabric care branched polysaccharide with 1,3- ⁇ -linked backbone is arabinogalactan (also named as galactoarabinan or epsilon-galactan).
  • Arabinogalactans are long, densely branched high-molecular weight polysaccharides.
  • Arabinogalactan that is useful in the composition of the present invention has a molecular weight range of from about 5,000 to about 500,000, preferably from about 6,000 to about 250,000, more preferably from about 10,000 to about 150,000.
  • polysaccharides are highly branched, consisting of a galactan backbone with side-chains of galactose and arabinose units (consisting of ⁇ -galactopyranose, ⁇ -arabinofuranose, and ⁇ -arabinopyranose).
  • the major source of arabinogalactan is the larch tree.
  • the genus Larix (larches) is common throughout the world. Two main sources of larch trees are western larch (Larix occidentalis) in Western North America and Mongolian larch (Larix dahurica).
  • Larch arabinogalactan is water soluble and is composed of arabinose and galactose units in about a 1 :6 ratio, with a trace of uronic acid.
  • Glycosyl linkage analysis of larch arabinogalactan is consistent with a highly branched structure comprising a backbone of 1,3- ⁇ -linked galactopyranose connected by 1,3- ⁇ -glycosidic linkages, comprised of 3,4,6-, 3,6-, and 3,4- as well as 3-linked residues.
  • the molecular weights of the preferred fractions of larch arabinogalactan include one fraction in the range of from about 14,000 to about 22,000, mainly from about 16,000 to about 21,000, and the other in the range of from about 60,000 to about 500,000, mainly from about 80,000 to about 120,000.
  • the fraction that has the average molecular weight of from about 16,000 to about 20,000 is highly preferred for use in direct applications to fabric, such as in spray-on products.
  • the high molecular weight fraction (of about 100,000 molecular weight), as well as the low molecular weight fraction are suitable for use in processes that involve subsequent water treatments, such as, pre-soak, wash-added and/or rinse-added laundry processes and products.
  • High grade larch arabinogalactan is composed of greater than about 98% arabinogalactan.
  • Larch arabinogalactan and some of its derivatives, such as cationic derivatives are commercially available from Larex, Inc., St Paul, Minnesota.
  • Arabinogalactans are also present as minor, water-soluble components of softwoods such as hemlock, black spruce, parana pine, mugo pine, Douglas fir, incense cedar, juniper, and the sapwood of sugar maple.
  • softwoods such as hemlock, black spruce, parana pine, mugo pine, Douglas fir, incense cedar, juniper, and the sapwood of sugar maple.
  • Many edible and inedible plants are also rich sources of arabinogalactans, mostly in glycoprotein form, bound to a protein spine of either threonine, proline, or serine (“arabinogalactan-protein"). These plants include leek seeds, carrots, radish, black gram beans, pear, maize, wheat, red wine, Italian ryegrass, tomatoes, ragweed, sorghum, bamboo grass, and coconut meat and milk.
  • Examples of other fabric care polysaccharides that have 1,3- ⁇ -linkage as a part of the backbone include: 1,3- ⁇ -xylan (from, e.g., Pencillus dumetosus), curdlen, a 1,3- ⁇ - glucan (from e.g., Alcaligenes faecalis), paramylon B, a 1,3- ⁇ -glucan (from, e.g., Euglena gracilis), lichenin, a (l,3),(l,4)- ⁇ -glucan (from various sources including Cetraria islandica), sceleroglucan, a (l,3),(l,6)- ⁇ -glucan (from, e.g., Sclerotium rolf ⁇ ), and lentinen, a (l,3),(l,6)- ⁇ -glucan (from, e.g., Lentinus edodes).
  • 1,3- ⁇ -xylan from, e.g.
  • Substituted and/or derivatised materials of arabinogalactans are also preferred in the present invention.
  • Nonlimiting examples of these materials include: carboxyl and hydroxymethyl substitutions (e.g., some uronic acid instead of neutral sugar units); amino polysaccharides (amine substitution); cationic quaternized polysaccharides; C ⁇ -C 18 alkylated polysaccharides; acetylated polysaccharide ethers; polysaccharides having amino acid residues attached (small fragments of glycoprotein); polysaccharides containing silicone moieties.
  • substituted and/or derivatised polysaccharides can provide additional benefits, such as: amine substitution can bind and/or condense with oxidatively damaged regions of the fiber to rejuvenate aged fabrics; acetylated sugar ethers can serve as bleach activators in subsequent processes where hydrogen peroxide is present; polysaccharides having amino acid residues can improve delivery of fabric care benefits for fabrics containing proteinaceous fibers, e.g., wool and silk; and silicone- derivatised polysaccharides can provide additional fabric softness and lubricity.
  • derivatised arabinogalactan include the 3-chloro-2-hydroxypropyltrimethyl ammonium chloride derivative, available from Larex, Inc and the arabinogalactan- proteins given hereinabove.
  • the 1,3- ⁇ -linked backbone of the fabric care polysaccharides of the present invention (as in 1,3- ⁇ -galactans, 1,3- ⁇ -D-mannans, 1,3- ⁇ -D-xylans and 1,3- ⁇ -D-glucans) has a pseudohelical conformation.
  • these polysaccharides have a backbone chain that is flexible and in aqueous solution, has a tendency to coil into a globular structure to substantially reduce their apparent dimension (gyration volume), as opposed to the backbone chain of 1,4- ⁇ -glucan which has an extended dimension.
  • polysaccharides with 1,3- ⁇ -linked backbone and extensive branching via 1 ,6-linkages, or polysaccharides with helical confirmation or polysaccharides with 1,6-linked backbone have added flexibility due to the "coiling" nature of the 1,6-linkages.
  • these polysaccharides with 1,3- ⁇ -linked backbone and 1 ,6-branching e.g., arabinogalactans
  • arabinogalactans have a globular conformation with high flexibility to coil into compact, flexible and deformable microscopic particles.
  • an arabinogalactan having a nominal molecular weight of about 18,000 has a size (gyration length) of only from 5 nm to about 10 nm in dilute aqueous solutions.
  • This structural feature of the globular polysaccharides with helical conformation and random coiling nature improves physical properties such as water-solubility, low viscosity and emulsification. It is believed that the globular, compact and flexible structural property and low viscosity of the fabric care polysaccharides with 1,3- ⁇ -linked backbone of the present invention, such as arabinogalactans, is important for providing the fabric care benefits, either via efficient deposition of the polysaccharide globules on the rough fabric surface or via appropriate fitting/filling of these globules in the openings and/or defective spaces on the fabric fiber surface, where they can orient itself to conform to the space available.
  • these low molecular weight (about 10,000 to about 150,000) polysaccharide globules of the present invention can very effectively bond fibers and/or microfibrils together by "spot bonding".
  • the fabric care polysaccharide globules can provide many desired benefits such as: fabric strengthening, fabric wear resistance and/or reduction, wrinkle removal and/or reduction, fabric pilling prevention and/or reduction, fabric color maintenance and/or fading reduction, color restoration, fabric soiling reduction, fabric shape retention, fabric shrinkage reduction, and/or improving fabric feel/smoothness, scratchiness reduction, for different types of fabrics such as cellulosic (cotton, rayon, etc.), wool, silk, and the like.
  • Polysaccharides with helical conformation, but not within the range, of the molecular weight range specified above have different physical properties such as low solubility and gelling characteristics (e.g., starch, a high molecular weight 1,4- ⁇ -D- glucan).
  • the fabric care polysaccharides with globular structure of the present invention can provide at least some fabric care benefits to all types of fabrics, including fabrics made of natural fibers, synthetic fibers, and mixtures thereof.
  • fabric types that can be treated with the fabric care compositions of the present invention, to obtain fabric care benefits include fabrics made of (1) cellulosic fibers such as cotton, rayon, linen, Tencel, (2) proteinaceous fibers such as silk, wool and related mammalian fibers, (3) synthetic fibers such as polyester, acrylic, nylon, and the like, (4) long vegetable fibers from jute, flax, ramie, coir, kapok, sisal, henequen, abaca, hemp and sunn, and (5) mixtures thereof.
  • the composition can contain from about 0.001% to about 20%) of fabric care polysaccharide with globular structure, preferably from about 0.01 % to about 10%), more preferably from about 0.1 % to about 5%, by weight of the usage composition.
  • the present invention also relates to concentrated liquid or solid compositions, which are diluted to form compositions with the usage concentrations, for use in the "usage conditions".
  • Concentrated compositions comprise a higher level of fabric care polysaccharide, typically from about 1% to about 99%, preferably from about 2% to about 65%), more preferably from about 3% to about 40%, by weight of the concentrated fabric care composition.
  • the concentrated compositions should also comprise proportionally higher levels of the desired optional ingredients.
  • Typical composition to be dispensed from a sprayer contains a level of fabric care polysaccharide with globular structure 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.
  • Typical usage compositions for a direct dipping and/or soaking treatment followed by a drying step contain a level of fabric care polysaccharide of from about 0.001% to about 2%, preferably from about 0.05% to about 1%, more preferably from about 0.1% to about 0.5%, by weight of the usage composition.
  • a concentrated composition containing typically from about 0.5%) to about 40%, preferably from about 1% to about 25%), more preferably from about 2% to about 15%), by weight of the concentrated composition, of fabric care polysaccharide with globular structure, to be diluted down in use to obtain the desirable usage dipping or soaking composition.
  • the concentrated compositions should also comprise proportionally higher levels of the desired optional ingredients.
  • a concentrated composition can also be used, and is provided, e.g., as a refill, to prepare usage composition for the spray product.
  • Wash-added compositions typically contain a level of fabric care polysaccharide with globular structure of from about 0.2% to about 30%, preferably from about 1% to about 20%), more preferably from about 2% to about 10%, by weight of the wash-added compositions.
  • Typical rinse-added compositions, including liquid fabric conditioner and other rinse additive compositions contain a level of fabric care polysaccharide with globular structure of from about 0.3% to about 40%, preferably from about 1% to about 25%, more preferably from about 2% to about 15%, by weight of the rinse-added compositions.
  • Typical usage compositions for a dipping and/or soaking pre-wash treatment and/or for use as a wash-cycle additive contain a level of fabric care polysaccharide with globular structure of from about 0.05% to about 40%, preferably from about 0.1% to about 20%), more preferably from about 0.5% to about 10%o, by weight of the usage composition.
  • More concentrated compositions comprise a higher level of fabric care polysaccharide, typically from about 1% to about 99%, preferably from about 2% to about 65% ⁇ , more preferably from about 3% to about 40%, by weight of the concentrated fabric care composition.
  • the concentrated compositions should also comprise proportionally higher levels of the desired optional ingredients.
  • Dryer-added compositions typically contain a level of fabric care polysaccharide with globular structure of from about 0.01 % to about 40%> by weight of the dryer-added compositions.
  • An optional but preferred adjunct fabric care agent in the present invention is selected from the group consisting of oligosaccharides, especially mixtures of oligosaccharides, especially, isomaltooligosaccharides (EVIO) (including mixtures), the individual components of said mixtures, substituted versions thereof, derivatised versions thereof, and mixtures thereof.
  • oligosaccharides especially mixtures of oligosaccharides, especially, isomaltooligosaccharides (EVIO) (including mixtures), the individual components of said mixtures, substituted versions thereof, derivatised versions thereof, and mixtures thereof.
  • EVIO isomaltooligosaccharides
  • adjunct fabric fabric care oligosaccharides help to provide some fabric benefits, such as wrinkle removal and/or reduction, anti-pilling, anti- wear, fabric color maintenance, and overall appearance benefits, especially to cellulosic fibers/fabrics, such as cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell (Tencel ®), polyester/cotton blends, other cotton blends, and the like, especially cotton, rayon, linen, polyester/cotton blends, and mixtures thereof.
  • cellulosic fibers/fabrics such as cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell (Tencel ®), polyester/cotton blends, other cotton blends, and the like, especially cotton, rayon, linen, polyester/cotton blends, and mixtures thereof.
  • Suitable adjunct fabric care oligosaccharides that are useful in the present invention include oligosaccharides with a degree of polymerization (DP) of from about 1 to about 15, preferably from about 2 to about 10, and wherein each monomer is selected from the group consisting of reducing saccharide containing 5 and/or 6 carbon atoms, including isomaltose, isomaltotriose, isomaltotetraose, isomaltooligosaccharide, fructooligosaccharide, levooligosaccharides, galactooligosaccharide, xylooligosaccharide, gentiooligosaccharides, disaccharides, glucose, fructose, galactose, xylose, mannose, arabinose, rhamnose, maltose, sucrose, lactose, maltulose, ribose, lyxose, allose, altrose, gulose, idose,
  • Oligosaccharides containing ⁇ -linkages are also preferred.
  • Preferred oligosaccharides are acyclic and have at least one linkage that is not an ⁇ -l,4-glycosidic bond.
  • a preferred oligosaccharide is a mixture containing IMO: from 0 to about 20 % by weight of glucose, from about 10 to about 65 % of isomaltose, from about 1% to about 45% of each of isomaltotriose, isomaltetraose and isomaltopentaose, from 0 to about 3 % of each of isomaltohexaose, isomaltoheptaose, isomaltooctaose and isomaltononaose, from about 0.2% to about 15%) of each of isomaltohexaose and isomaltoheptaose, and from 0 to about 50 % by weight of said mixture being isomal
  • Trisaccharides maltotriose, panose, isomaltotriose
  • Disaccharides maltose, isomaltose
  • Trisaccharides maltotriose, panose, isomaltotriose
  • Disaccharides maltose, isomaltose
  • Trisaccharides raffinose 0-10%
  • Oligosaccharide mixtures are either prepared by enzymatic reactions or separated as natural products from plant materials.
  • the enzymatic synthesis of oligosaccharides involves either adding monosaccharides, one at a time, to a di- or higher saccharide to produce branched oligosaccharides, or it can involve the degradation of polysaccharides followed by transfer of saccharides to branching positions.
  • Oligosaccharide Mixtures I and II are prepared by enzymatic hydrolysis of starch to maltooligosaccharides, which are then converted to isomaltooligosaccharides by a transglucosidase reaction.
  • Oligosaccharide Mixture III for example, is a mixture of oligosaccharides isolated from soybean. Soybean oligosaccharides such as Mixture III, are of pure natural origin.
  • Cyclic oligosaccharides can also be useful in the fabric care composition of the present invention.
  • Preferred cyclic oligosaccharides include ⁇ -cyclodextrin, ⁇ - cyclodextrin, ⁇ -cyclodextrin, their branched derivatives such as glucosyl- -cyclodextrin, diglucosyl- ⁇ -cyclodextrin, maltosyl- ⁇ -cyclodextrin, glucosyl- ⁇ -cyclodextrin, diglucosyl- ⁇ -cyclodextrin, and mixtures thereof.
  • the cyclodextrins also provide an optional but very important benefit of odor control, and are disclosed more fully hereinbelow.
  • Substituted and/or derivatised materials of the oligosaccharides listed hereinabove are also preferred in the present invention.
  • Nonlimiting examples of these materials include: carboxyl and hydroxymethyl substitutions (e.g., glucuronic acid instead of glucose); amino oligosaccharides (amine substitution, e.g., glucosamine instead of glucose); cationic quaternized oligosaccharides; C ⁇ -C 6 alkylated oligosaccharides; acetylated oligosaccharide ethers; oligosaccharides having amino acid residues attached (small fragments of glycoprotein); oligosaccharides containing silicone moieties.
  • substituted and/or derivatised oligosaccharides can provide additional benefits, such as: carboxyl and hydroxymethyl substitutions can introduce readily oxidizable materials on and in the fiber, thus reducing the probability of the fiber itself being oxidized by oxidants, such as bleaches; amine substitution can bind and/or condense with oxidatively damaged regions of the fiber to rejuvenate aged fabrics; acetylated sugar ethers can serve as bleach activators in subsequent processes where hydrogen peroxide is present; oligosaccharides having amino acid residues can improve delivery of fabric care benefits for fabrics containing proteinaceous fibers, e.g., wool and silk; and silicone-derivatised oligosaccharides can provide additional fabric softness and lubricity.
  • C 6 alkyl oligosaccharide is disclosed (along with other higher, viz., C6-C30, alkyl polysaccharides) in U.S. Pat. 4,565,647, issued Jan. 21, 1986 to Llenado, for use as foaming agent in foaming compositions such as laundry detergents, personal and hair cleaning compositions, and fire fighting compositions.
  • the C 6 alkyl oligosaccharide is a poor surfactant and not preferred for use as surfactant in the detergent compositions of the present invention, but preferably can be used to provide the fabric care benefits that are not known, appreciated and/or disclosed in U.S. Pat No. 4,565,647.
  • U.S. Pat. No. 4,488,981 issued Dec.
  • C]-C 6 alkylated oligosaccharides lower alkyl glycosides
  • C ⁇ -C 6 alkylated oligosaccharides are not preferred for use as viscosity and phase modifiers in the liquid detergent compositions of the present invention, but can be used to provide the fabric care benefits that are not known, appreciated and/or disclosed in U.S. Pat No.4,488,981. These patents are inco ⁇ orated herein by reference.
  • the fabric care oligosaccharide is adsorbed and binds with cellulosic fabrics to improve the properties of the fabrics. It is believed that the fabric care oligosaccharide is bound to the cellulosic fibers, diffuses in and fills the defect sites (the amo ⁇ hous region) of the fiber, to provide the above dewrinkling, increased strength and improved appearance benefits.
  • the extent of the amo ⁇ hous, non-crystalline region varies with cellulosic fiber types, e.g., the relative crystallinity of cotton is about 70.% and for regenerated cellulose, such as, rayon it is about 30.% , as reported by P. H. Hermans and A.
  • the composition can contain from about 0.001%) to about 20%) of the optional, but preferred oligosaccharide, preferably from about 0.01% to about 10%), more preferably from about 0.1% to about 5%, by weight of the usage composition.
  • the present invention also relates to concentrated liquid or solid compositions, which are diluted to form compositions with the usage concentrations, for use in the "usage conditions". Concentrated compositions comprise a higher level of the optional fabric care oligosaccharide, typically from about 1% to about 50%, preferably from about 2% to about 40%, more preferably from about 3% to about 20%, by weight of the concentrated fabric care composition.
  • Typical composition to be dispensed from a sprayer contains a level of optional fabric care oligosaccharide of from about 0.01% to about 3%, preferably from about 0.05%) to about 2%, more preferably from about 0.1% to about 1%, by weight of the usage composition.
  • Typical usage compositions for a direct dipping and/or soaking treatment followed by a fabric drying step contain a level of optional fabric care oligosaccharide of from about 0.001%> to about 2%, preferably from about 0.05% to about 1%, more preferably from about 0.1% to about 0.5%, by weight of the usage composition.
  • a concentrated composition containing typically from about 1% to about 40%, preferably from about 1% to about 25%o, more preferably from about 2% to about 15%, by weight of the concentrated composition, of the optional fabric care oligosaccharide, to be diluted down in use to obtain the desirable usage dipping or soaking compositions.
  • a concentrated composition can also be used, and is provided, e.g., as a refill, to prepare usage composition for the spray product.
  • Wash-added compositions typically contain a level of optional fabric care oligosaccharide of from about 0.2% to about 30%, preferably from about 1% to about 20%), more preferably from about 2% to about 12%, by weight of the wash-added compositions.
  • Typical rinse-added compositions, including liquid fabric conditioner and other rinse additive compositions contain a level of optional fabric care oligosaccharide of from about 0.1% to about 50%, preferably from about 1% to about 35%, more preferably from about 2% to about 18%, and even more preferably from about 2% to about 10%), by weight of the rinse-added compositions.
  • Dryer-added compositions typically contain a level of optional fabric care oligosaccharide of from about 0.01% to about 40%, preferably from about 0.1% to about 20%, more preferably from about 1% to about 10%, by weight of the dryer-added compositions.
  • Aqueous dryer-added compositions to be applied directly to the fabric, e.g., via a spraying mechanism, contain lower levels of fabric care polysaccharide, typically from about 0.01% to about 25%, preferably from about 0.1% to about 10%, more preferably from about 0.2% to about 5%, even more preferably from about 0.3% to about 3%, by weight of the compositions.
  • Both the fabric care polysaccharides and the optional fabric care oligosaccharides have a compact structure, but they have different sizes.
  • the smaller oligosaccharides are believed to be able to diffuse and penetrate into small defective sites, such as the amo ⁇ hous region of cotton fibers, while the larger polysaccharides can fill in larger openings and/or defective sites on the fabric fiber surface. Therefore depending on the fabric care benefit target, the fabric care polysaccharides can be used alone, or in mixtures with the optional fabric care oligosaccharides.
  • the weight ratio between said oligosaccharides and the fabric care polysaccharides is typically from about 1 :99 to about 99:1, preferably from about 15:85 to about 85:15, and more preferably from about 30:70 to about 70:30.
  • the fabric care compositions of the present invention can contain other optional ingredients either to improve the performance of the fabric care polysaccharide with globular structure, e.g., in the areas of wrinkle control, anti-wear, soil release, and the like, or to provide additional benefits, such as odor control, antimicrobial, and the like.
  • optional ingredients are given hereinbelow.
  • the fabric care composition of the present invention can comprise optional fiber lubricants to impart a lubricating property, or increased gliding ability, to fibers in fabric, particularly clothing.
  • fiber lubricants facilitate the movement of fibers with respect to one another (glide) to release the fibers from the wrinkle condition in wet or damp fabrics.
  • the fiber lubricant especially silicone, can provide lubricity to reduce the tendency of fabric to rewrinkle.
  • the present invention can use silicone, a preferred fiber lubricant, to impart a lubricating property, or increased gliding ability, to fibers in fabric, particularly clothing.
  • useful silicones in the composition of the present invention include noncurable silicones such as polydimethylsilicone and volatile silicones, and curable silicones such as aminosilicones, phenylsilicones and hydroxysilicones.
  • the word "silicone” as used herein preferably refers to emulsified silicones, including those that are commercially available and those that are emulsified in the composition, unless otherwise described.
  • the silicones are hydrophobic; are neither irritating, toxic, nor otherwise harmful when applied to fabric or when they come in contact with human skin; are chemically stable under normal use and storage conditions; and are capable of being deposited on fabric.
  • the noncurable silicones such as polydimethylsilicone, especially the volatile silicones
  • Curable and/or reactive silicones such as amino-functional silicones and silicones with reactive groups such as Si-OH, Si-H, silanes, and the like, are less preferred in this situation, because the portion of the composition that is sprayed but misses the garment, and falls instead on flooring surfaces, such as rug, ca ⁇ et, concrete floor, tiled floor, linoleum floor, bathtub floor, can leave a silicone layer that is cured and/or bonded to the flooring surfaces.
  • Such silicones that are bonded to surfaces are difficult to be removed from the flooring surfaces.
  • the curable and reactive silicones can be used in compositions specifically designed for use in articles such as a flexible bag, and in other, non-spray fabric treatment processes, such as dipping, soaking, in-the-wash, in-the-rinse, and in-the-dryer processes.
  • non-spray fabric treatment processes such as dipping, soaking, in-the-wash, in-the-rinse, and in-the-dryer processes.
  • Many types of amino functional silicones also cause fabric yellowing.
  • the silicones that cause fabric discoloration are also not preferred.
  • the preferred silicone is volatile silicone fluid which can be a cyclic silicone fluid of the formula [(CH3)2SiO] n where n ranges between about 3 to about 7, preferably about 5 (D5), or a linear silicone polymer fluid having the formula (CH3)3SiO[(CH3)2SiO] Si(CH3)3 where m can be 0 or greater and has an average value such that the viscosity at 25°C of the silicone fluid is preferably about 5 centistokes or less.
  • non-volatile silicones that are useful and preferred in the composition of the present invention is polyalkyl and/or phenylsilicones silicone fluids and gums with the following structure:
  • the alkyl groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) can have any structure as long as the resulting silicones remain fluid at room temperature.
  • Each R group preferably can be alkyl, aryl, hydroxy, or hydroxyalkyl group, and mixtures thereof, more preferably, each R is methyl, ethyl, propyl or phenyl group, most preferably R is methyl.
  • Each A group which blocks the ends of the silicone chain can be hydrogen, methyl, methoxy, ethoxy, hydroxy, propoxy, and aryloxy group, preferably methyl. Suitable A groups include hydrogen, methyl, methoxy, ethoxy, hydroxy, and propoxy.
  • q is preferably an integer from about 7 to about 8,000.
  • the preferred silicones are polydimethyl siloxanes; more preferred silicones are polydimethyl siloxanes having a viscosity of from about 50 to about 1000,000 centistokes at 25°C. Mixtures of volatile silicones and non-volatile polydimethyl siloxanes are also preferred. Suitable examples include silicones offered by Dow Corning Co ⁇ oration and General Electric Company.
  • silicone materials which can be used correspond to the formulas: (Rl) a G 3 . a -Si-(-OSiG 2 ) n -(OSiG b (Rl)2-b)m-0-SiG 3 . a (Rl) a wherein G is selected from the group consisting of hydrogen, phenyl, OH, and/or Ci -Cg alkyl; a denotes 0 or an integer from 1 to 3; b denotes 0 or 1; the sum of n + m is a number from 1 to about 2,000; Rl is a monovalent radical of formula C p H2pL in which p is an integer from 2 to 8 and L is selected from the group consisting of:
  • each R 2 is chosen from the group consisting of hydrogen, phenyl, benzyl, saturated hydrocarbon radical, and each A" denotes compatible anion, e.g., a halide ion;
  • R denotes a long chain alkyl group
  • f denotes an integer of at least about 2.
  • Another silicone material which can be used, but is less preferred than polydimethyl siloxanes, has the formula: (CH 3 )3Si— [O-Si(CH 3 )2]n— ⁇ OSi(CH3)[(CH 2 )3-NH-(CH2)2-NH2] ⁇ m — OSi(CH 3 )3 wherein n and m are the same as before.
  • the preferred silicones of this type are those which do not cause fabric discoloration.
  • the silicone material can be provided as a moiety or a part of a oligosaccharide molecule. These materials provide a lubricity benefit in addition to the expected fabric care benefits.
  • Other examples of dual function silicone materials useful in the present invention are adjunct shape retention copolymers having siloxane macromers grafted thereto.
  • the non-silicone backbone of such polymers should have a molecular weight of from about 5,000 to about 1,000,000, and the polymer should have a glass transition temperature (Tg), i.e., the temperature at which the polymer changes from a brittle vitreous state to a plastic state, of greater than about -20°C.
  • Adjunct fabric shape retention silicone-containing polymers useful in the present invention are described in more detailed herein below along with other adjunct shape retention polymers.
  • silicone When silicone is present, it is present at least an effective amount to provide lubrication of the fibers, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3%, more preferably from about 0.3% to about 2%, by weight of the usage composition.
  • Silicone is also a useful optional ingredient in the rinse-added fabric care compositions of the present invention.
  • the silicone can be either a polydimethyl siloxane (polydimethyl silicone or PDMS), or a derivative thereof, e.g., amino silicones, ethoxylated silicones, etc.
  • the PDMS is preferably one with a low molecular weight, e.g., one having a viscosity of from about 2 to about 5000 cSt, preferably from about 5 to about 500 cSt, more preferably from about 25 to about 200 cSt. Silicone emulsions can conveniently be used to prepare the compositions of the present invention.
  • the silicone is preferably one that is, at least initially, not emulsified. I.e., the silicone should be emulsified in t he composition itself.
  • the silicone is preferably added to the "water seat", which comprises the water and, optionally, any other ingredients that normally stay in the aqueous phase.
  • Low molecular weight PDMS is preferred for use in the fabric softener compositions of this invention.
  • the low molecular weight PDMS is easier to formulate without pre-emulsification.
  • Silicone derivatives such as amino-functional silicones, quaternized silicones, and silicone derivatives containing Si-OH, Si-H, and/or Si-Cl bonds, can be used. However, these silicone derivatives are normally more substantive to fabrics and can build up on fabrics after repeated treatments to actually cause a reduction in fabric absorbency.
  • the fabric softener composition When added to water, the fabric softener composition deposits the cationic fabric softening active on the fabric surface to provide fabric softening effects.
  • cotton fabric water absorbency can be appreciably reduced at high softening active levels and/or after multiple cycles. The silicone improves the fabric water absorbency, especially for freshly treated fabrics, when used with this level of fabric softening active without adversely affecting the fabric softening performance.
  • the amount of PDMS needed to provide a noticeable improvement in water absorbency is dependent on the initial rewettability performance, which, in turn, is dependent on the detergent type used in the wash. Effective amounts range from about 2 ppm to about 50 ppm in the rinse water, preferably from about 5 to about 20 ppm.
  • the PDMS to softening active ratio is from about 2:100 to about 50:100, preferably from about 3:100 to about 35:100, more preferably from about 4:100 to about 25:100. This typically requires from about 0.2% to about 20%, preferably from about 0.5%> to about 10%), more preferably from about 1% to about 5% silicone.
  • Solid polymeric particles of average particle size smaller than about 10 microns, preferably smaller than 5 microns, more preferably smaller than about 1 micron can be used as a lubricant, since they can provide a "roller-bearing" action.
  • solid polymeric particles When solid polymeric particles are present, they are present at an effective amount to provide lubrication of the fibers, typically from about 0.01% to about 3%, preferably from about 0.05%> to about 1%, more preferably from about 0.1 % to about 0.5%, by weight of the usage composition.
  • polymers can be natural, or synthetic, and can act by forming a film, and/or by providing adhesive properties.
  • the present invention can optionally use film-forming and/or adhesive polymer to impart shape retention to fabric, particularly clothing.
  • adheresive it is meant that when applied as a solution or a dispersion to a fiber surface and dried, the polymer can attach to the surface.
  • the polymer can form a film on the surface, or when residing between two fibers and in contact with the two fibers, it can bond the two fibers together.
  • Other polymers such as starches can form a film and/or bond the fibers together when the treated fabric is pressed by a hot iron. Such a film will have adhesive strength, cohesive breaking strength, and cohesive breaking strain.
  • Nonlimiting examples for natural polymers are starches and their derivatives, and chitins and their derivatives.
  • the synthetic polymers useful in the present invention are comprised of monomers.
  • monomers which can be used to form the synthetic polymers of the present invention include: low molecular weight C1 -C6 unsaturated organic mono-carboxylic and polycarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half esters, itaconic acid, and mixtures thereof; esters of said acids with C1-C12 alcohols, such as methanol, ethanol, 1- propanol, 2-propanol, 1-butanol, 2-methyl-l-propanol, 1-pentanol, 2-pentanol, 3- pentanol, 2-methyl- 1-butanol, 1 -methyl- 1-butanol, 3-methyl- 1-butanol, 1-methyl-l- pentanol, 2-methyl- 1-pentanol, 3-methyl- 1-pentanol, t-butanol, cyclohexanol, 2-
  • Nonlimiting examples of said esters are methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, methoxy ethyl methacrylate, and mixtures thereof; amides and imides of said acids, such as N,N-dimethylacrylamide, N-t-butyl acrylamide, maleimides; low molecular weight unsaturated alcohols such as vinyl alcohol (produced by the hydrolysis of vinyl acetate after polymerization), allyl alcohol; esters of said alcohols with low molecular weight carboxylic acids, such as, vinyl acetate, vinyl propionate; ethers of said alcohols such as methyl vinyl ether; aromatic vinyl such as styrene, alpha-methylstyrene, t-butylstyrene, vinyl toluene, polystyrene macromer, and the like; polar vinyl heterocyclics, such as vinyl pyrroli
  • said monomers are selected from the group consisting of vinyl alcohol; acrylic acid; methacrylic acid; methyl acrylate; ethyl acrylate; methyl methacrylate; t-butyl acrylate; t-butyl methacrylate; n-butyl acrylate; n-butyl methacrylate; isobutyl methacrylate; 2-ethylhexyl methacrylate; dimethylaminoethyl methacrylate; N,N-dimethyl acrylamide; N,N-dimethyl methacrylamide; N-t-butyl acrylamide; vinylpyrrolidone; vinyl pyridine; adipic acid; diethylenetriamine; salts thereof and alkyl quaternized derivatives thereof, and mixtures thereof.
  • said monomers form homopolymers and/or copolymers (i.e., the film- forming and/or adhesive polymer) having a glass transition temperature (Tg) of from about -20°C to about 150°C, preferably from about -10°C to about 150°C, more preferably from about 0°C to about 100°C, most preferably, the adhesive polymer hereof, when dried to form a film will have a Tg of at least about 25°C, so that they are not unduly sticky, or "tacky" to the touch.
  • said polymer is soluble and/or dispersible in water and/or alcohol.
  • Said polymer typically has a molecular weight of at least about 500, preferably from about 1,000 to about 2,000,000, more preferably from about 5,000 to about 1,000,000, and even more preferably from about 30,000 to about 300,000 for some polymers.
  • homopolymers and copolymers which can be used as film-forming and/or adhesive polymers of the present invention are: adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer; adipic acid/epoxypropyl diethylenetriamine copolymer; poly(vinylpyrrolidone/ dimethylaminoethyl methacrylate); polyvinyl alcohol; polyvinylpyridine n-oxide; methacryloyl ethyl betaine/methacrylates copolymer; ethyl acrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer; polyamine resins; and polyquaternary amine resins; poly(ethenylformamide); poly(vinylamine) hydrochloride; poly(vinyl alcohol-co-6% vinylamine); poly(vinyl alcohol-co-12% vinylamine); poly(vinyl alcohol-co-6%.
  • said copolymer and/or homopolymers are selected from the group consisting of adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer; poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); polyvinyl alcohol; ethyl acrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer; methacryloyl ethyl betaine/methacrylates copolymer; polyquaternary amine resins; poly(ethenylformamide); poly(vinylamine) hydrochloride; poly(vinyl alcohol-co- 6%) vinylamine); poly( vinyl alcohol-co-12% vinylamine); poly( vinyl alcohol-co-6%> vinylamine hydrochloride); and poly( vinyl alcohol-co-12%) vinylamine hydrochloride).
  • Nonlimiting examples of the preferred polymer that are commercially available are: polyvinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, such as
  • Copolymer 958 molecular weight of about 100,000 and Copolymer 937, molecular weight of about 1,000,000, available from GAF Chemicals Co ⁇ oration; adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer, such as Cartaretin F-
  • methacryloyl ethyl (R) betaine/methacrylates copolymer such as Diaformer Z-SM , available from Mitsubishi
  • polyquaternary amine resins such as Kymene 557H , available from
  • Preferred polymers useful in the present invention are selected from the group consisting of copolymers of hydrophilic monomers and hydrophobic monomers.
  • the polymer can be linear random or block copolymers, and mixtures thereof.
  • Such hydrophobic/hydrophilic copolymers typically have a hydrophobic monomer/hydrophilic monomer ratio of from about 95:5 to about 20:80, preferably from about 90:10 to about 40:60, more preferably from about 80:20 to about 50:50 by weight of the copolymer.
  • the hydrophobic monomer can comprise a single hydrophobic monomer or a mixture of hydrophobic monomers
  • the hydrophilic monomer can comprise a single hydrophilic monomer or a mixture of hydrophilic monomers.
  • hydrophobic is used herein consistent with its standard meaning of lacking affinity for water, whereas “hydrophilic” is used herein consistent with its standard meaning of having affinity for water.
  • hydrophobic means substantially water insoluble; “hydrophilic” means substantially water soluble.
  • substantially water insoluble shall refer to a material that is not soluble in distilled (or equivalent) water, at 25°C, at a concentration of about 0.2% by weight, and preferably not soluble at about 0.1%) by weight (calculated on a water plus monomer or polymer weight basis).
  • Substantially water soluble shall refer to a material that is soluble in distilled (or equivalent) water, at 25°C, at a concentration of about 0.2%) by weight, and are preferably soluble at about 1%> by weight.
  • soluble soluble
  • solubility corresponds to the maximum concentration of monomer or polymer, as applicable, that can dissolve in water or other solvents to form a homogeneous solution, as is well understood to those skilled in the art.
  • Nonlimiting examples of useful hydrophobic monomers are acrylic acid Ci-Ci ⁇ alkyl esters, such as methyl acrylate, ethyl acrylate, t-butyl acrylate; methacrylic C1-C18 alkyl esters, such as methyl methacrylate, 2-ethyl hexyl methacrylate, methoxy ethyl methacrylate; vinyl alcohol esters of carboxylic acids, such as, vinyl acetate, vinyl propionate, vinyl neodecanoate; aromatic vinyls, such as styrene, t-butyl styrene, vinyl toluene; vinyl ethers, such as methyl vinyl ether; vinyl chloride; vinylidene chloride; ethylene, propylene and other unsaturated hydrocarbons; and the like; and mixtures thereof.
  • acrylic acid Ci-Ci ⁇ alkyl esters such as methyl acrylate, ethyl acrylate, t-butyl
  • Some preferred hydrophobic monomers are methyl acrylate, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and mixtures thereof.
  • Nonlimiting examples of useful hydrophilic monomers are unsaturated organic mono-carboxylic and polycarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half esters, itaconic acid; unsaturated alcohols,- such as vinyl alcohol, allyl alcohol; polar vinyl heterocyclics, such as vinyl pyrrolidone, vinyl caprolactam, vinyl pyridine, vinyl imidazole; vinyl amine; vinyl sulfonate; unsaturated amides, such as acrylamides, e.g., N,N-dimethylacrylamide, N-t-butyl acrylamide; hydroxyethyl methacrylate; dimethylaminoethyl methacrylate; salts of acids and amines listed above; and the like; and mixtures thereof.
  • unsaturated organic mono-carboxylic and polycarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half est
  • Some preferred hydrophilic monomers are acrylic acid, methacrylic acid, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N-t-butyl acrylamide, dimethylamino ethyl methacrylate, vinyl pyrrolidone, salts thereof and alkyl quaternized derivatives thereof, and mixtures thereof.
  • Non limiting examples of polymers for use in the present invention include the following, where the composition of the copolymer is given as approximate weight percentage of each monomer used in the polymerization reaction used to prepare the polymer: vinyl pyrrolidone/vinyl acetate copolymers (at ratios of up to about 30% by weight of vinyl pyrrolidone); dimethyl acrylamide/ t-butyl acrylate/ethyl hexyl methacrylate copolymer (10/45/45); vinyl pyrrolidone/vinyl acetate/butyl acrylate copolymer (10/78/12 and 10/70/20); vinyl pyrrolidone/vinyl propionate copolymer (5/95); vinyl caprolactam/vinyl acetate copolymer (5/95); acrylic acid/t-butyl acrylate
  • Luviset CA 66 by BASF (vinyl acetate/crotonic acid copolymer 90/10); Luviset CAP by BASF (vinyl acetate/vinyl propionate/crotonic acid 50/40/10);
  • Resyn 28-2930 by National Starch (vinyl acetate/vinyl neodecanoate/crotonic acid
  • adjunct shape retention polymers contain an effective amount of monomers having carboxylic groups.
  • Highly preferred adjunct shape retention copolymers contain hydrophobic monomers and hydrophilic monomers which comprise unsaturated organic mono-carboxylic and polycarboxylic acid monomers, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half esters, itaconic acid, and salts thereof, and mixtures thereof; and optionally other hydrophilic monomers.
  • examples of the hydrophilic unsaturated organic mono-carboxylic and polycarboxylic acid monomers are acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half esters, itaconic acid, and mixtures thereof.
  • Nonlimiting examples of the hydrophobic monomers are esters of the unsaturated organic mono-carboxylic and polycarboxylic acids cited hereinabove with C1-C12 alcohols, such as methanol, ethanol, 1-propanol, 2- propanol, 1-butanol, 2-methyl- 1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, 1 -methyl- 1-butanol, 3-methyl- 1-butanol, 1 -methyl- 1-pentanol, 2-methyl-l- pentanol, 3-methyl- 1-pentanol, t-butanol, cyclohexanol, 2-ethyl- 1-butanol, and mixtures thereof, preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl- 1- propanol, t-butanol, and mixtures thereof.
  • One highly preferred copolymer contains acrylic acid and t-butyl acrylate monomeric units, preferably with acrylic acid/t-butyl acrylate ratios of from about 90:10 to about 10:90, preferably from about 70:30 to about 15:85, more preferably from about 40:60 to about 20:80.
  • Nonlimiting examples of acrylic acid/tert-butyl acrylate copolymers useful in the present invention are those typically with a molecular weight of from about 1,000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, and more preferably from about 30,000 to about 300,000, and 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, and those 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.
  • the film-forming and/or adhesive polymer of the present invention is present at least an effective amount to provide shape retention, typically from about 0.05% to about 10%), preferably from about 0.1 %> to about 5%, more preferably from about 0.2%> to about 3%o, even more preferably from about 0.3% to about 1.5%, by weight of the usage composition.
  • the adhesive polymer is present in the composition in a sufficient amount to result in an amount of from about 0.001% to about 1%, preferably from about 0.01% to about 0.5%), more preferably from about 0.02% to about 0.4%o by weight of polymer per weight of dry fabrics.
  • Silicones and film-forming polymers can be combined to produce preferred wrinkle reducing actives.
  • the weight ratio of silicone to film-forming polymer is from about 10:1 to about 1 :10, preferably from about 5: 1 to about 1 :5, and more preferably from about 2:1 to about 1 :2.
  • the preferred wrinkle reducing active of silicone plus polymer is present at a level of from about 0.1%o to about 8%, preferably from about 0.3% to about 5%, more preferably from about 0.5% to about 3%, by weight of the composition.
  • Optional but preferred adhesive and/or film forming polymers that are useful in the composition of the present invention actually contain silicone moieties in the polymers themselves.
  • These preferred polymers include graft and block copolymers of silicone with moieties containing hydrophilic and/or hydrophobic monomers described hereinbefore.
  • the silicone-containing copolymers in the spray composition of the present invention provide shape retention, body, and/or good, soft fabric feel.
  • Highly preferred silicone-containing copolymers contain hydrophobic monomers and hydrophilic monomers which comprise unsaturated organic mono-carboxylic and/or polycarboxylic acid monomers, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half esters, itaconic acid, and salts thereof, and mixtures thereof; and optionally other hydrophilic monomers.
  • hydrophobic monomers and hydrophilic monomers which comprise unsaturated organic mono-carboxylic and/or polycarboxylic acid monomers, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half esters, itaconic acid, and salts thereof, and mixtures thereof; and optionally other hydrophilic monomers.
  • the silicone portion is covalently attached to the non-silicone portion
  • the molecular weight of the silicone portion is from about 1 ,000 to about 50,000.
  • the non-silicone portion must render the entire copolymer soluble or dispersible in the wrinkle control composition vehicle and permit the copolymer to deposit on/adhere to the treated fabrics.
  • Suitable silicone copolymers include the following:
  • Preferred silicone-containing polymers are the silicone graft copolymers comprising acrylate groups described, along with methods of making them, in U.S. Patent No. 5,658,557, Bolich et al., issued Aug. 19, 1997, U.S. Patent No. 4,693,935, Mazurek, issued Sept. 15, 1987, and U.S. Patent No. 4,728,571, Clemens et al., issued Mar. 1, 1988. Additional silicone-containing polymers are disclosed in U.S. Pat. Nos. 5,480,634, Hayama et al, issued Oct. 2, 1996, 5,166,276, Hayama et al., issued Nov. 24, 1992, 5,061,481, issued Oct.
  • These polymers preferably include copolymers having a vinyl polymeric backbone having grafted onto it monovalent siloxane polymeric moieties, and components consisting of non-silicone hydrophilic and hydrophobic monomers.
  • the silicone-containing monomers are exemplified by the general formula:
  • X is a polymerizable group, such as a vinyl group, which is part of the backbone of the polymer;
  • Y is a divalent linking group;
  • R is a hydrogen, hydroxyl, lower alkyl (e.g. C1-C4), aryl, alkaryl, alkoxy, or alkylamino;
  • Z is a monovalent polymeric siloxane moiety having an average molecular weight of at least about 500, is essentially unreactive under copolymerization conditions, and is pendant from the vinyl polymeric backbone described above;
  • n is 0 or 1; and
  • m is an integer from 1 to 3.
  • the preferred silicone-containing monomer has a weight average molecular weight of from about 1,000 to about 50,000, preferably from about 3,000 to about 40,000, most preferably from about 5,000 to about 20,000.
  • Nonlimiting examples of preferred silicone-containing monomers have the following formulas:
  • R is hydrogen or -COOH, preferably hydrogen;
  • R is hydrogen, methyl or -CH2COOH, preferably methyl;
  • Z is
  • R , R , and R independently are lower alkyl, alkoxy, alkylamino, hydrogen or hydroxyl, preferably alkyl; and r is an integer of from about 10 to about 700, preferably from about 40 to about 600, more preferably from about 70 to about 300. Most prefer
  • Silicone-containing adhesive and/or film-forming copolymers useful in the present invention comprise from 0% to about 90%, preferably from about 10%> to about 80%, more preferably from about 40% to about 75%> of hydrophobic monomer, from about 0%) to about 90%, preferably from about 5% to about 80% of hydrophilic monomer, and from about 5% to about 50%, preferably from about 10% to about 40%, more preferably from about 15% to about 25% of silicone-containing monomer.
  • any particular copolymer will help determine its formulation properties.
  • the copolymer can be optimized for inclusion in specific vehicles.
  • polymers which are soluble in an aqueous formulation preferably contain from 0% to about 70%, preferably from about 5% to about 70% of hydrophobic monomer, and from about 30%o to about 98%, preferably from about 30% to about 80%), of hydrophilic monomer, and from about 1% to about 40% of silicone-containing monomer.
  • Polymers which are dispersible preferably contain from 0%) to about 70%), more preferably from about 5% to about 70%, of hydrophobic monomer, and from about 20% to about 80%, more preferably from about 20%> to about 60%, of hydrophilic monomer, and from about 1% to about 40% of silicone-containing monomer.
  • the silicone-containing copolymers preferably have a weight average molecular weight of from about 10,000 to about 1,000,000, preferably from about 30,000 to about 300,000.
  • the preferred polymers comprise a vinyl polymeric backbone, preferably having a Tg or a Tm as defined above of about -20°C. and, grafted to the backbone, a polydimethylsiloxane macromer having a weight average molecular weight of from about 1,000 to about 50,000, preferably from about 5,000 to about 40,000, most preferably from about 7,000 to about 20,000.
  • the polymer is such that when it is formulated into the finished composition, and then dried, the polymer phase separates into a discontinuous phase which includes the polydimethylsiloxane macromer and a continuous phase which includes the backbone.
  • exemplary silicone grafted polymers for use in the present invention include the following, where the composition of the copolymer is given with the approximate weight percentage of each monomer used in the polymerization reaction to prepare the copolymer: N,N-dimethylacrylamide/isobutyl methacrylate/(PDMS macromer - 20,000 approximate molecular weight)(PDMS is polydimethylsiloxane) (20/60/20 w/w/w), copolymer of average molecular weight of about 400,000; N,N-dimethylacrylamide/(PDMS macromer -20,000 approximate molecular weight) (80/20 w/w), copolymer of average molecular weight of about 300,000; t-butylacrylate/N,N-dimethylacrylamide/
  • adjunct shape retention copolymers of this type contain hydrophobic monomers, silicone-containing monomers and hydrophilic monomers which comprise unsaturated organic mono- and polycarboxylic acid monomers, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half esters, itaconic acid, and salts thereof, and mixtures thereof.
  • a highly preferred copolymer is composed of acrylic acid, t-butyl acrylate and silicone-containing monomeric units, preferably with from about 20%) to about 90%>, preferably from about 30%> to about 80%>, more preferably from about 50%) to about 75%> t-butyl acrylate; from about 5%> to about 60%>, preferably from about 8% to about 45%o, more preferably from about 10%> to about 30% of acrylic acid; and from about 5%o to about 50%, preferably from about 7%> to about 40%, more preferably from about 10% to about 30%> of polydimethylsiloxane of an average molecular weight of from about 1,000 to about 50,000, preferably from about 5,000 to about 40,000, most preferably from about 7,000 to about 20,000.
  • Nonlimiting examples of acrylic acid tert-butyl acrylate/polydimethyl siloxane macromer copolymers useful in the present invention, with approximate monomer weight ratio, are: t- butylacrylate/acrylic acid/(polydimethylsiloxane macromer, 10,000 approximate molecular weight) (70/10/20 w/w/w), copolymer of average molecular weight of about 300,000; t-butylacrylate/acrylic acid/(polydimethylsiloxane macromer, 10,000 approximate molecular weight) (65/25/10 w/w/w), copolymer of average molecular weight of about 200,000; t-butyl acrylate/acrylic acid/(polydimethylsiloxane macromer, 10,000 approximate molecular weight) (63/20/17), copolymer of average molecular weight of from about 120,000 to about 150,000; and n-butylmethacrylate/acrylic acid (polydimethylsilox
  • a useful copolymer of this type is Diahold ® ME from Mitsubishi Chemical Co ⁇ ., which is a t-butyl acrylate/acrylic acid/ (polydimethylsiloxane macromer, 12,000 approximate molecular weight) (60/20/20), copolymer of average molecular weight of about 128,000.
  • silicone block copolymers comprising repeating block units of polysiloxanes.
  • silicone-containing block copolymers examples include U.S. Patent No. 5,523,365, to Geek et al., issued June 4, 1996; U.S. Patent No. 4,689,289, to Crivello, issued Aug. 25, 1987; U.S. Patent No. 4,584,356, to Crivello, issued April 22, 1986; Macromolecular Design, Concept & Practice, Ed: M. K. Mishra, Polymer Frontiers International, Inc., Hopewell Jet., NY (1994), and Block Copolymers, A. Noshay and J. E. McGrath, Academic Press, NY (1977), which are all inco ⁇ orated by reference herein in their entirety.
  • Other silicone block copolymers suitable for use herein are those described, along with methods of making them, in the above referenced and inco ⁇ orated U.S. Patent No. 5,658,577.
  • the silicone-containing block copolymers useful in the present invention can be described by the formulas A-B, A-B-A, and -(A-B) n - wherein n is an integer of 2 or greater.
  • A-B represents a diblock structure
  • A-B-A represents a triblock structure
  • - (A-B) n - represents a multiblock structure.
  • the block copolymers can comprise mixtures of diblocks, triblocks, and higher multiblock combinations as well as small amounts of homopolymers.
  • the silicone block portion, B can be represented by the following polymeric structure
  • each R is independently selected from the group consisting of hydrogen, hydroxyl, Ci -Cg alkyl, Ci -Cg alkoxy, C2-Cg alkylamino, styryl, phenyl, C ⁇ -Cg alkyl or alkoxy-substituted phenyl, preferably methyl; and m is an integer of about 10 or greater, preferablyof about 40 or greater, more preferably of about 60 or greater, and most preferably of about 100 or greater.
  • the non-silicone block, A comprises monomers selected from the monomers as described hereinabove in reference to the non-silicone hydrophilic and hydrophobic monomers for the silicone grafted copolymers. Vinyl blocks are preferred co-monomers.
  • the block copolymers preferably contain one or more non-silicone blocks, and up to about 50%), preferably from about 10%> to about 20%, by weight of one or more polydimethyl siloxane blocks.
  • sulfur-linked silicone containing copolymers including block copolymers.
  • the term "sulfur-linked” means that the copolymer contains a sulfur linkage (i.e., -S-), a disulfide linkage (i.e., -S-S-), or a sulfhydryl group (i.e.,-SH).
  • each G5 and Gg is independently selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and — ZSA, wherein A represents a vinyl polymeric segment consisting essentially of polymerized free radically polymerizable monomer, and Z is a divalent linking group (Useful divalent linking groups Z include but are not limited to the following: C ⁇ to C O alkylene, alkarylene, arylene, and alkoxyalkylene.
  • Z is selected from the group consisting of methylene and propylene for reasons of commercial availability.); each G2 comprises A; each G4 comprises A; each Ri is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl (Preferably, Ri represents monovalent moieties which can independently be the same or different selected from the group consisting of Ci .4 alkyl and hydroxyl for reasons of commercial availability.
  • R ⁇ is methyl.
  • each R is a divalent linking group (Suitable divalent linking groups include but are not limited to the following: C ⁇ to CI Q alkylene, arylene, alkarylene, and alkoxyalkylene.
  • R2 is selected from the group consisting of C 1.3 alkylene and C7-C10 alkarylene due to ease of synthesis of the compound.
  • R2 is selected from the group consisting of — CH2 — , 1,3-propylene, and
  • each R3 represents monovalent moieties which can independently be the same or different and are selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl (Preferably, R3 represents monovalent moieties which can independently be the same or different selected from the group consisting of C 1.4 alkyl and hydroxyl for reasons of commercial availability. Most preferably, R3 is methyl.); each R4 is a divalent linking group(Suitable divalent linking groups include but are not limited to the following: C ⁇ to C10 alkylene, arylene, alkarylene, and alkoxyalkylene.
  • R4 is selected from the group consisting of C 1.3 alkylene and C7-C10 alkarylene for ease of synthesis. Most preferably, R4 is selected from the group consisting of — CH ? — , 1,3-propylene, and
  • G5 comprises at least one — ZSA moiety
  • G comprises at least one — ZSA moiety.
  • A is a vinyl polymeric segment formed from polymerized free radically polymerizable monomers.
  • the selection of A is typically based upon the intended uses of the composition, and the properties the copolymer must possess in order to accomplish its intended pu ⁇ ose. If A comprises a block in the case of block copolymers, a polymer having AB and/or ABA architecture will be obtained depending upon whether a mercapto functional group — SH is attached to one or both terminal silicon atoms of the mercapto functional silicone compounds, respectively.
  • the weight ratio of vinyl polymer block or segment, to silicone segment of the copolymer can vary.
  • the preferred copolymers are those wherein the weight ratio of vinyl polymer segment to silicone segment ranges from about 98:2 to 50:50, in order that the copolymer possesses properties inherent to each of the different polymeric segments while retaining the overall polymer's solubility.
  • silicone-containing polymers are those containing hydrophilic portions, such as polyvinylpyrrolidone/quaternaries, polyacrylates, polyacrylamides, polysulfonates, and mixtures thereof, and are disclosed, e.g., in U.S. Pat. No. 5,120,812, inco ⁇ orated herein by reference.
  • the film-forming and/or adhesive silicone-containing copolymer of the present invention is present at least an effective amount to provide shape retention, typically from about 0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2%> to about 3%, even more preferably from about 0.3% to about 1.5%), by weight of the usage composition.
  • the silicone-containing copolymer is present in the composition in a sufficient amount to result in an amount of from about 0.001% to about 1%>, preferably from about 0.01% to about 0.5%, more preferably from about 0.02% to about 0.4% by weight of polymer per weight of dry fabrics.
  • the polymer useful in providing shape retention in the composition of the present invention should be cyclodextrin-compatible, that is it should not substantially form complexes with cyclodextrin so as to diminish performance of the cyclodextrin and/or the polymer.
  • Complex formation affects both the ability of the cyclodextrin to absorb odors and the ability of the polymer to impart shape retention to fabric.
  • the monomers having pendant groups that can complex with cyclodextrin are not preferred because they can form complexes with cyclodextrin.
  • Examples of such monomers are acrylic or methacrylic acid esters of Cy-C ⁇ g alcohols, such as neodecanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-l-heptanol, 2-ethyl-l-hexanol, 3,5-dimethyl-l-hexanol, 3,5,5-trimethyl-l-hexanol, and 1-decanol; aromatic vinyls, such as styrene; t- butylstyrene; vinyl toluene; and the like.
  • Cy-C ⁇ g alcohols such as neodecanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-l-heptanol, 2-ethyl-l-hexanol, 3,5-dimethyl-l-hexanol, 3,5,5-trimethyl-l-hexanol, and 1-decanol
  • Starch is not normally preferred, since it makes the fabric resistant to deformation. However, it does provide increased "body” which is often desired. Starch is particularly preferred in compositions of this invention to be used with ironing. When used, starch is solubilized or dispersed in the composition. Any type of starch, e.g. those derived from corn, wheat, rice, grain sorghum, waxy grain sorghum, waxy maize or tapioca, or mixtures thereof and water soluble or dispersible modifications or derivatives thereof, can be used in the composition of the present invention.
  • Low viscosity commercially available propoxylated and/or ethoxylated starches are useable in the present composition and are preferred since their low viscosity at relatively high solids concentrations make them very adaptable to spraying processes.
  • Suitable alkoxylated, low viscosity starches are submicron sized particles of hydrophobic starch that are readily dispersed in water and are prepared by alkoxylation of granular starch with a monofunctional alkoxylating agent which provides the starch with ether linked hydrophilic groups. A suitable method for their preparation is taught in U.S. Pat. No. 3,462,283.
  • the propoxylated or ethoxylated starch derivatives are dispersed in the aqueous medium in an amount of from about 0.1% to about 10%, preferably from about 0.5% to about 6%>, more preferably from about 1%> to about 4% by weight of the usage composition.
  • Lithium Salts are dispersed in the aqueous medium in an amount of from about 0.1% to about 10%, preferably from about 0.5% to about 6%>, more preferably from about 1%> to about 4% by weight of the usage composition.
  • Optional lithium salts are useful in the fabric care compositions of the present invention for providing improved fabric wrinkle control.
  • Nonlimiting examples of lithium salts that are useful in the present invention are lithium bromide, lithium chloride, lithium lactate, lithium benzoate, lithium acetate, lithium sulfate, lithium tartrate, and/or lithium bitartrate, preferably lithium bromide and/or lithium lactate.
  • Some water soluble salts such as , lithium benzoate are not preferred when the optional cyclodextrin is present because they can form complexes with cyclodextrin.
  • Useful levels of lithium salts are from about 0.1% to about 10%, preferably from about 0.5% to about 7%), more preferably from about 1% to about 5%, by weight of the usage composition.
  • the composition can contain a hydrophilic plasticizer to soften both the fabric fibers, especially cotton fibers, and the adjunct adhesive and/or film-forming shape retention polymers.
  • a hydrophilic plasticizer to soften both the fabric fibers, especially cotton fibers, and the adjunct adhesive and/or film-forming shape retention polymers.
  • the preferred hydrophilic plasticizers are short chain low molecular weight polyhydric alcohols, such as is glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, sorbitol, erythritol or mixtures thereof, more preferably diethylene glycol, dipropylene glycol, ethylene glycol, propylene glycol and mixtures thereof.
  • a hydrophilic plasticizer is used, it is present in the at a level of from 0.01%> to 5%, preferably from 0.05% to 2%, more preferably from 0. 1%> to 1%) by weight of the usage composition.
  • Surfactant is an optional but highly preferred ingredient of the present invention. Surfactant is especially useful in the composition to facilitate the dispersion and/or solubilization of wrinkle control agents such as silicones and/or certain relatively water insoluble adjunct shape retention polymers.
  • the surfactant can provide some plasticizing effect to the adjunct shape retention polymers resulting in a more flexible polymer network.
  • Such surfactant is preferably included when the composition is used in a spray dispenser in order to enhance the spray characteristics of the composition and allow the composition, including the fabric care polysaccharide with globular structure, to distribute more evenly, and to prevent clogging of the spray apparatus. The spreading of the composition can also allow it to dry faster, so that the treated material is ready to use sooner.
  • the surfactant facilitates the dispersion of many actives such as antimicrobial actives and perfumes in the concentrated aqueous compositions.
  • Suitable surfactant useful in the present invention is nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, and mixtures thereof.
  • surfactant When surfactant is used in the composition of the present invention, it is added at an effective amount to provide one, or more of the benefits described herein, typically from about 0.01%) to about 5%, preferably from about 0.05% to about 3%, more preferably from about 0.1% to about 2%, and even more preferably, from about 0.2% to about 1%, by weight of the usage composition.
  • a preferred type of surfactant is ethoxylated surfactant, such as addition products of ethylene oxide with fatty alcohols, fatty acids, fatty amines, etc.
  • addition products of mixtures of ethylene oxide and propylene oxide with fatty alcohols, fatty acids, fatty amines can be used.
  • the ethoxylated surfactant includes compounds having the general formula:
  • R8-Z-(CH 2 CH 2 O) s B wherein R° is an alkyl group or an alkyl aryl group, selected from the group consisting of primary, secondary and branched chain alkyl hydrocarbyl groups, primary, secondary and branched chain alkenyl hydrocarbyl groups, and/or primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups having from about 6 to about 20 carbon atoms, preferably from about 8 to about 18, more preferably from about 10 to about 15 carbon atoms; s is an integer from about 2 to about 45, preferably from about 2 to about 20, more preferably from about 2 to about 15; B is a hydrogen, a carboxylate group, or a sulfate group; and linking group Z is -O-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)-, and mixtures thereof, in which R, when present,
  • nonionic surfactants herein are characterized by an HLB (hydrophilic- lipophilic balance) of from 5 to 20, preferably from 6 to 15.
  • HLB hydrophilic- lipophilic balance
  • Nonlimiting examples of preferred ethoxylated surfactant are: o
  • R being C ⁇ -Cl8 alkyl and/or alkenyl group, more preferably C10-C14, and s being from about 2 to about 8, preferably from about 2 to about 6;
  • R being C8-C18 alkyl and/or alkenyl, e.g., 3-hexadecyl, 2-octadecyl, 4-eicosanyl, and 5-eicosanyl, and s being from about 2 to about 10;
  • alkyl phenol ethoxylates wherein the alkyl phenols having an alkyl or alkenyl group containing from 3 to 20 carbon atoms in a primary, secondary or branched chain configuration, preferably from 6 to 12 carbon atoms, and s is from about 2 to about 12, preferably from about 2 to about 8;
  • branched chain primary and secondary alcohols or Guerbet alcohols which are available, e.g., from the well-known "OXO" process or modification thereof are ethoxylated.
  • alkyl ethoxylate surfactants with each R ⁇ being C8-C16 straight chain and/or branch chain alkyl and the number of ethyleneoxy groups s being from about 2 to about 6, preferably from about 2 to about 4, more preferably with R being C8-C15 alkyl and s being from about 2.25 to about 3.5.
  • These nonionic surfactants are characterized by an HLB of from 6 to about 11, preferably from about 6.5 to about 9.5, and more preferably from about 7 to about 9.
  • nonionic surfactant selected from the group consisting of fatty acid (C 12- ⁇ s) esters of ethoxylated (EO 5- ⁇ 0 o) sorbitans. More preferably said surfactant is selected from the group consisting of mixtures of laurate esters of sorbitol and sorbitol anhydrides; mixtures of stearate esters of sorbitol and sorbitol anhydrides; and mixtures of oleate esters of sorbitol and sorbitol anhydrides.
  • said surfactant is selected from the group consisting of Polysorbate 20, which is a mixture of laurate esters of sorbitol and sorbitol anhydrides consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; Polysorbate 60 which is a mixture of stearate esters of sorbitol and sorbitol anhydride, consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; Polysorbate 80 which is a mixture of oleate esters of sorbitol and sorbitol anhydrides, consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; and mixtures thereof. Most preferably, said surfactant is Polysorbate 60.
  • ethoxylated surfactant examples include carboxylated alcohol ethoxylate, also known as ether carboxylate, with R ⁇ having from about 12 to about 16 carbon atoms and s being from about 5 to about 13; ethoxylated quaternary ammonium surfactants, such as PEG-5 cocomonium methosulfate, PEG- 15 cocomonium chloride, PEG-15 oleammonium chloride and bis(polyethoxyethanol)tallow ammonium chloride.
  • carboxylated alcohol ethoxylate also known as ether carboxylate, with R ⁇ having from about 12 to about 16 carbon atoms and s being from about 5 to about 13
  • ethoxylated quaternary ammonium surfactants such as PEG-5 cocomonium methosulfate, PEG- 15 cocomonium chloride, PEG-15 oleammonium chloride and bis(polyethoxyethanol)tallow ammonium chloride.
  • Suitable nonionic ethoxylated surfactants are ethoxylated alkyl amines derived from the condensation of ethylene oxide with hydrophobic alkyl amines, with R° having from about 8 to about 22 carbon atoms and s being from about 3 to about 30.
  • alkylpolysaccharides which are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 8 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkylpolyglycosides have the formula
  • R 2 O(C n H 2n O)t(glycosyl) x
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • silicone surfactants Another class of preferred surfactants that are useful in the formulation of the compositions of the present invention, to solubilize and/or disperse silicone lubricants and/or silicone-containing adjunct shape retention copolymers, are silicone surfactants. They can be used alone and/or preferably in combination with the preferred alkyl ethoxylate surfactants described herein above.
  • Nonlimiting examples of silicone surfactants are the polyalkylene oxide polysiloxanes having a dimethyl polysiloxane hydrophobic moiety and one or more hydrophilic polyalkylene side chains, and having the general formula:
  • R 1 (CH 3 )2SiO— [(CH 3 ) 2 SiO] a — [(CH 3 )(R 1 )SiO]b— Si(CH 3 )2— R 1 " wherein a + b are from about 1 to about 50, preferably from about 3 to about 30 , more preferably from about 10 to about 25, and each R is the same or different and is selected from the group consisting of methyl and a poly(ethyleneoxide/propyleneoxide) copolymer group having the general formula:
  • each R2 is the same or different and is selected from the group consisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group, preferably hydrogen and methyl group.
  • Each polyalkylene oxide polysiloxane has at least one R group being a poly(ethyleneoxide/propyleneoxide) copolymer group.
  • Nonlimiting examples of this type of surfactants are the Silwet® surfactants which are available OSi Specialties, Inc., Danbury, Connecticut.
  • Representative Silwet surfactants which contain only ethyleneoxy (C2H4O) groups are as follows.
  • Nonlimiting examples of surfactants which contain both ethyleneoxy (C2 H4 O) and propyleneoxy (C3 Hg O) groups are as follows.
  • the molecular weight of the polyalkyleneoxy group (R*) is less than or equal to about 10,000.
  • the molecular weight of the polyalkyleneoxy group is less than or equal to about 8,000, and most preferably ranges from about 300 to about 5,000.
  • the values of c and d can be those numbers which provide molecular weights within these ranges.
  • the number of ethyleneoxy units (-C2H4O) in the polyether chain (R*) must be sufficient to render the polyalkylene oxide polysiloxane water dispersible or water soluble. If propyleneoxy groups are present in the polyalkylenoxy chain, they can be distributed randomly in the chain or exist as blocks.
  • Silwet surfactants which contain only propyleneoxy groups without ethyleneoxy groups are not preferred.
  • Preferred Silwet surfactants are L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof.
  • the most preferred Silwet surfactant for solubilizing and/or dispersing the adjunct silicone- containing shape retention polymers and/or the volatile silicone is the low molecular weight L-77.
  • polyalkylene oxide polysiloxane surfactants can also provide other benefits, such as antistatic benefits, lubricity and softness to fabrics.
  • silicone surfactants are those having a hydrophobic moiety and hydrophilic ionic groups, including, e.g., anionic, cationic, and amphoteric groups.
  • anionic silicone surfactants are silicone sulfosuccinates, silicone sulfates, silicone phosphates, silicone carboxylates, and mixtures thereof, as disclosed respectively in U.S. Pat. Nos, 4,717,498, 4,960,845, 5,149,765, and 5,296,434.
  • Nonlimiting examples of cationic silicone surfactants are silicone alkyl quats (quaternary ammoniums), silicone amido quats, silicone imidazoline quats, and mixtures thereof, as disclosed respectively in U.S. Pat. Nos.
  • Nonlimiting examples of amphoteric silicone surfactants are silicone betaines, silicone amino proprionates, silicone phosphobetaines, and mixtures thereof, as disclosed respectively in U.S. Pat. Nos. 4,654,161, 5,073,619, and 5,237,035. All of these patents are inco ⁇ orated herein by reference.
  • Fabric care composition of the present invention to be used in the wash cycle can be either used along with a general laundry detergent or actually a detergent composition comprising a fabric care polysaccharide with globular structure.
  • the detergent compositions according to the present invention comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.
  • the surfactant is typically present at a level of from 0.1 %> to 60%> by weight. More preferred levels of inco ⁇ oration are 1% to 35%) by weight, most preferably from % to 30% by weight of detergent compositions in accord with the invention.
  • the surfactant is preferably formulated to be compatible with the fabric care polysaccharide with globular structure present in the composition.
  • nonionic, anionic, cationic, ampholytic, zwitterionic and semi-polar nonionic surfactants are disclosed in U.S. Patent Nos. 5,707,950 and 5,576,282, inco ⁇ orated herein by reference.
  • Nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:
  • R - C(O) - N(R!) - Z wherein Rl is H, or R* is C1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is 05.3 ⁇ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R* is methyl
  • R2 is a straight C1 1.15 alkyl or C16-I8 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably Ci 2-C ⁇ g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • the laundry detergent compositions of the present invention typically comprise from about 1%> to about 40%, preferably from about 3% to about 20%) by weight of such anionic surfactants.
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
  • R ⁇ R 2 R3R4N+X- wherein R ⁇ is Cg-Ci 6 alkyl, each of R2, R3 and R4 is independently C1 -C4 alkyl, C1 - C4 hydroxy alkyl, benzyl, and -(C2H4Q) 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 detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of such cationic surfactants.
  • the detergent compositions of the present invention typically comprise from 0.2% to about 15%>, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
  • the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1%> to about 10%> by weight of such zwitterionic surfactants.
  • the detergent compositions of the present invention typically comprise from 0.2%> to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
  • the detergent composition of the present invention can further comprise a cosurfactant selected from the group of primary or tertiary amines.
  • Suitable primary amines for use herein include amines according to the formula RjNH2 wherein R is a 5-C12 preferably Cg-Ci Q alkyl chain or R4X(CH2) n> X is - O-, -C(O)NH- or -NH- R4 is a Cg-Ci 2 alkyl chain n is between 1 to 5, preferably 3.
  • R ⁇ alkyl chains can be straight or branched and can 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 can be selected from 1 -hexylamine, 1 -octylamine, 1- decylamine and laurylamine.
  • Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amido propylamine and amido propylamine.
  • Suitable tertiary amines for use herein include tertiary amines having the formula Ri R2R3N wherein R ⁇ and R2 are C1 -C ⁇ alkyl chains or
  • R5 ( C H 2 — CH ⁇ ) x H
  • R3 is either a Cg-Ci 2, preferably Cg-C ⁇ o alkyl chain, or R3 is R4X(CH2) n , whereby X is -O-, -C(O)NH- or -NH- R4 is a C4-C12, n is between 1 to 5, preferably 2-3, R5 is H or C1-C2 alkyl and x is between 1 to 6 .
  • R3 and R4 can be linear or branched ; R3 alkyl chains can be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
  • Preferred tertiary amines are R1 R2R3N where Ri is a Cg-Ci 2 alkyl chain, R2 and R3 are C1 -C3 alkyl or
  • Ri is C6-C12 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1 -C4
  • Most preferred amines of the present invention include 1-octylamine, 1- hexylamine, 1 -decylamine, l-dodecylamine,C8-10oxypropylamine, N coco 1- 3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyethyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8- 10 amidopropyldimethylamine and CIO amidopropyldimethylamine.
  • the most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1 -decylamine, 1-dodecylamine. Especially desirable are n- dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
  • compositions for odor control are of the type disclosed in U.S. Pats. 5,534,165; 5,578,563; 5,663,134; 5,668,097; 5,670,475; and 5,714,137, Trinh et al. issued Jul. 9, 1996; Nov. 26, 1996; Sep. 2, 1997; Sep. 16, 1997; Sep. 23, 1997; and Feb. 3, 1998 respectively, all of said patents being inco ⁇ orated herein by reference.
  • Fabric care compositions of the present invention can contain several different optional odor control agents, preferably cyclodextrins, water soluble zinc salts, water soluble copper salts, and mixtures thereof.
  • Cyclodextrin includes any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives and/or mixtures thereof.
  • the alpha-cyclodextrin consists of six glucose units
  • the beta-cyclodextrin consists of seven glucose units
  • the gamma-cyclodextrin consists of eight glucose units arranged in donut-shaped rings.
  • the specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structures with hollow interiors of specific volumes.
  • the "lining" of each internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms; therefore, this surface is fairly hydrophobic.
  • the unique shape and physical-chemical properties of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. Many odorous molecules can fit into the cavity including many malodorous molecules and perfume molecules.
  • cyclodextrins and especially mixtures of cyclodextrins with different size cavities, can be used to control odors caused by a broad spectrum of organic odoriferous materials, which may, or may not, contain reactive functional groups.
  • the complexation between cyclodextrin and odorous molecules occurs rapidly in the presence of water.
  • the extent of the complex formation also depends on the polarity of the absorbed molecules.
  • strongly hydrophilic molecules (those which are highly water-soluble) are only partially absorbed, if at all. Therefore, cyclodextrin does not complex effectively with some very low molecular weight organic amines and acids when they are present at low levels on wet fabrics.
  • the fabric is being dried off, some low molecular weight organic amines and acids have more affinity and will complex with the cyclodextrins more readily.
  • the cavities within the cyclodextrin in the solution of the present invention should remain essentially unfilled (the cyclodextrin remains uncomplexed) while in solution, in order to allow the cyclodextrin to absorb various odor molecules when the solution is applied to a surface.
  • Non-derivatised (normal) beta-cyclodextrin can be present at a level up to its solubility limit of about 1.85% (about 1.85g in 100 grams of water) at room temperature. Beta-cyclodextrin is not preferred in compositions which call for a level of cyclodextrin higher than its water solubility limit.
  • Non-derivatised beta-cyclodextrin is generally not preferred when the composition contains surfactant since it affects the surface activity of most of the preferred surfactants that are compatible with the derivatised cyclodextrins.
  • the odor absorbing solution of the present invention is clear.
  • the term "clear” as defined herein means transparent or translucent, preferably transparent, as in “water clear,” when observed through a layer having a thickness of less than about 10 cm.
  • the cyclodextrins used in the present invention are highly water- soluble such as, alpha-cyclodextrin and/or derivatives thereof, gamma-cyclodextrin and/or derivatives thereof, derivatised beta-cyclodextrins, and/or mixtures thereof.
  • the derivatives of cyclodextrin consist mainly of molecules wherein some of the OH groups are converted to OR groups.
  • Cyclodextrin derivatives include, e.g., those with short chain alkyl groups such as methylated cyclodextrins, and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those with hydroxyalkyl substituted groups, such as hydroxypropyl cyclodextrins and/or hydroxyethyl cyclodextrins, wherein R is a - CH2-CH(OH)-CH3 or a "CH2CH2-OH group; branched cyclodextrins such as maltose- bonded cyclodextrins; cationic cyclodextrins such as those containing 2-hydroxy-3- (dimethylamino)propyl ether, wherein R is CH2-CH(OH)-CH2-N(CH3)2 which is cationic at low pH; quaternary ammonium, e.g., 2-hydroxy-3-(trimethyl
  • Highly water-soluble cyclodextrins are those having water solubility of at least about 10 g in 100 ml of water at room temperature, preferably at least about 20 g in 100 ml of water, more preferably at least about 25 g in 100 ml of water at room temperature.
  • the availability of solubilized, uncomplexed cyclodextrins is essential for effective and efficient odor control performance. Solubilized, water-soluble cyclodextrin can exhibit more efficient odor control performance than non-water-soluble cyclodextrin when deposited onto surfaces, especially fabric.
  • Examples of preferred water-soluble cyclodextrin derivatives suitable for use herein are hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin.
  • Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from about 1 to about 14, more preferably from about 1.5 to about 7, wherein the total-number of OR groups per cyclodextrin is defined as the degree of substitution.
  • Methylated cyclodextrin derivatives typically have a degree of substitution of from about 1 to about 18, preferably from about 3 to about 16.
  • a known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl- ⁇ -cyclodextrin, commonly known as DIMEB, in which each glucose unit has about 2 methyl groups with a degree of substitution of about 14.
  • DIMEB heptakis-2,6-di-O-methyl- ⁇ -cyclodextrin
  • a preferred, more commercially available, methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin, commonly known as RAMEB, having different degrees of substitution, normally of about 12.6.
  • RAMEB is more preferred than DIMEB, since DIMEB affects the surface activity of the preferred surfactants more than RAMEB.
  • the preferred cyclodextrins are available, e.g., from Cerestar USA, Inc. and Wacker Chemicals (USA), Inc.
  • cyclodextrins absorb odors more broadly by complexing with a wider range of odoriferous molecules having a wider range of molecular sizes.
  • the cyclodextrins is alpha- cyclodextrin and its derivatives thereof, gamma-cyclodextrin and its derivatives thereof, and/or derivatised beta-cyclodextrin, more preferably a mixture of alpha-cyclodextrin, or an alpha-cyclodextrin derivative, and derivatised beta-cyclodextrin, even more preferably a mixture of derivatised alpha-cyclodextrin and derivatised beta-cyclodextrin, most preferably a mixture of hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta- cyclodextrin, and/or a mixture of methylated alpha-cyclod
  • the composition is preferably used as a spray.
  • Typical levels of cyclodextrin in usage compositions for usage conditions are from about 0.01% to about 5%, preferably from about 0.1% to about 4%, more preferably from about 0.5%) to about 2%> by weight of the composition. It is preferable that the treated fabric contains a level of less than about 5 mg of cyclodextrin per gram of fabric, more preferably less than about 2 mg of cyclodextrin per gram of fabric.
  • Low Molecular Weight Polyols Low molecular weight polyols with relatively high boiling points, as compared to water, such as ethylene glycol, propylene glycol and/or glycerol are preferred optional ingredients for improving odor control performance of the composition of the present invention when cyclodextrin is present. Not to be bound by theory, it is believed that the inco ⁇ oration of a small amount of low molecular weight glycols into the composition of the present invention enhances the formation of the cyclodextrin inclusion complexes as the fabric dries.
  • the polyols ability to remain on the fabric for a longer period of time than water, as the fabric dries allows it to form ternary complexes with the cyclodextrin and some malodorous molecules.
  • the addition of the glycols is believed to fill up void space in the cyclodextrin cavity that is unable to be filled by some malodor molecules of relatively smaller sizes.
  • the glycol used is glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol or mixtures thereof, more preferably ethylene glycol and/or propylene glycol. Cyclodextrins prepared by processes that result in a level of such polyols are highly desirable, since they can be used without removal of the polyols.
  • Some polyols e.g., dipropylene glycol, are also useful to facilitate the solubilization of some perfume ingredients in the composition of the present invention.
  • glycol is added to the composition of the present invention at a level of from about 0.01 % to about 3%, by weight of the composition, preferably from about 0.05%) to about 1%, more preferably from about 0.1% to about 0.5%, by weight of the composition.
  • the preferred weight ratio of low molecular weight polyol to cyclodextrin is from about 2:1,000 to about 20:100, more preferably from about 3:1,000 to about 15:100, even more preferably from about 5:1,000 to about 10:100, and most preferably from about 1 :100 to about 7:100.
  • the present invention can include metallic salts for added odor abso ⁇ tion and/or antimicrobial benefit for the cyclodextrin solution when cyclodextrin is present.
  • the metallic salts are selected from the group consisting of copper salts, zinc salts, and mixtures thereof.
  • Copper salts have some antimicrobial benefits. Specifically, cupric abietate acts as a fungicide, copper acetate acts as a mildew inhibitor, cupric chloride acts as a fungicide, copper lactate acts as a fungicide, and copper sulfate acts as a germicide. Copper salts also possess some malodor control abilities. See U. S. Pat. No. 3,172,817, Leupold, et al., which discloses deodorizing compositions for treating disposable articles, comprising at least slightly water-soluble salts of acylacetone, including copper salts and zinc salts, all of said patents are inco ⁇ orated herein by reference.
  • the preferred zinc salts possess malodor control abilities.
  • Zinc has been used most often for its ability to ameliorate malodor, e.g., in mouth wash products, as disclosed in U.S. Pat. Nos. 4,325,939, issued Apr. 20, 1982 and 4,469,674, issued Sept. 4, 1983, to N. B. Shah, et al, all of which are inco ⁇ orated herein by reference.
  • Highly- ionized and soluble zinc salts such as zinc chloride, provide the best source of zinc ions.
  • Zinc borate functions as a fungistat and a mildew inhibitor
  • zinc caprylate functions as a fungicide
  • zinc chloride provides antiseptic and deodorant benefits
  • zinc ricinoleate functions as a fungicide
  • zinc sulfate heptahydrate functions as a fungicide
  • zinc undecylenate functions as a fungistat.
  • the metallic salts are water-soluble zinc salts, copper salts or mixtures thereof, and more preferably zinc salts, especially ZnCl2- These salts are preferably present in the present invention primarily to absorb amine and sulfur-containing compounds that have molecular sizes too small to be effectively complexed with the cyclodextrin molecules.
  • Low molecular weight sulfur-containing materials e.g., sulfide and mercaptans, are components of many types of malodors, e.g., food odors (garlic, onion), body/perspiration odor, breath odor, etc.
  • Low molecular weight amines are also components of many malodors, e.g., food odors, body odors, urine, etc.
  • metallic salts When metallic salts are added to the composition of the present invention they are typically present at a level of from about 0.1% to about 10%>, preferably from about 0.2%o to about 8%, more preferably from about 0.3% to about 5% by weight of the usage composition.
  • the pH of the solution is adjusted to less than about 7, more preferably less than about 6, most preferably, less than about 5, in order to keep the solution clear.
  • Water-soluble alkali metal carbonate and/or bicarbonate salts such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, sodium carbonate, and mixtures thereof can be added to the composition of the present invention in order to help to control certain acid-type odors.
  • Preferred salts are sodium carbonate monohydrate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and mixtures thereof. When these salts are added to the composition of the present invention, they are typically present at a level of from about 0.1% to about 5%, preferably from about 0.2%) to about 3%, more preferably from about 0.3% to about 2%, by weight of the composition.
  • incompatible metal salts not be present in the invention.
  • the composition should be essentially free of zinc and other incompatible metal ions, e.g., Ca, Fe, Ba, etc. which form water-insoluble salts.
  • zeolites and/or activated carbon can also be used.
  • a preferred class of zeolites is characterized as "intermediate" silicate/aluminate zeolites.
  • the intermediate zeolites are characterized by SiO2/AlO2 molar ratios of less than about 10. Preferably the molar ratio of SiO2/AlO2 ranges from about 2 to about 10.
  • the intermediate zeolites have an advantage over the "high" zeolites.
  • the intermediate zeolites have a higher affinity for amine-type odors, they are more weight efficient for odor abso ⁇ tion because they have a larger surface area, and they are more moisture tolerant and retain more of their odor absorbing capacity in water than the high zeolites.
  • a wide variety of intermediate zeolites suitable for use herein are commercially available as Valfor® CP301-68, Valfor® 300-63, Valfor® CP300-35, and Valfor® CP300-56, available from PQ Co ⁇ oration, and the CBV100® series of zeolites from Conteka.
  • Zeolite materials marketed under the trade name Abscents and Smellrite , available from The Union Carbide Co ⁇ oration and UOP are also preferred. These materials are typically available as a white powder in the 3-5 micron particle size range. Such materials are preferred over the intermediate zeolites for control of sulfur- containing odors, e.g., thiols, mercaptans.
  • the carbon material suitable for use in the present invention is the material well known in commercial practice as an absorbent for organic molecules and/or for air purification pu ⁇ oses. Often, such carbon material is referred to as "activated” carbon or "activated” charcoal. Such carbon is available from commercial sources under such trade names as; Calgon-Type CPG®; Type PCB®; Type SGL®; Type CAL®; and Type OL®.
  • the fabric care composition of the present invention can also optionally provide a "scent signal" in the form of a pleasant odor which provides a freshness impression to the treated fabrics.
  • the scent signal can be designed to provide a fleeting perfume scent. When perfume is added as a scent signal, it is added only at very low levels, e.g., from about 0.001% to about 0.5%, preferably from about 0.003% to about 0.3%, more preferably from about 0.005% to about 0.2%, by weight of the usage composition.
  • Perfume can also be added as a more intense odor in product and on fabrics. When stronger levels of perfume are preferred, relatively higher levels of perfume can be added.
  • perfume can be inco ⁇ orated into the composition of the present invention.
  • the preferred perfume ingredients are those suitable for use to apply on fabrics and garments. Typical examples of such preferred ingredients are given in U.S. Pat. 5,445,747, issued Aug. 29, 1995 to Kvietok et al., inco ⁇ orated herein by reference.
  • perfume includes fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances.
  • natural i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants
  • artificial i.e., a mixture of different nature oils or oil constituents
  • synthetic i.e., synthetically produced
  • perfumes are complex mixtures of a plurality of organic compounds.
  • perfume ingredients useful in the perfumes of the present invention compositions include, but are not limited to, those materials disclosed in said patents.
  • the perfumes useful in the present invention compositions are preferably substantially free of halogenated materials and nitromusks.
  • Suitable solvents, diluents or carriers for perfumes ingredients mentioned above are for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc.
  • the amount of such solvents, diluents or carriers inco ⁇ orated in the perfumes is preferably kept to the minimum needed to provide a homogeneous perfume solution.
  • Perfume can be present at a level of from 0% to about 15%, preferably from about 0.1% to about 8%, and more preferably from about 0.2%> to about 5%, by weight of the finished fabric care composition.
  • cyclodextrin When cyclodextrin is present, it is essential that the perfume be added at a level wherein even if all of the perfume in the composition were to complex with the cyclodextrin molecules when cyclodextrin is present, there will still be an effective level of uncomplexed cyclodextrin molecules present in the solution to provide adequate odor control.
  • perfume is typically present at a level wherein less than about 90%> of the cyclodextrin complexes with the perfume, preferably less than about 50%) of the cyclodextrin complexes with the perfume, more preferably, less than about 30% of the cyclodextrin complexes with the perfume, and most preferably, less than about 10% of the cyclodextrin complexes with the perfume.
  • the cyclodextrin to perfume weight ratio should be greater than about 8:1, preferably greater than about 10:1, more preferably greater than about 20:1, even more preferably greater than 40:1 and most preferably greater than about 70:1.
  • the perfume is hydrophilic and is composed predominantly of ingredients selected from two groups of ingredients, namely, (a) hydrophilic ingredients having a ClogP of less than about 3.5, more preferably less than about 3.0, and (b) ingredients having significant low detection threshold, and mixtures thereof.
  • a hydrophilic ingredients having a ClogP of less than about 3.5, more preferably less than about 3.0 ingredients having significant low detection threshold, and mixtures thereof.
  • at least about 50%>, preferably at least about 60%, more preferably at least about 70%>, and most preferably at least about 80%> by weight of the perfume is composed of perfume ingredients of the above groups (a) and (b).
  • the cyclodextrin to perfume weight ratio is typically of from about 2:1 to about 200:1; preferably from about 4:1 to about 100:1, more preferably from about 6:1 to about 50:1, and even more preferably from about 8:1 to about 30:1.
  • the hydrophilic perfume ingredients are more soluble in water, have less of a tendency to complex with the cyclodextrins, and are more available in the odor absorbing composition than the ingredients of conventional perfumes.
  • the degree of hydrophobicity of a perfume ingredient can be correlated with its octanol/water partition coefficient P.
  • the octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. A perfume ingredient with a greater partition coefficient P is considered to be more hydrophobic. Conversely, a perfume ingredient with a smaller partition coefficient P is considered to be more hydrophilic.
  • the partition coefficients of the perfume ingredients normally have high values, they are more conveniently given in the form of their logarithm to the base 10, logP.
  • the preferred perfume hydrophilic perfume ingredients of this invention have logP of about 3.5 or smaller, preferably of about 3.0 or smaller.
  • the logP of many perfume ingredients have been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP” program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database.
  • the "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cfi, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p.
  • the fragment approach is based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
  • the ClogP values which are the most reliable and widely used estimates for this physicochemical property, are used instead of the experimental logP values in the selection of perfume ingredients which are useful in the present invention.
  • Non-limiting examples of the more preferred hydrophilic perfume ingredients are allyl amyl glycolate, allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisyl acetate, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, calone, camphor gum, laevo-carveol, d-carvone, laevo-carvone, cinnamic alcohol, cinnamyl acetate, cinnamic alcohol, cinnamyl formate, cinnamyl propionate, cis-jasmone, cis-3-hexenyl acetate, coumarin, cuminic alcohol, cuminic aldehyde, Cyclal C,
  • Nonlimiting examples of other preferred hydrophilic perfume ingredients which can be used in perfume compositions of this invention are allyl heptoate, amyl benzoate, anethole, benzophenone, carvacrol, citral, citronellol, citronellyl nitrile, cyclohexyl ethyl acetate, cymal, 4-decenal, dihydro isojasmonate, dihydro myrcenol, ethyl methyl phenyl glycidate, fenchyl acetate, florhydral, gamma-nonalactone, geranyl formate, geranyl nitrile, hexenyl isobutyrate, alpha-ionone, isobornyl acetate, isobutyl benzoate, isononyl alcohol, isomenthol, para-isopropyl phenylacetaldehyde, isopulegol, linalyl
  • the preferred perfume compositions used in the present invention contain at least 4 different hydrophilic perfume ingredients, preferably at least 5 different hydrophilic perfume ingredients, more preferably at least 6 different hydrophilic perfume ingredients, and even more preferably at least 7 different hydrophilic perfume ingredients. Most common perfume ingredients which are derived from natural sources are composed of a multitude of components. When each such material is used in the formulation of the preferred perfume compositions of the present invention, it is counted as one single ingredient, for the pu ⁇ ose of defining the invention.
  • the odor detection threshold of an odorous material is the lowest vapor concentration of that material which can be olfactorily detected.
  • the odor detection threshold and some odor detection threshold values are discussed in, e.g., "Standardized Human Olfactory Thresholds", M. Devos et al, IRL Press at Oxford University Press, 1990, and "Compilation of Odor and Taste Threshold Values Data", F. A. Fazzalari, editor, ASTM Data Series DS 48 A, American Society for Testing and Materials, 1978, both of said publications being inco ⁇ orated by reference.
  • perfume ingredients that have low odor detection threshold values can improve perfume odor character, even though they are not as hydrophilic as perfume ingredients of group (a) which are given hereinabove.
  • Perfume ingredients that do not belong to group (a) above, but have a significantly low detection threshold, useful in the composition of the present invention are selected from the group consisting of ambrox, bacdanol, benzyl salicylate, butyl anthranilate, cetalox, damascenone, alpha-damascone, gamma- dodecalactone, ebanol, herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-ionone, alpha-isomethylionone, lilial, methyl nonyl ketone, gamma-undecalactone, undecylenic aldehyde, and mixtures thereof.
  • These materials are preferably present at low levels in addition to the hydrophilic ingredients of group (a), typically less than about 20%>, preferably less than about 15%>, more preferably less than about 10%>, by weight of the total perfume compositions of the present invention. However, only low levels are required to provide an effect.
  • hydrophilic ingredients of group (a) that have a significantly low detection threshold, and are especially useful in the composition of the present invention.
  • these ingredients are allyl amyl glycolate, anethole, benzyl acetone, calone, cinnamic alcohol, coumarin, cyclogalbanate, Cyclal C, cymal, 4-decenal, dihydro isojasmonate, ethyl anthranilate, ethyl-2-m ethyl butyrate, ethyl methylphenyl glycidate, ethyl vanillin, eugenol, flor acetate, florhydral, fructone, frutene, heliotropin, keone, indole, iso cyclo citral, isoeugenol, lyral, methyl heptine carbonate, linalool, methyl anthranilate, methyl dihydrojasmon
  • the fabric care composition of the present invention comprise an effective amount, to kill, or reduce the growth of microbes, of antimicrobial active; preferably from about 0.001% to about 2%>, more preferably from about 0.002%> to about 1%), even more preferably from about 0.003% to about 0.3%>, by weight of the usage composition.
  • the effective antimicrobial active can function as disinfectants/sanitizers, and is useful in providing protection against organisms that become attached to the fabrics.
  • antimicrobial actives which are useful in the present invention: Pyrithiones, especially the zinc complex (ZPT); Octopirox; Parabens, including Methylparaben, Propylparaben, Butylparaben, Ethylparaben, Isopropylparaben, Isobutylparaben, Benzylparaben, Sodium Methylparaben, and Sodium Propylparaben; DMDM Hydantoin (Glydant); Methylchloroisothiazolinone/methylisothiazolinone (Kathon CG); Sodium Sulfite; Sodium Bisulfite; Imidazohdinyl Urea; Diazolidinyl Urea (Germail 2); Sorbic Acid/Potassium Sorbate; Dehydroacetic Acid/Sodium Dehydroacetate; Benzyl Alcohol; Sodium Borate; 2-Bromo-2-nitropropane-l,
  • Phenolic Compounds - including phenol and its homologs, mono- and poly-alkyl and aromatic halophenols, resorcinol and its derivatives, bisphenolic compounds and halogenated salicylanilides); Phenol and its Homologs including Phenol, 2-Methyl Phenol, 3-Methyl Phenol, 4-Methyl Phenol, 4-Ethyl Phenol, 2,4-Dimethyl Phenol, 2,5- Dimethyl Phenol, 3,4-Dimethyl Phenol, 2-,6-Dimethyl Phenol, 4-n-Propyl Phenol, 4-n- Butyl Phenol, 4-n-Amyl Phenol, 4-tert-Amyl Phenol, 4-n-Hexyl Phenol, and 4-n-Heptyl Phenol; Mono- and Poly-Alkyl and Aromatic Halophenols including p-Chlor
  • Resorcinol and its Derivatives including Resorcinol, Methyl Resorcinol, Ethyl Resorcinol, n-Propyl Resorcinol, n-Butyl Resorcinol, n-Amyl Resorcinol, n-Hexyl Resorcinol, n-Heptyl Resorcinol, n-Octyl Resorcinol, n-Nonyl Resorcinol, Phenyl Resorcinol, Benzyl Resorcinol, Phenylethyl Resor
  • natural antibacterial actives are the so-called "natural" antibacterial actives, referred to as natural essential oils. These actives derive their names from their natural occurrence in plants.
  • natural essential oil antibacterial actives include oils of anise, lemon, orange, rosemary, wintergreen, thyme, lavender, cloves, hops, tea tree, citronella, wheat, barley, lemongrass, cedar leaf, cedarwood, cinnamon, fleagrass, geranium, sandalwood, violet, cranberry, eucalyptus, vervain, peppermint, gum benzoin, Hydastis carradensis, Berberidaceae. daceae, Ratanhiae and Curcuma longa.
  • Also included in this class of natural essential oils are the key chemical components of the plant oils which have been found to provide the antimicrobial benefit. These chemicals include, but are not limited to anethol, catechole, camphene, thymol, eugenol, eucalyptol, ferulic acid, farnesol, hinokitiol, tropolone, limonene, menthol, methyl salicylate, salicylic acid, thymol, te ⁇ ineol, verbenone, berberine, ratanhiae extract, caryophellene oxide, citronellic acid, curcumin, nerolidol, geraniol and benzoic acid.
  • anethol catechole, camphene, thymol, eugenol, eucalyptol, ferulic acid, farnesol, hinokitiol, tropolone, limonene, menthol, methyl salicylate,
  • Additional active agents are antibacterial metal salts.
  • This class generally includes salts of metals in groups 3b-7b, 8 and 3a-5a. Specifically are the salts of aluminum, zirconium, zinc, silver, gold, copper, lanthanum, tin, mercury, bismuth, selenium, strontium, scandium, yttrium, cerium, praseodymiun, neodymium, promethum, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and mixtures thereof.
  • Preferred antimicrobial agents for use herein are the broad spectrum actives selected from the group consisting of Triclosan, phenoxyisopropanol, phenoxyethanol, PCMX, natural essential oils and their key ingredients, and mixtures thereof.
  • the most preferred antimicrobial active for use in the present invention is Triclosan.
  • Quaternary Compounds A wide range of quaternary compounds can also be used as antimicrobial actives, in conjunction with the preferred surfactants, for compositions of the present invention.
  • useful quaternary compounds include: (1) benzalkonium chlorides and/or substituted benzalkonium chlorides such as commercially available Barquat® (available from Lonza), Maquat® (available from Mason), Variquat® (available from Witco/Sherex), and Hyamine® (available from Lonza); (2) di(C6-Ci4)alkyl di-short chain (C ⁇ _4 alkyl and/or hydroxyalkyl) quaternary such as Bardac® products of Lonza.
  • These quaternary compounds contain two relatively short chains, e.g., Ci-4 alkyl and/or hydroxy alkyl groups and two C6-12 > preferably C6-10 > and more preferably C ⁇ , alkyl groups,(3) N-(3- chloroallyl) hexaminium chlorides such as Dowicide® and Dowicil® available from Dow; (4) benzethonium chloride such as Hyamine® 1622 from Rohm & Haas; (5) methylbenzethonium chloride represented by Hyamine® 1 OX supplied by Rohm & Haas, (6) cetylpyridinium chloride such as Cepacol chloride available from of Merrell Labs.
  • Examples of the preferred dialkyl quaternary compounds are di(C8-Ci2)dialkyl dimethyl ammonium chloride, such as didecyldimethylammonium chloride (Bardac 22), and dioctyldimethylammonium chloride (Bardac 2050).
  • Typical concentrations for biocidal effectiveness of these quaternary compounds range from about 0.001%o to about 0.8%>, preferably from about 0.005%> to about 0.3%>, more preferably from about 0.01 %> to 0.2%, by weight of the usage composition.
  • the corresponding concentrations for the concentrated compositions are from about 0.003% to about 2%, preferably from about 0.006%) to about 1.2%, and more preferably from about 0.1% to about 0.8% by weight of the concentrated compositions.
  • the solubilized, water-soluble antimicrobial active is useful in providing protection against organisms that become attached to the treated fabrics.
  • the antimicrobial should be cyclodextrin-compatible, e.g., not substantially forming complexes with the cyclodextrin in the odor absorbing composition when cyclodextrin is present.
  • the free, uncomplexed antimicrobial, e.g., antibacterial, active provides an optimum antibacterial performance.
  • compositions of the present invention containing, antimicrobial materials, e.g., antibacterial halogenated compounds, quaternary compounds, and phenolic compounds.
  • antimicrobial materials e.g., antibacterial halogenated compounds, quaternary compounds, and phenolic compounds.
  • Some of the more robust cyclodextrin-compatible antimicrobial halogenated compounds which can function as disinfectants/sanitizers as well as finish product preservatives (vide infra), and are useful in the compositions of the present invention include l,l'-hexamethylene bis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, and its salts, e.g., with hydrochloric, acetic and gluconic acids.
  • the digluconate salt is highly water-soluble, about 70% in water, and the diacetate salt has a solubility of about 1.8% in water.
  • chlorhexidine When chlorhexidine is used as a sanitizer in the present invention it is typically present at a level of from about 0.001% to about 0.4%, preferably from about 0.002%) to about 0.3%, and more preferably from about 0.05% to about 0.2%), by weight of the usage composition. In some cases, a level of from about 1 % to about 2% may be needed for virucidal activity.
  • Other useful biguanide compounds include Cosmoci® CQ®, Vantocil® IB, including poly (hexamethylene biguanide) hydrochloride.
  • Other useful cationic antimicrobial agents include the bis-biguanide alkanes.
  • Usable water soluble salts of the above are chlorides, bromides, sulfates, alkyl sulfonates such as methyl sulfonate and ethyl sulfonate, phenylsulfonates such as p-methylphenyl sulfonates, nitrates, acetates, gluconates, and the like.
  • Suitable bis biguanide compounds are chlorhexidine; l,6-bis-(2- ethylhexylbiguanidohexane)dihydrochloride; 1 ,6-di-(N 1 ,Nj '-phenyldiguanido-N5,N5')- hexane tetrahydrochloride; 1 ,6-di-(Nj ,N ⁇ '-phenyl -Ni ,Nj '-methyldiguanido-N5.N5 1 )- hexane dihydrochloride; 1 ,6-di(Nj ,Nj '-o-chlorophenyldiguanido-N5,N5')-hexane dihydrochloride; l,6-di(N ⁇ ,N ⁇ '-2,6-dichlorophenyldiguanido-N5,N5')hexane dihydrochloride; l,
  • omega. omega. '-di-(N ⁇ ,N ⁇ '-phenyldiguanido-N5,N5')-di-n-propylether dihydrochloride; .omega: omega'-di(N ⁇ ,N ⁇ '-p-chlorophenyldiguanido-N5 ,N5 ')-di-n- propylether tetrahydrochloride; 1 ,6-di(N ⁇ ,N ⁇ '-2,4-dichlorophenyldiguanido-
  • N5,N5')hexane tetrahydrochloride l,6-di[N ⁇ ,N ⁇ '-.alpha.-(p-chlorophenyl) ethyldiguanido-N5,N5'] hexane dihydrochloride;. omega.:, omega.
  • Preferred antimicrobials from this group are l,6-di-(N ⁇ ,N ⁇ '-phenyldiguanido-N5,N5 l )-hexane tetrahydrochloride; l,6-di(N ⁇ ,N ⁇ '-o- chlorophenyldiguanido-N5,N5')-hexane dihydrochloride; l,6-di(N ⁇ ,N ⁇ '-2,6- dichlorophenyldiguanido-N5,N5')hexane dihydrochloride; 1 ,6-di(N ⁇ ,Nj '-2,4- dichlorophenyldiguanido-N5,N5')hexane tetrahydrochloride; 1 ,6-di[N ⁇ ,N] '-.alpha.-(p- chlorophenyl) ethyldiguanido-N5,N5'] he
  • omega. omega. :.omega.'di(Nj, N 1 '-p-chlorophenyldiguanido-N5.N5 ')m-xylene dihydrochloride; 1 , 12-di(N ⁇ ,N ⁇ '-p- chlorophenyldiguanido-N5,N5') dodecane dihydrochloride; l,6-di(N ⁇ ,N ⁇ '-o- chlorophenyldiguanido-N5,N5') hexane dihydrochloride; l,6-di(N ⁇ ,N ⁇ '-p- chlorophenyldiguanido-N5,N5')-hexane tetrahydrochloride; and mixtures thereof; more preferably, 1 ,6-di(N ⁇ ,N ⁇ '-o-chlorophenyldiguanido-N5,N5')-hexane dihydrochloride;
  • the surfactants when added to the antimicrobials tend to provide improved antimicrobial action. This is especially true for the siloxane surfactants, and especially when the siloxane surfactants are combined with the chlorhexidine antimicrobial actives.
  • Chelators e.g., ethylenediaminetetraacetic acid (EDTA), hydroxyethylene- diaminetriacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and their salts, and mixtures thereof, can optionally be used to increase antimicrobial and preservative effectiveness against Gram-negative bacteria, especially Pseudomonas species.
  • EDTA ethylenediaminetetraacetic acid
  • hydroxyethylene- diaminetriacetic acid diethylenetriaminepentaacetic acid
  • other aminocarboxylate chelators and mixtures thereof, and their salts, and mixtures thereof
  • sensitivity to EDTA and other aminocarboxylate chelators is mainly a characteristic of Pseudomonas species
  • other bacterial species highly susceptible to chelators include Achromobacter, Alcali genes, Azotobacter, Escherichia. Salmonella. Spirillum, and Vibrio.
  • aminocarboxylate chelators can help, e.g., maintaining product clarity, protecting fragrance and perfume components, and preventing rancidity and off odors.
  • aminocarboxylate chelators may not be potent biocides in their own right, they function as potentiators for improving the performance of other antimicrobials/preservatives in the compositions of the present invention.
  • Aminocarboxylate chelators can potentiate the performance of many of the cationic, anionic, and nonionic antimicrobials/preservatives, phenolic compounds, and isothiazolinones, that are used as antimicrobials/preservatives in the composition of the present invention.
  • Nonlimiting examples of cationic antimicrobials/preservatives potentiated by aminocarboxylate chelators in solutions are chlorhexidine salts (including digluconate, diacetate, and dihydrochloride salts), and Quaternium-15, also known as Dowicil 200, Dowicide Q, Preventol DI, benzalkonium chloride, cetrimonium, myristalkonium chloride, cetylpyridinium chloride, lauryl pyridinium chloride, and the like.
  • Nonlimiting examples of useful anionic antimicrobials/preservatives which are enhanced by aminocarboxylate chelators are sorbic acid and potassium sorbate.
  • Nonlimiting examples of useful nonionic antimicrobials/preservatives which are potentiated by aminocarboxylate chelators are DMDM hydantoin, phenethyl alcohol, monolaurin, imidazohdinyl urea, and Bronopol (2-bromo-2-nitropropane-l,3-diol).
  • Examples of useful phenolic antimicrobials/preservatives potentiated by these chelators are chloroxylenol, phenol, tert-butyl hydroxyanisole, salicylic acid, resorcinol, and sodium o-phenyl phenate.
  • Nonlimiting examples of isothiazolinone antimicrobials/preservatives which are enhanced by aminocarboxylate chelators are Kathon, Proxel and Promexal.
  • the optional chelators are present in the compositions of this invention at levels of, typically, from about 0.01% to about 0.3%, more preferably from about 0.02%> to about 0.1%), most preferably from about 0.02%> to about 0.05% by weight of the usage compositions to provide antimicrobial efficacy in this invention.
  • Free, uncomplexed aminocarboxylate chelators are required to potentiate the efficacy of the antimicrobials.
  • excess alkaline earth especially calcium and magnesium
  • transitional metals iron, manganese, copper, and others
  • free chelators are not available and antimicrobial potentiation is not observed.
  • higher levels may be required to allow for the availability of free, uncomplexed aminocarboxylate chelators to function as antimicrobial/preservative potentiators.
  • an antimicrobial preservative can be added to the composition of the present invention, preferably solubilized, water-soluble, antimicrobial preservative, to protect the fabric care polysaccharide with globular structure and/or other easily degradable organic ingredients such as cyclodextrin, because these molecules are made up, e.g., of varying numbers of glucose units which can make them a prime breeding ground for certain microorganisms, especially when in aqueous compositions.
  • This drawback can lead to the problem of storage stability of fabric care solutions for any significant length of time. Contamination by certain microorganisms with subsequent microbial growth can result in an unsightly and/or malodorous solution.
  • an antimicrobial preservative preferably solubilized, water- soluble, antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear, aqueous odor-absorbing solution containing the fabric care polysaccharide with globular structure.
  • a broad spectrum preservative e.g., one that is effective on both bacteria (both gram positive and gram negative) and fungi.
  • a limited spectrum preservative e.g., one that is only effective on a single group of microorganisms, e.g., fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary and/or supplementary activity.
  • a mixture of broad spectrum preservatives can also be used.
  • aminocarboxylate chelators can be used alone or as potentiators in conjunction with other preservatives.
  • chelators which include, e.g., ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and their salts, and mixtures .thereof, can increase preservative effectiveness against Gram-negative bacteria, especially Pseudomonas species.
  • EDTA ethylenediaminetetraacetic acid
  • hydroxyethylenediaminetriacetic acid hydroxyethylenediaminetriacetic acid
  • diethylenetriaminepentaacetic acid diethylenetriaminepentaacetic acid
  • other aminocarboxylate chelators and mixtures thereof, and their salts, and mixtures .thereof, can increase preservative effectiveness against Gram-negative bacteria, especially Pseudomonas species.
  • Antimicrobial preservatives useful in the present invention include biocidal compounds, i.e., substances that kill microorganisms, or biostatic compounds, i.e., substances that inhibit and/or regulate the growth of microorganisms. Suitable preservatives are disclosed in U.S. Pats. 5,534,165; 5,578,563; 5,663,134; 5,668,097; 5,670,475; and 5,714,137, Trinh et al. issued Jul. 9, 1996; Nov. 26, 1996; Sep. 2, 1997; Sep. 16, 1997; Sep. 23, 1997; and Feb. 3, 1998 respectively, all of said patents being inco ⁇ orated hereinbefore by reference. Many antimicrobial preservatives are given under the section on Antimicrobial Active given herein above.
  • Water insoluble antimicrobial preservatives such as paraben and triclosan are useful in the fabric care compositions of the present invention, but they require the use of a solubilizer, an emulsifier, a dispersing agent, or the like, such as a surfactant and/or cyclodextrin to effectively distribute said preservative in the liquid composition.
  • Preferred antimicrobial preservatives are those that are water-soluble and are effective at low levels.
  • Water- soluble preservatives useful in the present invention are those that have a solubility in water of at least about 0.3 g per 100 ml of water, i.e., greater than about 0.3% at room temperature, preferably greater than about 0.5%> at room temperature.
  • the water-soluble antimicrobial preservative in the present invention is included at an effective amount.
  • effective amount means a level sufficient to prevent spoilage, or prevent growth of inadvertently added microorganisms, for a specific period of time.
  • the preservative is not being used to kill microorganisms on the surface onto which the composition is deposited in order to eliminate odors produced by microorganisms. Instead, it is preferably being used to prevent spoilage of the fabric care polysaccharide with globular structure solution in order to increase the shelf-life of the composition.
  • Preferred levels of preservative are from about 0.0001% to about 0.5%, more preferably from about 0.0002% to about 0.2%, most preferably from about 0.0003% to about 0.1%, by weight of the usage composition.
  • the preservative can be any organic preservative material which will not cause damage to fabric appearance, e.g., discoloration, coloration, bleaching.
  • Preferred water- soluble preservatives include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary ammonium compounds, dehydroacetic acid, phenyl and phenolic compounds, and mixtures thereof.
  • the preservatives of the present invention can be used in mixtures in order to control a broad range of microorganisms.
  • Bacteriostatic effects can sometimes be obtained for aqueous compositions by adjusting the composition pH to an acid pH, e.g., less than about pH 4, preferably less than about pH 3, or a basic pH, e.g., greater than about 10, preferably greater than about 11.
  • an acid pH e.g., less than about pH 4, preferably less than about pH 3, or a basic pH, e.g., greater than about 10, preferably greater than about 11.
  • the fabric care composition herein can optionally contain fabric softening active.
  • a liquid rinse- added composition typically contains from about 1%> to about 75%, preferably from about 2%> to about 65%o, more preferably from about 3%> to about 45%, and even more preferably from about 4%o to about 35% by weight of the composition, of a fabric softener active.
  • the levels are from about 1% to about 99%o, preferably from about 10%) to about 80%, more preferably from about 20% to about 70%), and even more preferably from about 25% to about 60% of fabric softening active.
  • For a spray-on composition the levels are from about 0.05%> to about 10%, preferably from about 0.1% to about 7%, more preferably from about 0.5% to about 5%>.
  • the rinse-added fabric care compositions containing fabric softening actives herein can comprise liquid compositions that can be either dispersions or clear. Dispersion Compositions
  • Stable "dispersion" compositions can be prepared like those disclosed in U.S. Pat. No. 4,661,269, issued April 28, 1987, to T. Trinh et al., and in U.S. Pat. No. 5,545,340, issued Aug. 13, 1996, to Wahl et al., said patents being inco ⁇ orated herein by reference. Suitable optional components in addition to the softening active are disclosed hereinafter.
  • the dispersion liquid compositions herein can be both dilute and concentrated, but are preferably concentrated. Clear Compositions
  • compositions are concentrate and clear, comprising: I. from about 2% to about 80%, preferably from about 13% to about 75%, more preferably from about 17%> to about 70%, and even more preferably from about 19%> to about 65%, by weight of the composition, of fabric softening active, having a phase transition temperature of less than about 50°C, preferably less than about 35°C, more preferably less than about 20°C, and even more preferably less than about 0°C, preferably being biodegradable fabric softening active containing unsaturated alkyl groups and/or branched fatty alkyl groups, said unsaturated alkyl groups having an average Iodine Value (IV) of at least about 40, a level of polyunsaturation preferably being at least about 5%, and with the level of C 18:3 acyl groups in the starting fatty acyl source feedstock for making the said softening active preferably being less than about 1 % by weight.
  • fabric softening active having a phase transition temperature of less
  • At least an effective level of principal solvent preferably having a ClogP of from about -2.0 to about 2.6 , more preferably from about -1.7 to about 1.6, and even more preferably from about - 1.0 to about 1.0, as defined hereinafter, typically at a level that is less than about 40%>, preferably from about 1% to about 25%, more preferably from about 3%> to about 8% by weight of the composition;
  • III optionally, but preferably, from about 0.1 % to about 10%o by weight, preferably from about 0.75 % to about 2.5 % by weight of the composition, and more preferably from about 1 % to about 2 % by weight of the composition of electrolyte as defined hereinafter;
  • composition of phase stabilizer optionally, but preferably, from 0%> to about 15%>, preferably from about 0.1% to about 7%, and more preferably from about 1% to about 6%>, by weight of the composition of phase stabilizer, preferably surfactant containing alkoxylation, and also preferably having an HLB of from about 8 to about 20, more preferably from about 10 to about 18, and even more preferably from about 11 to about 15; and
  • V the balance water, minor ingredients and/or water soluble solvents.
  • the preferred principal solvent and/or electrolyte levels, as well as the identity of the principal solvent, are selected normally according to the level and identity of the softener.
  • Preferred levels and identity of principal solvent, electrolyte, and phase stabilizer which will yield clear stable compositions are taught in copending U.S. Patent Application Serial No. 09/309,128, filed May 10, 1999, Frankenbach et al., inco ⁇ orated herein by reference.
  • ClogP of a solvent is the calculated logarithm to the base 10 of the octanol/water partition coefficient (P) of said solvent.
  • ClogP values are conveniently calculated by the "CLOGP” program, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California.
  • the "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, inco ⁇ orated herein by reference).
  • the fragment approach is based on the chemical structure of each ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
  • Other methods that can be used to compute ClogP include, e.g., Crippen's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984). Fabric Softening Actives
  • Fabric softening actives that can be used herein are disclosed, at least generically for the basic structures, in U.S. Pat. Nos.: 3,408,361, Mannheimer, issued Oct. 29, 1968; 4,709,045; Kubo et al., issued Nov. 24, 1987; 4,233,451, Pracht et al., issued Nov. 11, 1980; 4,127,489, Pracht et al., issued Nov. 28, 1979; 3,689,424, Berg et al, issued Sept. 5, 1972; 4,128,485, Baumann et al., issued Dec. 5, 1978; 4,161,604, Elster et al., issued July 17, 1979; 4,189,593, Wechsler et al, issued Feb.
  • Any fabric softening active including quaternary and non-quaternary softening actives, with saturated, partially saturated, unsaturated an/or highly unsaturated, with straight, linear alkyl chains and/or branched alkyl groups, can be use in the rinse-added fabric care composition of the present invention.
  • Biodegradable fabric softening actives are preferred.
  • a preferred fabric care composition herein uses fabric softening active with highly unsaturated and/or branched hydrophobic chains, preferably biodegradable, selected from the highly unsaturated and/or branched fabric softening actives, and mixtures thereof.
  • These highly unsaturated and/or branched fabric softening actives have the required properties for permitting high usage levels to provide additional fabric appearance benefits, including recovery of fabric color appearance, improved color integrity, and anti-wrinkling benefits.
  • Fabric softening actives with saturated and/or low degree of unsaturation e.g., Iodine Value of less than about 10
  • fabric softening actives with unsaturated chains having the trans configuration can normally provide a better softening performance per unit weight, but are more difficult to concentrate, thus can be used in compositions with lower levels of fabric softening active, typically below about 30%, preferably below 25%>, more preferably below 20%, by weight of the composition.
  • Preferred fabric softening actives of the invention comprise a majority of compounds as follows:
  • the first type of DEQA preferably comprises, as the principal active, compounds of the formula
  • each R substituent is either hydrogen, a short chain Cj-C , preferably C1 -C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, poly (C2-3 lko y) preferably polyethoxy group, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to about 4; each Y is -O-(O)C-, -C(O)-O-, -NR-C(O)- , or -C(O)-NR-; the sum of carbons in each Rl, plus one when Y is -O-(O)C- or -NR- C(O) -, is Ci2-C22 > preferably Ci 4-C20 > with each R being
  • a second type of DEQA active has the general formula:
  • each R is a methyl or ethyl group and preferably each R 1 is in the range of C ⁇ $ to C19.
  • biodegradable quaternary ammonium fabric softening compounds preferably contain the group C(O)R* which is derived, primarily from saturated fatty acids, such as stearic acid, but more preferably derived from partially saturated fatty acids and/or partially hydrogenated fatty acids from natural sources, e.g., derived from animal fat, such as tallow fatty acids.
  • unsaturated fatty acids e.g., oleic acid
  • polyunsaturated fatty acids such as those derived from vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc.
  • Non-limiting examples of fatty acids (FA) are listed in U.S. Pat. No. 5,759,990 at column 4, lines 45-66. Fabric softening actives containing unsaturated and polyunsaturated fatty acids are preferred in formulating concentrated, clear fabric softening compositions of the present invention.
  • fatty acids can be used, and are preferred.
  • Nonlimiting examples of fatty acids that can be blended, to form fatty acid mixtures (FA's) of this invention are as follows:
  • FA* is a partially hydrogenated fatty acid prepared from canola oil
  • FA 2 is a fatty acid prepared from soy bean oil
  • FA 3 is a slightly hydrogenated tallow fatty acid.
  • Iodine Value (referred to as "IV" herein) is used to define the level of unsaturation of a fatty acid.
  • Iodine Value of the "parent" fatty acid, or “corresponding" fatty acid that the R ⁇ group is derived from, is also used to define the level of unsaturation of a fabric softening active.
  • the JN of the parent fatty acids of these Rl group is from about 0 to about 140, more preferably from about 40 to about 130, on the average.
  • the IV is preferably from about 70 to about 140, more preferably from about 80 to about 130, and even more preferably from about 90 to about 115, on the average.
  • the fatty acyl groups are unsaturated, e.g., from about 50%> to 100%, preferably from about 55% to about 100%, more preferably from about 60% to about 100%.
  • the cis/trans ratio for the unsaturated fatty acyl groups is important, with a preferred cis/trans ratio of from 1 : 1 to about 50: 1, the minimum being 1 :1, preferably at least 3:1, and more preferably from about 4:1 to about 20:1.
  • the long chain hydrocabon groups can also comprise branched chains, e.g., from isostearic acid, for at least part of the groups.
  • the total of active represented by the branched chain groups, when they are present, is typically from about 1%> to about 100%, preferably from about 10% to about 70%, more preferably from about 20% to about 50%.
  • the unsaturated, including the polyunsaturated, fatty acyl groups not only provide su ⁇ risingly effective softening, but also provide better absorbency characteristics, good antistatic characteristics, and superior recovery after freezing and thawing.
  • These highly unsaturated/branched materials provide excellent softening while minimizing loss of water absorbency and "greasy" fabric feel. These two characteristics allow one to use higher levels of softening active than would be ordinarily desirable, which provides several additional benefits, including noticeable color maintenance, protection, and/or recovery for colored fabrics, especially colored cotton and cotton blend fabrics, improved anti -wrinkling benefit, improved fiber integrity, i.e., less damage to fabrics, improved antistatic benefits, and a high level of softness.
  • the highly unsaturated materials are also easier to formulate into concentrated premixes that maintain their low viscosity and are therefore easier to process, e.g., pump, mixing, etc.
  • These highly unsaturated materials with only a low amount of solvent that normally is associated with such materials i.e., from about 5% to about 20%, preferably from about 8%> to about 25%, more preferably from about 10% to about 20%, weight of the total softening active/solvent mixture, are also easier to formulate into concentrated, stable dispersion compositions of the present invention, even at ambient temperatures.
  • substituents R and R can optionally be substituted with various groups such as alkoxyl or hydroxyl groups, so long as the R* groups maintain their basically hydrophobic character.
  • the preferred compounds can be considered to be biodegradable diester variations of ditallow dimethyl ammonium chloride (hereinafter referred to as "DTDMAC”), which is a widely used fabric softening active.
  • DTDMAC ditallow dimethyl ammonium chloride
  • a preferred long chain DEQA is the DEQA prepared from sources containing high levels of polyunsaturation, i.e., N,N-di(acyl-oxyethyl)-N,N-dimethyl ammonium chloride, where the acyl is derived from fatty acids containing sufficient polyunsaturation.
  • at least about 70% of the DEQA is in the diester form, and from 0% to about 30% can be DEQA monoester.
  • the percentage of monoester should be as low as possible, preferably no more than about 15%.
  • some monoester or monoamide can be preferred.
  • the overall ratios of diester to monoester, or diamide to monoamide are from about 100:1 to about 2:1, preferably from about 50:1 to about 5:1, more preferably from about 13:1 to about 8:1. Under high detergent carryover conditions, the di/monoester ratio is preferably about 11 :1.
  • the level of monoester, or monoamide, present can be controlled in manufacturing the DEQA.
  • DEQA softening active that is suitable for the formulation of the concentrated, liquid fabric care compositions of the present invention, has the above formula (1) wherein one R group is a Cj_4 hydroxy alkyl group, or polyalkoxy group, preferably hydroxy alkyl, more preferably hydroxyethyl, group.
  • R group is a Cj_4 hydroxy alkyl group, or polyalkoxy group, preferably hydroxy alkyl, more preferably hydroxyethyl, group.
  • An example of such a hydroxyethyl ester active is di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate, where the acyl is derived from the fatty acids described hereinbefore, e.g., oleic acid.
  • Such DEQA is a quaternized product of condensation between: (a)-a fraction of saturated or unsaturated, linear or branched fatty acids, or of derivatives of said acids, said fatty acids or derivatives each possessing a hydrocarbon chain in which the number of atoms is between 5 and 21, and (b) triethanolamine, characterized in that said condensation product has an acid value, measured by titration of the condensation product with a standard KOH solution against a phenolphthalein indicator, of less than about 6.5.
  • the acid value is preferably less than or equal to about 5, more preferably less than about 3. Indeed, the lower the AV, the better softness performance is obtained.
  • the acid value is determined by titration of the condensation product with a standard KOH solution against a phenolphthalein indicator according to ISO#53402.
  • the AV is expressed as mg KOH/g of the condensation product.
  • the reactants are present in a molar ratio of fatty acid fraction to triethanolamine of from about 1 :1 to about 2.5:1.
  • the optimum softness performance is also affected by the detergent carry-over laundry conditions, and more especially by the presence of the anionic surfactant in the solution in which the softening composition is used. Indeed, the presence of anionic surfactant that is usually carried over from the wash will interact with the softener compound, thereby reducing its performance. Thus, depending on usage conditions, the mole ratio of fatty acid/ triethanolamine can be critical. Accordingly, where no rinse occurs between the wash cycle and the rinse cycle containing the softening compound, a high amount of anionic surfactant will be carried over in the rinse cycle containing the softening compound.
  • a fatty acid fraction/triethanolamine mole ratio of about 1.4:1 to about 1.8:1 is preferred.
  • high amount of anionic surfactant it is meant that the presence of anionic in the rinse cycle at a level such that the molar ratio anionic surfactant/cationic softener compound of the invention is at least about 1/10.
  • compositions can also contain medium-chain cationic ammonium fabric softening compound, including DEQAs having the above formula (1) and/or formula (2), below, wherein: each Y is -O-(O)C-, -(R)N-(O)C-, -C(O)-N(R)-, or -C(O)-O-, preferably -O-(O)C-
  • each Rl, or YRI hydrophobic group is a saturated, C -Cj4 preferably a C12-I4 hydrocarbyl, or substituted hydrocarbyl substituent (the IV is preferably about 10 or less, more preferably less than about 5), [The sum of the carbons in the hydrophobic group is the number of carbon atoms in the Rl group, or in the YRI group when Y is -O-(O)C- or -(R)N-(O)C-.] and the counterion, A", is the same as above.
  • a " does not include phosphate salts.
  • the saturated Cg-Ci 4 fatty acyl groups can be pure derivatives or can be mixed chainlengths.
  • Suitable fatty acid sources for said fatty acyl groups are coco, lauric, caprylic, and capric acids.
  • the groups are preferably saturated, e.g., the IV is preferably less than about 10, preferably less than about 5.
  • substituents R and R can optionally be substituted with various groups such as alkoxyl or hydroxyl groups, and can be straight, or branched so long as the R groups maintain their basically hydrophobic character.
  • the DEQA actives described hereinabove can contain a low level of the fatty acids which can be unreacted starting material and/or by-product of any partial degradation, e.g., hydrolysis, of the softening actives in the finished compositions. It is preferred that the level of free fatty acid be low, preferably below about 10%>, more preferably below about 5%>, by weight of the softening active.
  • the DEQA actives described hereinabove also include the neutralized amine softening actives wherein at least one R group is a hydrogen atom.
  • a non-limiting example of actives of this type is the chloride salt of (unsaturated alkoyloxyethyl)(unsaturated alkylamidotrimethylene)methylamine.
  • suitable amine softening actives are disclosed in PCT application WO 99/06509, K. A. Grimm, D. R. Bacon, T. Trinh, E. H. Wahl, and H. B. Tordil, published on Feb. 11, 1999, said application being inco ⁇ orated herein by reference.
  • Fabric softening actives carrying more than one positive quaternary ammonium charge are also useful in the rinse-added compositions of the present invention.
  • An example of this type of softening active is that having the formula:
  • each R is H or a short chain C1 -C , preferably -C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R2 O)2-4H; each R is a C6-C22 ; preferably C14-C20 hydrocarbyl, or substituted hydrocarbyl substituent, preferably C10-C20 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as "alkylene"), most preferably C ⁇ -Cjg alkyl or alkenyl; each R2 is a Cj_6 alkylene group, preferably an ethylene group; and A" are defined as below. Fabric softening actives having the following formula:
  • R l is derived from oleic acid is available from Witco Company.
  • each R, R 1 , and A" have the definitions given above; each R is a C ⁇ . ⁇ alkylene group, preferably an ethylene group; and G is an oxygen atom or an -NR- group; (7) Softening active having the formula:
  • Rl, R2 and G are defined as above;
  • R 1 C(O)— NH— R 2 — NH— R 3 — NH— C(O)— R 1 wherein Rl, R2 are defined as above, and each R 3 is a C ⁇ . alkylene group, preferably an ethylene group;
  • reaction product of substantially unsaturated and/or branched chain higher fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1, said reaction products containing compounds of the formula:
  • Examples of Compound (5) are dialkylenedimethylammonium salts such as dicanoladimethylammonium chloride, dicanoladimethylammonium methylsulfate, di(partially hydrogenated soybean, cis/trans ratio of about 4:l)dimethylammonium chloride, dioleyldimethylammonium chloride. Dioleyldimethylammonium chloride and di(canola)dimethylammonium chloride are preferred.
  • An example of commercially available dialkylenedimethylammonium salts usable in the present invention is dioleyldimethylammonium chloride available from Witco Co ⁇ oration under the trade name Adogen® 472.
  • Compound (6) is 1 -methyl- l-oleylamid ⁇ ethyl-2- oleylimidazolinium methylsulfate wherein R* is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, G is a NH group, R ⁇ is a methyl group and A " is a methyl sulfate anion, available commercially from the Witco Co ⁇ oration under the trade name Varisoft® 3690.
  • Compound (7) is l-oleylamidoethyl-2-oleylimidazoline wherein R ⁇ is an acyclic aliphatic C15-C17 hydrocarbon group, R is an ethylene group, and G is a NH group.
  • Compound (8) is reaction products of oleic acids with diethylenetriamine in a molecular ratio of about 2:1, said reaction product mixture containing N,N"-dioleoyldiethylenetriamine with the formula:
  • R ⁇ -C(O) is oleoyl group of a commercially available oleic acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021 , available from Henkel Co ⁇ oration, and R and R 3 are divalent ethylene groups.
  • Compound (9) is a difatty amidoamine based softening active having the formula:
  • Compound (10) is reaction products of oleic acids with N-2- hydroxyethyl ethyl enediamine in a molecular ratio of about 2:1, said reaction product mixture containing a compound of the formula:
  • Emersol® 223 LL or Emersol® 7021 available from Henkel Co ⁇ oration.
  • the above individual Compounds (actives) can be used individually or as mixtures.
  • One type of optional but highly desirable cationic compound which can be used in combination with the above softening actives are compounds containing one long chain acyclic C -C22 hydrocarbon group, selected from the group consisting of: wherein R ⁇ is hydrogen or a Ci -C4 saturated alkyl or hydroxyalkyl group, and Rl and A " are defined as herein above;
  • R? is hydrogen or a Ci -C4 saturated alkyl or hydroxyalkyl group, and Rl and A " are defined as hereinabove;
  • R ⁇ is a C1-C4 alkyl or hydroxyalkyl group, and R , R2, and A ⁇ are as defined above;
  • R ⁇ is an acyclic aliphatic Cg-C22 hydrocarbon group and A" is an anion;
  • Alkanamide alkylene pyridinium salts having the formula: wherein Rl, R2 and A" are defined as herein above;
  • Examples of Compound (12) are the monoalkenyltrimethylammonium salts such as monooleyltrimethylammonium chloride, monocanolatrimethylammonium chloride, and soyatrimethylammonium chloride. Monooleyltrimethylammonium chloride and monocanolatrimethylammonium chloride are preferred.
  • Compound (12) are soyatrimethylammonium chloride available from Witco Co ⁇ oration under the trade name Adogen® 415, erucyltrimethylammonium chloride wherein R ⁇ is a C22 hydrocarbon group derived from a natural source; soyadimethylethylammonium ethylsulfate wherein Rl is a Ci -C ⁇ hydrocarbon group, R ⁇ is a methyl group, R ⁇ is an ethyl group, and A" is an ethylsulfate anion; and methyl bis(2- hydroxyethyl)oleylammonium chloride wherein R ⁇ is a Cj hydrocarbon group, R ⁇ is a 2-hydroxyethyl group and R ⁇ is a methyl group.
  • Adogen® 415 erucyltrimethylammonium chloride
  • R ⁇ is a C22 hydrocarbon group derived from a natural source
  • Compound (14) is 1 -ethyl- l-(2-hydroxyethyl)-2- isoheptadecylimidazolinium ethylsulfate wherein Rl is a C17 hydrocarbon group, R2 is an ethylene group, R-> is an ethyl group, and A" is an ethylsulfate anion.
  • Compound (17) is N-tallow pentamethyl propane diammonium dichloride, with the formula:
  • the anion A- which is any softening active compatible anion, provides electrical neutrality.
  • the anion used to provide electrical neutrality in these salts is from a strong acid, especially a halide, such as chloride, methylsulfate, bromide, or iodide.
  • a halide such as chloride, methylsulfate, bromide, or iodide.
  • other anions can be used, such as ethylsulfate, acetate, formate, sulfate, carbonate, and the like. Chloride and methylsulfate are preferred herein as anion A.
  • Dryer-Added Compositions The fabric softening compound, or compounds, which are useful in the dryer-added fabric care composition can be selected from cationic, nonionic, amphoteric and/or anionic fabric softening compound.
  • the typical cationic fabric softening compounds include the water-insoluble quaternary-ammonium fabric softening actives, the most commonly used having been di(long alkylchain)dimethylammonium (C1-C4 alkyl)sulfate or chloride, preferably the methyl sulfate, compounds including the following:
  • DTDMAMS di(tallowalkyl)dimethylammonium methyl sulfate
  • DTDMAC di(hydrogenated tallowalkyl)dimethylammonium chloride
  • the currently preferred compounds, like 12) and 13) are more environmentally- friendly materials, being rapidly biodegradable quaternary ammonium compounds that are alternatives to the traditionally used di(long alkyl chain)dimethylammonium methyl sulfate.
  • Such quaternary ammonium compounds can contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups.
  • Said materials and fabric softening compositions containing them are disclosed in numerous publications such as EP-A-0,040,562, and EP-A-0,239,910. Similar quaternary ammonium compounds useful in the dryer-added compositions are those given hereinabove for rinse-added compositions.
  • Nonionic softening actives can also be used in dryer-added compositions of the present invention.
  • such nonionic fabric softening materials have an HLB of from about 2 to about 9, more typically from about 3 to about 7.
  • the materials selected should be relatively crystalline, higher melting, (e.g., >25°C, preferably >40°C) and relatively water-insoluble.
  • the level of nonionic softener in the solid composition when present, is typically from about 0.1 % to about 50%, preferably from about 5% to about 30%>.
  • Highly preferred optional nonionic softening agents for use in the present invention are C10-C26 acyl sorbitan esters and polyglycerol monostearate.
  • Sorbitan esters are esterified dehydration products of sorbitol.
  • Sorbitol which is typically prepared by the catalytic hydrogenation of glucose, can be dehydrated in well known fashion to form mixtures of 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides. (See U.S. Pat. No.
  • the preferred sorbitan ester comprises a member selected from the group consisting of Ci 0-C26 ac Y ⁇ sorbitan monoesters and C10-C26 acyl sorbitan diesters. It is also preferred that a significant amount of trisorbitan esters are present in the ester mixture. Ester mixtures having from 20-50%> mono-ester, 25-50%) di-ester and 10-35% of tri- and tetra-esters are preferred. For the pu ⁇ ose of the present invention, sorbitan esters containing unsaturation (e.g., sorbitan monooleate) can be utilized.
  • unsaturation e.g., sorbitan monooleate
  • sorbitan esters herein especially the "lower" ethoxylates thereof, i.e., mono-, di-, and tri-esters wherein one or more of the unesterified -OH groups contain one to about twenty ethylene oxide units (e.g., Tweens®) are also useful in the composition of the present invention. Therefore, for pu ⁇ oses of the present invention, the term "sorbitan ester" includes such derivatives.
  • nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and each fatty acid moiety contains from about 8 to about 30, preferably from about 12 to about 20, carbon atoms.
  • such softeners contain from about one to about 3, preferably about 2 fatty acid groups per molecule.
  • the polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, and/or pentaerythritol.
  • Dryer-added fabric care compositions employed herein can contain as a softener component, at a level of from about 1% to about 60%, preferably from about 5% to about 50%), more preferably from about 10%> to about 40%, by weight of the composition of a carboxylic acid salt of a tertiary amine and/or ester amine which has the formula:
  • R ⁇ is a long chain aliphatic group containing from about 8 to about 30 carbon atoms;
  • R" and R ⁇ are the same or different from each other and are selected from the group consisting of aliphatic groups containing from about 1 to about 30, preferably 1, carbon atoms, hydroxyalkyl groups of the Formula -R ⁇ OH wherein R ⁇ is an alkylene group of from about 2 to about 30 carbon atoms, and alkyl ether groups of the formula R9(OC n H2 n ) m - wherein R9 is alkyl or alkenyl of from about 1 to about 30, preferably 2 or 3, carbon atoms or hydrogen, n is 2 or 3, and m is from about 1 to about 30, preferably from 1 to about 5; wherein R ⁇ , R5, R6 ; R8 ; an( ⁇ R9 chains can be ester interrupted groups; and wherein R ⁇ is selected from the group consisting of unsubstituted alkyl, alkenyl, aryl, alkaryl and
  • This component provides the following benefits: superior odor, and/or improved fabric softening performance, compared to similar composition which utilize primary amine or ammonium compounds as the sole fabric conditioning agent.
  • Either R ⁇ , R * , R", R ' , R°, and/or R ⁇ chains can contain unsaturation.
  • Examples of preferred tertiary amines as starting material for the reaction between the amine and carboxylic acid to form the tertiary amine salts are: lauryldimethylamine, myristyldimethylamine, stearyldimethylamine, tallowdimethylamine, coconutdimethylamine, dilaurylmethylamine, distearylmethylamine, ditallowmethylamine, oleyldimethylamine, dioleylmethylamine, lauryldi(3- hydroxypropyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethylmethylamine, and
  • Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and mixtures thereof.
  • the amine salt can be formed by a simple addition reaction, well known in the art, disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec. 2, 1980, which is inco ⁇ orated herein by reference. Excessive levels of free amines can result in odor problems, and generally free amines provide poorer softening performance than the amine salts.
  • the principal solvent when present, is typically used at an effective level up to about 40%) by weight, preferably from about 1 % to about 25%o, more preferably from about 3 % to about 8 %>, by weight of the composition.
  • the principal solvent can be used most effectively when in combination with high electrolyte level and/or the phase stabilizers, as disclosed in U.S. Patent Application Serial No. 09/309,128.
  • the ClogP of the principal solvent system disclosed therein would typically be limited to a range of from about 0.15 to about 0.64 as disclosed in U.S. Pat. No. 5,747,443.
  • phase stabilizer as defined hereinafter, in combination with a very low level of principal solvent is sufficient to provide good clarity and/or stability of the composition when the electrolyte is present.
  • Said electrolyte and/or said phase stabilizer can be used to either make a composition translucent or clear, or can be used to increase the temperature range at which the composition is translucent or clear.
  • solvents are efficient in that they provide the maximum advantage for a given weight of solvent. It is understood that "solvent”, as used herein, refers to the effect of the principal solvent and not to its physical form at a given temperature, since some of the principal solvents are solids at ambient temperature. Principal solvents that can be present are selected to minimize solvent odor impact in the composition and to provide a low viscosity to the final composition.
  • the principal solvents are typically selected from those having a ClogP of from - 2.0 to 2.6, preferably from -1.7 to 1.6, and more preferably from -1.0 to 1.0.
  • the most preferred solvents can be identified by the appearance of the dilute treatment compositions used to treat fabrics. These dilute compositions have dispersions of fabric softener that exhibit a more uni-lamellar appearance than conventional fabric softener compositions. The closer to uni-lamellar the appearance, the better the compositions seem to perform. These compositions provide su ⁇ risingly good fabric softening as compared to similar compositions prepared in the conventional way with the same fabric softener active.
  • Operable solvents have been disclosed, listed under various listings, e.g., aliphatic and/or alicyclic diols with a given number of carbon atoms; monols; derivatives of glycerine; alkoxylates of diols; and mixtures of all of the above can be found in said U.S. Pats. Nos.
  • an effective amount of the principal solvents of this invention is at least greater than about 1%, preferably more than about 3%, more preferably more than about 5% of the composition, when at least about 15%> of the softener active is also present.
  • Principal solvents preferred for improved clarity at 50 °F are 1,2-hexanediol; 1,2- pentanediol; hexylene glycol; 1,2-butanediol; 1,4-cyclohexanediol; pinacol; 1,5- hexanediol; 1 ,6-hexanediol; and/or 2,4-dimethyl-2,4-pentanediol.
  • the clear rinse-added fabric care compositions containing a high level of fabric softening agent of this invention can optionally, but preferably, contain an effective amount of electrolyte, e.g., from about 0.5% to about 10%o, preferably from about 0.75% to about 3%>, and more preferably from about 1%> to about 2%, by weight of the composition.
  • an effective amount of electrolyte e.g., from about 0.5% to about 10%o, preferably from about 0.75% to about 3%>, and more preferably from about 1%> to about 2%, by weight of the composition.
  • U.S. Pat. No. 5,759,990, inco ⁇ orated herein by reference discloses that the principal solvent in clear formulations should have a ClogP of from about 0.15 to about 0.64.
  • An effective amount of electrolyte allows the use of principal solvents with a ClogP of from about -2.0 to about 2.6, preferably from about -1.7 to about 1.6, and more preferably from about -1.0 to about 1.0.
  • the principal solvents are also more effective with the high electrolyte level, thus allowing one to use less of such principal solvents.
  • Electrolyte also helps to alleviate a thickening phenomenon some concentrate, clear fabric softener compositions are diluted.
  • Suitable inorganic salts for use as electrolyte include Mgl , MgBr 2 , MgCl 2 , Mg(NO 3 ) 2 , Mg 3 (PO 4 ) 2 , Mg 2 P 2 O 7 , MgSO 4 , magnesium silicate, Nal, NaBr, NaCl, NaF, Na 3 (PO 4 ), NaSO 3 , Na 2 SO 4 , Na 2 SO 3 , NaNO 3 , NaIO 3 , Na 3 (PO 4 ), Na 4 P 2 O 7 , sodium silicate, sodium metasilicate, sodium tetrachloroaluminate, sodium tripolyphosphate (STPP), Na 2 Si 3 O 7 , sodium zirconate, CaF 2 , CaCl 2 , CaBr 2 , Cal 2 , CaSO 4 , Ca(NO 3 ) 2 , Ca, KI, KBr, KC1, KF, KNO 3 , KIO 3 , K 2 SO 4 , K 2 SO 3
  • potassium alum AlK(SO 4 ) 2 and salts with mixed anions e.g. potassium tetrachloroaluminate and sodium tetrafluoroaluminate.
  • Salts inco ⁇ orating cations from groups Ilia, IYa, Va, Via, Vila, Vi ⁇ , lb, and lib on the periodic chart with atomic numbers > 13 are also useful in reducing dilution viscosity but less preferred due to their tendency to change oxidation states and thus they can adversely affect the odor or color of the formulation or lower weight efficiency.
  • Salts with cations from group la or Ila with atomic numbers > 20 as well as salts with cations from the lactinide or actinide series are useful in reducing dilution viscosity, but less preferred due to lower weight efficiency or toxicity. Mixtures of above salts are also useful.
  • Organic salts useful in this invention include, magnesium, sodium, lithium, potassium, zinc, and aluminum salts of the carboxylic acids including formate, acetate, proprionate, pelargonate, citrate, gluconate, lactate aromatic acids e.g. benzoates, phenolate and substituted benzoates or phenolates, such as phenolate, salicylate, polyaromatic acids terephthalates, and polyacids e.g. oxylate, adipate, succinate, benzenedicarboxylate, benzenetricarboxylate.
  • carboxylic acids including formate, acetate, proprionate, pelargonate, citrate, gluconate, lactate aromatic acids e.g. benzoates, phenolate and substituted benzoates or phenolates, such as phenolate, salicylate, polyaromatic acids terephthalates, and polyacids e.g. oxylate, adipate, succinate, benzenedicarboxylate
  • Electrolytes can comprise mixed salts of the above, salts neutralized with mixed cations such as potassium/sodium tartrate, partially neutralized salts such as sodium hydrogen tartrate or potassium hydrogen phthalate, and salts comprising one cation with mixed anions.
  • inorganic electrolytes are preferred over organic electrolytes for better weight efficiency and lower costs.
  • Mixtures of inorganic and organic salts can be used.
  • Typical levels of electrolyte in the compositions are less than about 10%.
  • Phase stabilizers are highly desirable to formulating a clear or translucent fabric softener composition with high electrolyte levels of the present invention.
  • the phase stabilizers provide an improved range of temperatures at which the compositions are clear and stable. They allow more electrolyte to be used without instability. They can also reduce the amount of principal solvent needed to achieve clarity and/or stability.
  • Typical levels of the optional phase stabilizer in the softening compositions are from about 0.1%) to about 15%>, preferably from about 0.3% to about 7%, more preferably from about 1% to about 5% by weight of the composition.
  • phase stabilizers useful in the compositions of the present invention are selected surface actives materials commonly comprise of hydrophobic and hydrophilic moieties.
  • a preferred hydrophilic moiety is polyalkoxylated group, preferably polyethoxylated group.
  • phase stabilizers are nonionic surfactants derived from saturated and/or unsaturated primary, secondary, and/or branched, amine, amide, amine-oxide fatty alcohol, fatty acid, alkyl phenol, and/or alkyl aryl carboxylic acid compounds, each preferably having from about 6 to about 22, more preferably from about 8 to about 18, carbon atoms in a hydrophobic chain, more preferably an alkyl or alkylene chain, wherein at least one active hydrogen of said compounds is ethoxylated with ⁇ 50, preferably ⁇ 30, more preferably from about 5 to about 15, and even more preferably from about 8 to about 12, ethylene oxide moieties to provide an HLB of from about 8 to about 20, preferably from about 10 to about 18, and more preferably from about 11 to about 15.
  • alkoxylated cationic materials or cationic surfactant complexes improve softness and provide enhanced wrinkle release benefits.
  • the preferred phase stabilizers are alkoxylated alkyls, alkoxylated acyl amides, alkoxylated alkyl amines or alkoxylated quaternary alkyl ammonium salts, surfactant complexes, and mixtures thereof.
  • Suitable phase stabilizers also include nonionic surfactants with bulky head groups selected from: a. surfactants having the formula
  • R is selected from the group consisting of saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain having a length of from about 6 to about 22;
  • Y' is selected from the following groups: - O-; -N(A)-; and mixtures thereof; and
  • A is selected from the following groups: H; R 1 ; - (R -O) 2 -H; -(CH ) X CH 3 ; phenyl, or substituted aryl, wherein 0 ⁇ x ⁇ about 3 and z is from about 5 to about 30;
  • each R 2 is selected from the following groups or combinations of the following groups: -(CH 2 ) n - and/or -[CH(CH 3 )CH 2 ]-; and
  • each R 5 is selected from the following groups: -OH; and -O
  • each R 5 is selected independently from the following:
  • polyhydroxy fatty acid amide surfactants of the formula: R 2 - C(O) - N(R1) - Z wherein: each Rl is H, C1-C4 hydrocarbyl, C1 -C4 alkoxyalkyl, or hydroxyalkyl; and R2 is a C5-C31 hydrocarbyl moiety; and each Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an ethoxylated derivative thereof; and each R' is H or a cyclic mono- or poly- saccharide, or alkoxylated derivative thereof; and d. mixtures thereof.
  • Suitable phase stabilizers also include surfactant complexes formed by one surfactant ion being neutralized with surfactant ion of opposite charge or an electrolyte ion that is suitable for reducing dilution viscosity and block copolymer surfactants comprising polyethylene oxide moieties and propylene oxide moieties
  • phase stabilizers examples include: (1)- Alkyl or alkyl-aryl alkoxylated nonionic surfactants
  • Suitable alkyl alkoxylated nonionic surfactants are generally derived from saturated or unsaturated primary, secondary, and branched fatty alcohols, fatty acids, alkyl phenols, or alkyl aryl (e.g., benzoic) carboxylic acid, where the active hydrogen(s) is alkoxylated with ⁇ about 30 alkylene, preferably ethylene, oxide moieties (e.g. ethylene oxide and/or propylene oxide).
  • nonionic surfactants for use herein preferably have from about 6 to about 22 carbon atoms on the alkyl or alkenyl chain, and are in either straight chain or branched chain configuration, preferably straight chain configurations having from about 8 to about 18 carbon atoms, with the alkylene oxide being present, preferably at the primary position, in average amounts of ⁇ about 30 moles of alkylene oxide per alkyl chain, more preferably from about 5 to about 15 moles of alkylene oxide, and most preferably from about 8 to about 12 moles of alkylene oxide.
  • Preferred materials of this class also have pour points of about 70°F and/or do not solidify in these clear formulations.
  • alkyl alkoxylated surfactants with straight chains examples include Neodol ® 91-8, 25-9, 1-9, 25-12, 1-9, and 45-13 from Shell, Plurafac ® B-26 and C-17 from BASF, and Brij ® 76 and 35 from ICI Surfactants.
  • Examples of branched alkyl alkoxylated surfactants include Tergitol ® 15-S-12, 15-S-15, and 15-S-20 from Union Carbide and Emulphogene ® BC-720 and BC-840 from GAF.
  • alkyl-aryl alkoxylated surfactants examples include Igepal ® CO-620 and CO-710, from Rhone Poulenc, Triton ® N-l 11 and N-150 from Union Carbide, Dowfax ® 9N5 from Dow and Lutensol ® AP9 and API 4, from BASF.
  • alkyl-aryl alkoxylated surfactants include Igepal ® CO-620 and CO-710, from Rhone Poulenc, Triton ® N-l 11 and N-150 from Union Carbide, Dowfax ® 9N5 from Dow and Lutensol ® AP9 and API 4, from BASF.
  • Suitable alkyl alkoxylated nonionic surfactants with amine functionality are generally derived from saturated or unsaturated, primary, secondary, and branched fatty alcohols, fatty acids, fatty methyl esters, alkyl phenol, alkyl benzoates, and alkyl benzoic acids that are converted to amines, amine-oxides, and optionally substituted with a second alkyl or alkyl-aryl hydrocarbon with one or two alkylene oxide chains attached at the amine functionality each having ⁇ about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine.
  • alkylene oxide moieties e.g. ethylene oxide and/or propylene oxide
  • the amine, amide or amine- oxide surfactants for use herein have from about 6 to about 22 carbon atoms, and are in either straight chain or branched chain configuration, preferably there is one hydrocarbon in a straight chain configuration having about 8 to about 18 carbon atoms with one or two alkylene oxide chains attached to the amine moiety, in average amounts of ⁇ 50 about moles of alkylene oxide per amine moiety, more preferably from about 5 to about 15 moles of alkylene oxide, and most preferably a single alkylene oxide chain on the amine moiety containing from about 8 to about 12 moles of alkylene oxide per amine moiety.
  • Preferred materials of this class also have pour points about 70°F and/or do not solidify m these clear formulations.
  • ethoxylated amine surfactants examples include Berol 397 and 303 from Rhone Poulenc and Ethomeens ® C/20, C25, T/25, S/20, S/25 and Ethodumeens ® T/20 and T25 from Akzo.
  • the compounds of the alkyl or alkyl-aryl alkoxylated surfactants and alkyl or alkyl-aryl amine, amide, and amine-oxide alkoxylated have the following general formula:
  • each R is selected from the group consisting of saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain preferably having a length of from about 6 to about 22, more preferably from about 8 to about 18 carbon atoms, and even more preferably from about 8 to about 15 carbon atoms, preferably, linear and with no aryl moiety; wherein each R 2 is selected from the following groups or combinations of the following groups: -(CH 2 ) n - and/or - [CH(CH 3 )CH 2 ]-; wherein about 1 ⁇ n ⁇ about 3; Y is selected from the following groups: -O-; -N(A) q -; -C(O)O-; - (O ⁇ )N(A) q -; -B-R 3 -O-; -B-R 3 -N(
  • the terminal hydrogen in each alkoxy chain can be replaced by a short chain C ⁇ - alkyl or acyl group to "cap" the alkoxy chain, z is from about 5 to about 30.
  • p is the number of ethoxylate chains, typically one or two, preferably one and m is the number of hydrophobic chains, typically one or two, preferably one and q is a number that completes the structure, usually one.
  • the preferred y is 0.
  • Suitable alkoxylated and non-alkoxylated phase stabilizers with bulky head groups are generally derived from saturated or unsaturated, primary, secondary, and branched fatty alcohols, fatty acids, alkyl phenol, and alkyl benzoic acids that are derivatized with a carbohydrate group or heterocyclic head group. This structure can then be optionally substituted with more alkyl or alkyl-aryl alkoxylated or non- alkoxylated hydrocarbons.
  • the heterocyclic or carbohydrate is alkoxylated with one or more alkylene oxide chains (e.g. ethylene oxide and or propylene oxide) each having ⁇ about 50, preferably ⁇ about 30, moles per mole of heterocyclic or carbohydrate.
  • the hydrocarbon groups on the carbohydrate or heterocyclic surfactant for use herein have from about 6 to about 22 carbon atoms, and are in either straight chain or branched chain configuration, preferably there is one hydrocarbon having from about 8 to about 18 carbon atoms with one or two alkylene oxide chains carbohydrate or heterocyclic moiety with each alkylene oxide chain present in average amounts of ⁇ about 50, preferably ⁇ about 30, moles of carbohydrate or heterocyclic moiety, more preferably from about 5 to about 15 moles of alkylene oxide per alkylene oxide chain, and most preferably between about 8 and about 12 moles of alkylene oxide total per surfactant molecule including alkylene oxide on both the hydrocarbon chain and on the heterocyclic or carbohydrate moiety.
  • phase stabilizers in this class are Tween ® 40, 60, and 80 available from ICI Surfactants.
  • the compounds of the alkoxylated and non-alkoxylated nonionic surfactants with bulky head groups have the following general formulas:
  • R is selected from the group consisting of saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain having a length of from about 6 to about 22;
  • Y' is selected from the following groups: -
  • A is selected from the following groups: H; R 1 ; -
  • each R is selected from the following groups or combinations of the following groups: -(CH ) n - and/or -[CH(CH 3 )CH ]-; and each R 5 is selected from the following groups: -OH; and -O(R 2 O) z -H ; and m is from about 2 to about 4;
  • each R is selected independently from the following: -CH 2 (CH 2 -(OR 2 ) z -H)-CH 2 - ction D above and z, z', and z" are all from about 5 ⁇ to ⁇ about 20, more preferably the total number of z + z' + z" is from about 5 ⁇ to ⁇ about 20.
  • R 6 - C(O) - N(R 7 ) - W Another group of surfactants that can be used are polyhydroxy fatty acid amide surfactants of the formula: R 6 - C(O) - N(R 7 ) - W wherein: each R 7 is H, C1 -C4 hydrocarbyl, C1-C4 alkoxyalkyl, or hydroxyalkyl, e.g., 2- hydroxyethyl, 2-hydroxypropyl, etc., preferably C1 -C4 alkyl, more preferably Ci or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl) or methoxyalkyl; and R ⁇ is a C5-C31 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain Ci 1 -C17 alkyl or alkenyl, or mixture thereof; and W
  • W preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably W is a glycityl moiety. W preferably will be selected from the group consisting of -CH2- (CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n -CH 2 OH, -CH 2 -
  • (CHOH) 2 (CHOR')(CHOH)-CH 2 OH where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ . Mixtures of the above W moieties are desirable.
  • R6 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N- isobutyl, N-2-hydroxyethyl, N-1-methoxypropyl, or N-2-hydroxypropyl.
  • R"-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • W can be 1 -deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1 -deoxylactityl, 1- deoxygalactityl, 1 -deoxymannityl, 1-deoxymaltotriotityl, etc. (4)- Alkoxylated cationic quaternary ammonium surfactants
  • Alkoxylated cationic quaternary ammonium surfactants suitable for this invention are generally derived from fatty alcohols, fatty acids, fatty methyl esters, alkyl substituted phenols, alkyl substituted benzoic acids, and/or alkyl substituted benzoate esters, and/or fatty acids that are converted to amines which can optionally be further reacted with another long chain alkyl or alkyl-aryl group; this amine compound is then alkoxylated with one or two alkylene oxide chains each having ⁇ about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine.
  • alkylene oxide moieties e.g. ethylene oxide and/or propylene oxide
  • Typical of this class are products obtained from the quaternization of aliphatic saturated or unsaturated, primary, secondary, or branched amines having one or two hydrocarbon chains from about 6 to about 22 carbon atoms alkoxylated with one or two alkylene oxide chains on the amine atom each having less than ⁇ about 50 alkylene oxide moieties.
  • the amine hydrocarbons for use herein have from about 6 to about 22 carbon atoms, and are in either straight chain or branched chain configuration, preferably there is one alkyl hydrocarbon group in a straight chain configuration having about 8 to about 18 carbon atoms.
  • Suitable quaternary ammonium surfactants are made with one or two alkylene oxide chains attached to the amine moiety, in average amounts of ⁇ about 50 moles of alkylene oxide per alkyl chain, more preferably from about 3 to about 20 moles of alkylene oxide, and most preferably from about 5 to about 12 moles of alkylene oxide per hydrophobic, e.g., alkyl group.
  • Preferred materials of this class also have a pour points below about 70°F and/or do not solidify in these clear formulations.
  • phase stabilizers of this type include Ethoquad ® 18/25, C/25, and O/25 from Akzo and Variquat ® -66 (soft tallow alkyl bis(polyoxyethyl) ammonium ethyl sulfate with a total of about 16 ethoxy units) from Witco.
  • the compounds of the ammonium alkoxylated cationic surfactants have the following general formula:
  • Surfactant complexes are considered to be surfactant ions neutralized with a surfactant ion of opposite charge or a surfactant neutralized with an electrolyte that is suitable for reducing dilution viscosity, an ammonium salt, or a polycationic ammonium salt.
  • a surfactant complex is formed by surfactants of opposite charge, it is preferable that the surfactants have distinctly different chain lengths e.g. a long-chain surfactant complexed with a short-chain surfactant to enhance the solubility of the complex and it is more preferable that the that the long chain surfactant be the amine or ammonium containing surfactant.
  • Long chain surfactants are defined as containing alkyl chains with from about 6 to about 22 carbon atoms. These alkyl chains can optionally contain a phenyl or substituted phenyl group or alkylene oxide moieties between the chain and the head group. Short chain surfactants are defined as containing alkyl chains with less than 6 carbons and optionally these alkyl chains could contain a phenyl or substituted phenyl group or alkylene oxide moieties between the alkyl chain and the head group.
  • Suitable surfactant complexes include mixtures of Armeen ® APA-10 and calcium xylene sulfonate, Armeen APA-10 and magnesium chloride, lauryl carboxylate and triethanol amine, linear alkyl benzene sulfonate and C 5 - dimethyl amine, or alkyl ethoxylated sulfate and tetrakis N,N,N'N' (2-hydroxylpropyl) ethylenediamine.
  • long-chain surfactants for making complexes have the following general formula:
  • R J -Y 2 wherein R 1 is as hereinbefore from section D above and Y 2 can be chosen from the following structures: -N(A) 2 ; -C(O)N(A) 2 ; -(O ⁇ -)N(A) 2 ; -B-R 3 -N(A) 2 ; -B-R 3 - C(O)N(A) 2 ; -B-R 3 -N( ⁇ O)(A) 2 ; -CO 2 " ; -SO 3 "2 ; -OSO 3 "2 ; -O(R 2 O) x CO 2 ' ; -O(R 2 O) x SO 3 "2 ; and -O(R 2 O) x OSO 3 "2 ; with B and R 3 as is hereinbefore section D above and 0 ⁇ x ⁇ 4 .
  • short-chain surfactants for making complexes have the following general formula:
  • R 4 -Y 2 wherein R 1 , R 3 , B, and Y 2 are as hereinbefore and R 4 can be chosen from the following: -(CH 2 ) y CH 3 ; -(CH 2 ) y -phenyl or -(CH 2 ) y -substituted phenyl with 0 ⁇ y ⁇ 6.
  • Suitable polymers include a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers are comprised of repeating units of ethylene and/or propylene terephthalate and polyethylene oxide terephthalate at a preferred molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from about 25:75 to about 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of this polymer is in the range of from about 5,000 to about 55,000.
  • Another preferred polymer is a crystallizable polyester with repeat units of ethylene terephthalate units containing from about 10%> to about 15%> by weight of ethylene terephthalate units together with from about 10%> to about 50%> by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1.
  • this polymer include the commercially available materials Zelcon ® 4780 (from DuPont) and Milease ® T (from ICI). Highly preferred polymers have the generic formula:
  • the R moieties are essentially 1 ,4-phenylene moieties.
  • the term "the Rl moieties are essentially 1 ,4-phenylene moieties” refers to compounds where the R i moieties consist entirely of 1 ,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof.
  • Arylene and alkarylene moieties which can be partially substituted for 1 ,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1 ,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene and mixtures thereof.
  • Alkylene and alkenylene moieties which can be partially substituted include ethylene, 1 ,2-propylene, 1 ,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1 ,7-heptamethylene, 1,8-octamethylene, 1 ,4-cyclohexylene, and mixtures thereof.
  • the degree of partial substitution with moieties other than 1 ,4-phenylene should be such that the desired properties of the compound are not adversely affected to any great extent.
  • the degree of partial substitution which can be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1 ,4-phenylene moieties.
  • compounds where the R ⁇ comprise from about 50%. to about 100%) 1 ,4-phenylene moieties (from 0 to about 50%> moieties other than 1 ,4-phenylene) are adequate.
  • the Rl moieties consist entirely of (i.e., comprise 100%) 1 ,4-phenylene moieties, i.e., each Rl moiety is 1 ,4-phenylene.
  • suitable ethylene or substituted ethylene moieties include ethylene, 1,2 -propylene, 1,2-butylene, 1 ,2-hexylene, 3-methoxy-l,2-propylene and mixtures thereof.
  • the R moieties are essentially ethylene moieties, 1,2-propylene moieties or mixture thereof.
  • 1 ,2-propylene moieties or a similar branched equivalent is desirable for inco ⁇ oration of any substantial part of the polymer in the liquid fabric softener compositions.
  • from about 75% to about 100%>, more preferably from about 90%> to about 100%, of the R2 moieties are 1,2-propylene moieties.
  • each n is at least about 6, and preferably is at least about 10.
  • the value for each n usually ranges from about 12 to about 113. Typically, the value for each n is in the range of from about 12 to about 43.
  • copolymers include surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
  • surfactants such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
  • the copolymer can optionally contain propylene oxide in an amount up to about 15%) by weight.
  • Other preferred copolymer surfactants can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty, inco ⁇ orated herein by reference.
  • Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound.
  • a particularly preferred copolymer contains from about 40% to about 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend comprising about 75%>, by weight of the blend, of a reverse block copolymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the blend, of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane.
  • Suitable for use as copolymer are those having relatively high hydrophilic- lipophilic balance (HLB).
  • polymers useful herein include the polyethylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds for example, have a melting point within the range of from about 30°C to about 100°C, can be obtained at molecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol with the requisite number of moles of ethylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol.
  • Suitable surfactants have the formula:
  • R C(O) - N(R 4 ) n - [(R'O) x (R 2 O) y R 3 ] m
  • R is C 7-21 linear alkyl, C 7-2 ⁇ branched alkyl, C 7-2 ⁇ linear alkenyl, C 7-2 ⁇ branched alkenyl, and mixtures thereof.
  • R is C 8- ⁇ 8 linear alkyl or alkenyl.
  • R 1 is -CH 2 -CH2-
  • R 2 is C 3 -C 4 linear alkyl, C 3 -C branched alkyl, and mixtures thereof; preferably R 2 is -CH(CH 3 )-CH 2 -.
  • Surfactants which comprise a mixture of Rl and R2 units preferably comprise from about 4 to about 12 -CH 2 -CH - units in combination with from about 1 to about 4 -CH(CH 3 )-CH - units.
  • the units may be alternating or grouped together in any combination suitable to the formulator.
  • the ratio of R 1 units to R 2 units is from about 4 : 1 to about 8 : 1.
  • an R 2 unit i.e. -C(CH 3 )H-CH 2 -
  • R 3 is hydrogen, Cj-C 4 linear alkyl, C 3 -C branched alkyl, and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen.
  • R 4 is hydrogen, C ⁇ -C 4 linear alkyl, C -C branched alkyl, and mixtures thereof; preferably hydrogen.
  • index m is equal to 2
  • index n must be equal to 0 and the R4 unit is absent.
  • the index m is 1 or 2, the index n is 0 or 1, provided that m + n equals 2;
  • 1 7 " preferably m is equal to 1 and n is equal to 1 , resulting in one - [(R O) x (R O) y R ] unit and R4 being present on the nitrogen.
  • the index x is from 0 to about 50, preferably from about 3 to about 25, more preferably from about 3 to about 10.
  • the index y is from 0 to about 10, preferably 0, however when the index y is not equal to 0, y is from 1 to about 4.
  • Preferably all the alkyleneoxy units are ethyleneoxy units.
  • ethoxylated alkyl amide surfactants are Rewopal R C 6 from Witco, Amidox ® C5 from Stepan, and Ethomid ® O / 17 and Ethomid ® HT / 60 from Akzo.; and (8).- Mixtures thereof.
  • Auxiliary whiteness preservatives are optionally, but preferably inco ⁇ orated in order to improve fabric whiteness. Auxiliary whiteness preservatives can be used together with the metal chelant to give an extra boost to whiteness maintenance. 1. Brighteners
  • Optical brighteners also known as fluorescent whitening agents (FWAs) or fluorescent brighteners preserve whiteness by compensating for the yellow appearance by adding a complementary color to the fabric and thus the undesired yellowing is rendered invisible.
  • FWAs fluorescent whitening agents
  • Optical brighteners preserve whiteness by compensating for the yellow appearance by adding a complementary color to the fabric and thus the undesired yellowing is rendered invisible.
  • a white fabric is stored for a length of time, it can appear to be yellow.
  • auto-oxidation of polyunsaturated materials such as body fatty acids or fabric softener actives generate compounds that appear yellow on white fabrics, because these compounds absorb short-wavelength light, light in the range of violet to blue or wavelengths between about 370 nm to 550 nm.
  • Optical brighteners absorb light in the range of ultraviolet light and emit light via fluorescence in the blue to blue violet range of the spectrum. Thus optical brighteners replace this missing part of the spectrum on yellowing fabric and so a white appearance is retained
  • the product contains from about 0.005% to about 5%, preferably from about 0.05%) to about 3%, more preferably from about 0.1% to about 2%, even more preferably from about 0.15% to about 1%, by weight of the composition, optical brightener.
  • Lower levels of brightener are used in the presence of the metal chelating compound. In the absence of the metal chelating compound, higher levels of brightener are preferred.
  • Preferred optical brighteners are colorless on the substrate and do not absorb in the visible part of the spectrum. Preferred optical brighteners are also lightfast, meaning that these do not degrade substantially in sunlight. Optical brighteners suitable for use in this invention absorb light in the ultraviolet portion of the spectrum between 275 nm and about 400 nm and emit light in the violet to violet-blue range of the spectrum from about 400 nm to about 550 nm. Preferably, the optical brightener will contain an uninterrupted chain of conjugated double bounds.
  • Optical brighteners are typically, but not limited to, derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, five-membered heterocycles such as triazoles, oxazoles, imidiazoles, etc., or six-membered heterocycles (coumarins, naphthalamide, s-triazine, etc.).
  • Many specific brightener structures are described in The Kirk-Othmer Encyclopedia of Chemistry 3 rd Ed., pp 214-226 and in references therein U. S. Pat. No. 5,759,990 at column 21, lines 15-60; said references being inco ⁇ orated herein by reference as suitable for use in this invention.
  • Ionic brighteners with a positive or negative charge are preferred as this improves solubility in the compositions disclosed herein and thus are easier to formulate and are more stable.
  • Cationic brighteners are also preferred since these can compete effectively with cationic fabric softeners to partition to the surface of the fabric.
  • Some preferred, but nonlimiting brighteners are Optiblanc ® GL and Optiblanc LSN from 3V Inc., Weehawken, New Jersey, Tinopals ® CBS SP Slurry 33, PLC, UNPA- GX, 4BM, 4BMS, 5BM, 5BMS, 5BM-GX, AMS-GX, DMS-X, DCS Liquid, K, ERN, LCS, LFW, and TAS, Univex ® , SK, ERN, and AT, from Ciba, High Point, North Carolina, Blankophor ® FBW, FB, LPG , and HRS, from Mobay. In addition to preventing auto-oxidation, some brighteners also prevent dye transfer.
  • Bluing agents also act to preserve whiteness by compensating for the yellow appearance by again adding a complementary color to the fabric and thus the undesired yellowing is no longer noticeable. Like optical brighteners, bluing agents replace this missing part of the spectrum and so a white appearance is retained.
  • UV absorbers can operate by protecting the fabric and any fabric softener compound deposited on the fabric from UV exposure. UV light is know to initiate auto-oxidation processes and UV absorbers can be deposited on fabric in such a way that UV light is blocked from the fabric and unsaturated fatty materials, thus preventing the initiation of auto-oxidation. 5. Oxidative Stabilizers
  • Oxidative stabilizers can be present in the compositions of the present invention and these prevent yellowing by acting as a scavenger for the oxidative processes, thus preventing and/or terminating auto-oxidation, or by reversing oxidation and thus reversing yellowing.
  • the term "oxidative stabilizer,” as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%), preferably from about 0.01% to about 0.2%>, more preferably from about 0.035%) to about 0.1% for antioxidants, and, preferably, from about 0.01% to about 0.2% for reductive agents.
  • antioxidants examples include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Teno ⁇ R PG and Tenox ® S-l ; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, available from Eastman Chemical Products, Inc., under the trade name Tenox ® -6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane ® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox ® TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox ® GT-l/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (C ⁇ -C )
  • Oxidative stabilizers can also be added at any point during the process of making fabric softener raw materials where polyunsaturated compounds would be present. E.g., these could be added into oils used to make fatty acids, during fatty acid making and/or storage during fabric softener making and/or storage. These assure good odor stability under long term storage conditions.
  • Other Optional Ingredients can also be added at any point during the process of making fabric softener raw materials where polyunsaturated compounds would be present. E.g., these could be added into oils used to make fatty acids, during fatty acid making and/or storage during fabric softener making and/or storage. These assure good odor stability under long term storage conditions.
  • the fabric care composition of the present invention can optionally contain adjunct odor-controlling materials, chelating agents, antistatic agents, insect and moth repelling agents, colorants, especially bluing agents, antioxidants, and mixtures thereof in addition to the cyclic silicone molecules.
  • the total level of optional ingredients is low, preferably less than about 5%, more preferably less than about 3%, and even more preferably less than about 2%, by weight of the usage composition. These optional ingredients exclude the other ingredients specifically mentioned hereinbefore.
  • Inco ⁇ orating adjunct odor-controlling materials can enhance the capacity of the cyclodextrin to control odors as well as broaden the range of odor types and molecule sizes which can be controlled.
  • Such materials include, for example, metallic salts, water- soluble cationic and anionic polymers, zeolites, water-soluble bicarbonate salts, and mixtures thereof. Water-Soluble Polyionic Polymers
  • water-soluble polyionic polymers e.g., water-soluble cationic polymer and water-soluble anionic polymers can be used in the composition of the present invention to provide additional odor control benefits.
  • Cationic polymers e.g., polyamines
  • Water-soluble cationic polymers e.g., those containing amino functionalities, amido functionalities, and mixtures thereof, are useful in the present invention to control certain acid-type odors.
  • Anionic polymers e.g., polvacrylic acid
  • Water-soluble anionic polymers e.g., polyacryhc acids and their water-soluble salts are useful in the present invention to control certain amine-type odors.
  • Preferred polyacryhc acids and their alkali metal salts have an average molecular weight of less than about 20,000, more preferably less than 5,000000, preferably less than 10,000, more preferably from about 500 to about 5,000.
  • Polymers containing sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, and their water-soluble salts, and mixtures thereof, and mixtures with carboxylic acid and carboxylate groups, are also suitable.
  • Water-soluble polymers containing both cationic and anionic functionalities are also suitable. Examples of these polymers are given in U.S. Pat. 4,909,986, issued March 20, 1990 to N. Kobayashi and A. Kawazoe, inco ⁇ orated herein by reference. Another example of water-soluble polymers containing both cationic and anionic functionalities is a copolymer of dimethyldiallyl ammonium chloride and acrylic acid, commercially available under the trade name Merquat 280® from Calgon.
  • a water-soluble polymer When a water-soluble polymer is used it is typically present at a level of from about 0.001% to about 3%, preferably from about 0.005%> to about 2%, more preferably from about 0.01%> to about 1%, and even more preferably from about 0.05%> to about 0.5%, by weight of the usage composition.
  • Antistatic Agents When a water-soluble polymer is used it is typically present at a level of from about 0.001% to about 3%, preferably from about 0.005%> to about 2%, more preferably from about 0.01%> to about 1%, and even more preferably from about 0.05%> to about 0.5%, by weight of the usage composition.
  • composition of the present invention can optionally contain an effective amount of antistatic agent to provide the treated clothes with in-wear static.
  • antistatic agents are those that are water soluble in at least an effective amount, such that the composition remains a clear solution.
  • these antistatic agents are monoalkyl cationic quaternary ammonium compounds, e.g., mono(Ci o _ Ci4 alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride, available under the trade name Dehyquart E® from Henkel, and ethyl bis(polyethoxy ethanol) alkylammonium ethylsulfate, available under the trade name Variquat 66® from Witco Co ⁇ ., polyethylene glycols, polymeric quaternary ammonium salts, such as polymers conforming to the general formula:
  • a no foaming, or low foaming, agent is used, to avoid foam formation during fabric treatment.
  • polyethoxylated agents such as polyethylene glycol or Variquat 66® are not used when alpha-cyclodextrin is used.
  • the polyethoxylate groups have a strong affinity to, and readily complex with, alpha- cyclodextrin which in turn depletes the uncomplexed cyclodextrin available for odor control.
  • an antistatic agent When used it is typically present at a level of from about 0.05%) to about 10%>, preferably from about 0.1% to about 5%, more preferably from about 0.3%) to about 3%>, by weight of the usage composition.
  • Insect and/or Moth Repelling Agent When used it is typically present at a level of from about 0.05%) to about 10%>, preferably from about 0.1% to about 5%, more preferably from about 0.3%) to about 3%>, by weight of the usage composition.
  • the composition of the present invention can optionally contain an effective amount of insect and/or moth repelling agents.
  • Typical insect and moth repelling agents are pheromones, such as anti-aggregation pheromones, and other natural and/or synthetic ingredients.
  • Preferred insect and moth repellent agents useful in the composition of the present invention are perfume ingredients, such as citronellol, citronellal, citral, linalool, cedar extract, geranium oil, sandalwood oil, 2-(diethylphenoxy)ethanol, 1-dodecene, etc.
  • Other examples of insect and/or moth repellents useful in the composition of the present invention are disclosed in U.S. Pat. Nos.
  • Colorant Colorants and dyes can be optionally added to the fabric care compositions for visual appeal and performance impression. When colorants are used, they are used at extremely low levels to avoid fabric staining.
  • Preferred colorants for use in the present compositions are highly water-soluble dyes, e.g., Liquitint® dyes available from Milliken Chemical Co.
  • Non-limiting examples of suitable dyes are, Liquitint Blue HP , Liquitint Blue 65 , Liquitint Patent Blue , Liquitint Royal Blue , Liquitint Experimental Yellow 8949-43®, Liquitint Green HMC®, Liquitint Yellow IT®, and mixtures thereof, preferably Liquitint Blue HP , Liquitint Blue 65 , Liquitint Patent Blue , Liquitint Royal Blue , Liquitint Experimental Yellow 8949-43® and mixtures thereof.
  • Optional Anti-Clogging Agent is, Liquitint Blue HP , Liquitint Blue 65 , Liquitint Patent Blue , Liquitint Royal Blue , Liquitint Experimental Yellow 8949-43® and mixtures thereof.
  • Optional anti-clogging agent which enhances the wetting and anti-clogging properties of the composition, especially when starch is present, is chosen from the group of polymeric glycols of alkanes and olefins having from 2 to about 6, preferably 2 carbon atoms.
  • the anti-clogging agent inhibits the formation of "plugs" in the spray nozzle.
  • An example of the preferred anti-clogging agent is polyethylene glycol having an average molecular weight of from about 800 to about 12,000, more preferably from about 1,400 to about 8,000.
  • the anti-clogging agent is present at a level of from about 0.01%) to about 1%, preferably from about 0.05%> to about 0.5%o, more preferably, from about 0.1% to about 0.3%> by weight of the usage composition.
  • compositions according to the present invention can further comprise a builder or builder system, especially for detergent compositions.
  • a builder or builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • Phosphate builders can also be used herein.
  • the present invention can include a suitable builder or detergency salt.
  • the level of detergent salt/builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least about 1%> builder and more typically from about 10%> to about 80%>, even more typically from about 15%> to about 50% by weight, of the builder. Lower or higher levels, however, are not meant to be excluded.
  • Inorganic or P-containing detergent salts include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates
  • carbonates including bicarbonates and sesquicarbonates
  • sulphates sulphates
  • aluminosilicates aluminosilicates.
  • non-phosphate salts are required in some locales.
  • compositions herein function su ⁇ risingly well even in 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.
  • Organic detergent builders suitable for the pu ⁇ oses of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • silicate builders examples include silicate builders, carbonate salts, aluminosilicate builders, polycarboxylate builders, citrate builders, 3,3-dicarboxy-4-oxa-l,6-hexanedioate builders and related compounds disclosed in U.S. Patent No. 4,566,984, to Bush, succinic acid builders, phosphorous-based builders and fatty acids, are disclosed in U.S. Patent Nos. 5,576,282, 5,728,671 and 5,707,950.
  • Additional suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
  • an inorganic ion exchange material commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
  • polycarboxylates suitable for the present invention are polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3- propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, .and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5, 6-hexane -hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS- 6), and a water-soluble carboxylate chelating agent such as citric acid.
  • a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS- 6)
  • a water-soluble carboxylate chelating agent such as citric acid.
  • Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a water soluble carboxylate chelating agent such as citric acid.
  • Preferred builder systems for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.
  • Suitable water-soluble organic salts are the homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1, 596,756.
  • Examples of such salts are polyacrylates of MW 2000- 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • Detergency builder salts are normally included in amounts of from 5% to 80%> by weight of the composition preferably from 10%> to 70% and most usually from 30%> to 60% by weight.
  • Bleaching Agent Additional optional detergent ingredients that can be included in the detergent compositions of the present invention include bleaching agents such as hydrogen peroxide, PBl, PB4 and percarbonate with a particle size of 400-800 microns. These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators. When present oxygen bleaching compounds will typically be present at levels of from about 1%> to about 25%.
  • the bleaching agent component for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.
  • the bleaching agent suitable for the present invention can be an activated or non- activated bleaching agent.
  • the hydrogen peroxide releasing agents can be used in combination with, for example, the bleach activators disclosed in U.S. Patent No. 5,707,950 or Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS), described in WO94/28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • suitable activators are acylated citrate esters.
  • bleaching agents including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in WO95/27772, WO95/27773, WO95/27774, WO95/27775 and U.S. Patent No. 5,707,950.
  • Metal-containing catalysts for use in bleach compositions include cobalt- containing catalysts such as pentamine acetate cobalt(III) salts and manganese-containing catalysts such as those described in EPA 549 271; EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416 and US 5,114,611.
  • Bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in the patent application No 94870206.3. All of the above patents and applications being inco ⁇ orated herein by reference.
  • the fabric care compositions of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering and conditioning operations involving colored fabrics.
  • Polymeric dye transfer inhibiting agents The fabric care compositions according to the present invention can also comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally inco ⁇ orated into fabric care compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash or the rinse.
  • Especially suitable polymeric dye transfer inhibiting agents are polyvinylpyrrolidone polymers, poly(4-vinylpyridine-N-oxide), polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • Examples of such dye transfer inhibiting agents are disclosed in U.S. Pat. No. 5,804,219, issued Sept. 8, 1998 to T. Trinh, S. L.-L. Sung, H. B. Tordil, and P. A. Wendland, and in U.S. Patent Nos. 5,707,950 and 5,707,951, all are inco ⁇ orated herein by reference.
  • 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 described in the Journal of Polymer Science, volume 22, pages 1035-1039.
  • the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure.
  • the cross-linked polymers entrap the dyes by swelling.
  • Chlorine scavenging agents are actives that react with chlorine, or with chlorine- generating materials, such as hypochlorite, to eliminate or reduce the bleaching activity of the chlorine materials. Chlorine is used in many parts of the world to sanitize water. To make sure that the water is safe, a small amount, typically about 1 to 2 ppm of chlorine is left in the water. It has been found that this small amount of chlorine in the tap water can cause fading of some fabric dyes. For rinse-added compositions, it is suitable to inco ⁇ orate enough chlorine scavenging agent to neutralize about 1 ppm, preferably 2 ppm, more preferably 3 ppm, and even more preferably 10 ppm of chlorine in rinse water. Suitable levels of the optional chlorine scavengers in the rinse-added composition of the present invention range from about 0.01% to about 10% > , preferably from about 0.02% to about 5%, more preferably from about 0.05% to about 4%.
  • the fabric softener compositions can contain an effective amount of chlorine scavenger, preferably selected from the group consisting of: a. amines and their salts; b. ammonium salts; c. amino acids and their salts; d. polyamino acids and their salts; e. polyethyleneimines and their salts; f. polyamines and their salts; g. polyamineamides and their salts; h. polyacrylamides; and i. mixtures thereof.
  • chlorine scavenger preferably selected from the group consisting of: a. amines and their salts; b. ammonium salts; c. amino acids and their salts; d. polyamino acids and their salts; e. polyethyleneimines and their salts; f. polyamines and their salts; g. polyamineamides and their salts; h. polyacrylamides; and i. mixtures thereof.
  • Non-limiting examples of chlorine scavengers include amines, preferably primary and secondary amines, including primary and secondary fatty amines, and alkanolamines; and their salts; ammonium salts, e.g., chloride, bromide, citrate, sulfate; amine-functional polymers and their salts; amino acid homopolymers with amino groups and their salts, such as polyarginine, polylysine, polyhistidine; amino acid copolymers with amino groups and their salts, including l,5-di-ammonium-2-methyl-panthene dichloride and lysine monohydrochloride; amino acids and their salts, preferably those having more than one amino group per molecule, such as arginine, histidine, and lysine, reducing anions such as sulfite, bisulfite, thiosulfate, and nitrite, antioxidants such as ascorbate, carbamate, phenols; and mixture
  • Preferred chlorine scavengers are water soluble, especially, low molecular weight primary and secondary amines of low volatility, e.g., monoethanolamine, diethanolamine, tris(hydroxymethyl)aminomethane, hexamethylenetetramine, and their salts, and mixtures thereof.
  • Suitable chlorine scavenger polymers include: water soluble amine-functional polymers, e.g., polyethyleneimines, polyamines, polyamineamides, polyacrylamides, and their salts, and mixtures thereof.
  • the preferred polymers are polyethyleneimines; the polyamines, including, e.g., di(higher alkyl)cyclic amines and their condensation products, and polymers containing amino groups; polyamineamides, and their salts; and mixtures thereof.
  • Preferred polymers for use in the fabric softening compositions of the present invention are polyethyleneimines and their salts.
  • Preferred polyethyleneimines have a molecular weight of less than about 2000, more preferably from about 200 to about 1500.
  • the water solubility is preferably at least about 1 g/100 g water, more preferably at least about 3 g/100 g water, even more preferably at least about 5 g/100 g water.
  • Some polyamines with the general formula (R )2N(CX2) n N(R2)2 can serve both as a chlorine scavenging agent and a "chelant" color care agent.
  • Non-limiting examples of such preferred polyamines are N,N,N',N'-tetrakis(2-hydroxypropyl) ethylenediamine and N,N,N',N",N"-penta(2-hydroxypropyl)diethylenetri amine.
  • Preferred polymeric chlorine scavengers have an average molecular weight of less than about 5,000, more preferably from about 200 to about 2,000, even more preferably from about 200 to about 1,000. Low molecular weight polymers are easier to remove from fabrics than higher molecular weight polymers, resulting in less buildup of the chlorine scavenger and therefore less discoloration of the fabrics.
  • Liquid chlorine scavengers can be used in liquid softener compositions, but amine-functional chlorine scavengers are preferably neutralized by an acid, before they are added into the compositions.
  • Soil release agents are especially desirable additives at levels of from about 0.05%. to about 5%, preferably from about 0.1 % to about 4%, more preferably from about 0.2% to about 3%.
  • Suitable soil release agents are disclosed in U.S. Pat. Nos.: 4,702,857, Gosselink, issued Oct. 27, 1987; 4,711,730, Gosselink and Diehl, issued Dec. 8, 1987; 4,713,194, Gosselink issued Dec. 15, 1987; 4,877,896, Maldonado, Trinh, and Gosselink, issued Oct. 31, 1989; 4,956,447, Gosselink, Hardy, and Trinh, issued Sep. 11, 1990; and 4,749,596, Evans, Huntington, Stewart, Wolf, and Zimmerer, issued June 7, 1988, said patents being inco ⁇ orated herein by reference.
  • Especially desirable optional ingredients are polymeric soil release agents comprising block copolymers of polyalkylene terephthalate and polyoxyethylene terephthalate, and block copolymers of polyalkylene terephthalate and polyethylene glycol.
  • the polyalkylene terephthalate blocks preferably comprise ethylene and/or propylene groups. Many such soil release polymers are nonionic.
  • a preferred nonionic soil release polymer has the following average structure:
  • the polymeric soil release agents useful in the present invention can include anionic and cationic polymeric soil release agents.
  • Suitable anionic polymeric or oligomeric soil release agents are disclosed in U.S. Pat. No. 4,018,569, Trinh, Gosselink and Rattinger, issued April 4, 1989, said patent being inco ⁇ orated herein by reference.
  • Other suitable polymers are disclosed in U.S. Pat. No. 4,808,086, Evans, Huntington, Stewart, Wolf, and Zimmerer, issued Feb. 24, 1989, said patent being inco ⁇ orated herein by reference.
  • Suitable cationic soil release polymers are described in U.S. Pat. No. 4,956,447, Gosselink, Hardy, and Trinh, issued Sept. 11, 1990, said patent being inco ⁇ orated hereinbefore by reference.
  • the optional dye fixing agents are materials which are useful to improve the appearance of dyed fabrics by minimizing the loss of dye from fabrics due to washing.
  • Cationic fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR® PMF and CROSCOLOR® NOFF available from Crosfield; INDOSOL® E-50 (polyethyleneamine-based) and SANDOFLX® TPS from Sandoz; and CARTAFIX® CB from Clariant..
  • SANDOFLX SWE a cationic resinous compound
  • Tinofix® ECO Tinofix® FRD and Solfin® from Ciba- Geigy.
  • Preferred optional dye fixing agents for use in the compositions of the. present invention are SANDOFLX TPS and CARTAFIX CB.
  • Optional dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid-diamine condensates inter alia the hydrochloride, acetate, metosulphate and benzyl hydrochloride salts of diamine esters.
  • ammonium compounds such as fatty acid-diamine condensates inter alia the hydrochloride, acetate, metosulphate and benzyl hydrochloride salts of diamine esters.
  • Non-limiting examples include oleyldiethyl aminoethylamide, oleylmethyl diethylenediamine methosulphate, monostearylethylene diaminotrirnethylammonium methosulphate.
  • N-oxides of tertiary amines are suitable for use as dye fixatives in the compositions of the present invention.
  • Another class of optional dye fixing agents suitable for use in the present invention are cellulose reactive dye fixing agents.
  • the cellulose reactive dye fixatives may be suitably combined with one or more dye fixatives described herein above in order to comprise a "dye fixative system”.
  • cellulose reactive dye fixing agent is defined herein as "a dye fixative agent which reacts with the cellulose fibers upon application of heat or upon a heat treatment either in situ or by the formulator".
  • cellulose reactive dye fixing agents are compounds which contain a cellulose reactive moiety.
  • Non limiting examples of these compounds include halogeno- triazines, vinyl sulphones, epichlorhydrine derivatives, hydroxyethylene urea derivatives, formaldehyde condensation products, polycarboxylates, glyoxal and glutaraldehyde derivatives, and mixtures thereof. Further examples can be found in "Textile Processing and Properties", Tyrone L. Vigo, at page 120 to 121, Elsevier (1997), which discloses specific electrophilic groups and their corresponding cellulose affinity.
  • Preferred hydroxyethylene urea derivatives include dimethyloldihydroxy ethylene, urea, and dimethyl urea glyoxal.
  • Preferred formaldehyde condensation products include the condensation products derived from formaldehyde and a group selected from an amino-group, an imino-group, a phenol group, an urea group, a cyanamide group and an aromatic group.
  • Commercially available compounds among this class are Sandofix WE 56 from Clariant, Zetex E from Zeneca and Levogen BF from Bayer.
  • Preferred polycarboxylates derivatives include butane tetracarboxilic acid derivatives, citric acid derivatives, polyacrylates and derivatives thereof.
  • a referred cellulosic reactive dye fixing agent is Indosol CR (hydroxyethylene urea derivative) from Clariant.
  • Other preferred cellulosic reactive dye fixing agents are Rewin DWR and Rewin WBS from CHT R. Beitlich.
  • compositions of the present invention optionally comprise from about 0.001%) to about 40%>, preferably from about 0.5% to more preferably to about 10%, more preferably from about 1% to about 5%, by weight of the fabric care composition, of one or more dye fixing agents.
  • Dispersants preferably from about 0.5% to more preferably to about 10%, more preferably from about 1% to about 5%, by weight of the fabric care composition, of one or more dye fixing agents.
  • the detergent composition of the present invention can also contain dispersants.
  • Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1, 596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 1 ,000 to 100,000.
  • copolymer of acrylate and methylacrylate such as the 480N having a molecular weight of 4000, at a level from 0.5-20%> by weight of composition can be added in the detergent compositions of the present invention.
  • compositions of the invention can contain a lime soap peptiser compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6.
  • LSDP lime soap dispersing power
  • the lime soap peptiser compound is preferably present at a level from 0% to 20%> by weight.
  • LSDP lime soap dispersant power
  • Surfactants having good lime soap peptizer capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.
  • Polymeric lime soap peptizers suitable for use herein are described in the article by M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989).
  • Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6- aminohexanoyljbenzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptizers compounds.
  • Optional enzymes are useful in the compositions , especially wash-added and rinse-added compositions, of the present invention to improve cleaning, odor control and/or fabric appearance benefits.
  • Preferred enzymes include laundry detergent and/or fabric care applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase.
  • proteases are described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; and WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.
  • Preferred enhancers are substituted phenthiazine and phenoxasine 10- Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10- phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said peroxidases are normally inco ⁇ orated in the detergent composition at levels from 0.0001%) to 2% of active enzyme by weight of the detergent composition.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent LAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • lipases such as Ml Lipase ⁇ anc * Lipomax ⁇ - (Gist-Brocades) and Lipolase ⁇ - and Lipolase Ultra ⁇ -(Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO 88/09367 (Genencor).
  • the lipases and/or cutinases are normally inco ⁇ orated in the detergent composition at levels from 0.0001%) to 2% of active enzyme by weight of the detergent composition.
  • amylases can be included for removal of carbohydrate-based stains.
  • WO 94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which inco ⁇ orate mutant amylases. See also WO94/18314, Genencor, published August 18, 1994 and WO95/10603, Novo Nordisk A/S, published April 20, 1995.
  • Other amylases known for use in detergent compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US Pat.
  • amylases include Purafact Ox Am ⁇ described in WO 94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95.
  • ⁇ -amylases examples are TERMAMYL®, BAN®, FUNGAMYL® and DURAMYL®, all available from Novo Nordisk A S Denmark.
  • WO95/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of TERMAMYL® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the PHADEBAS® ⁇ -amylase activity assay.
  • Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
  • the cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit).
  • CEVU Cellulose Viscosity Unit
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS- 2.247.832 and WO95/26398.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
  • suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801, Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471.
  • Said cellulases are normally inco ⁇ orated in the detergent composition at levels from 0.0001%) to 2%o of active enzyme by weight of the detergent composition.
  • the above-mentioned enzymes can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Purified or non-purified forms of these enzymes can be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned.
  • Enzymes are normally inco ⁇ orated in the detergent composition at levels from 0.0001%) to 2%> of active enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates).
  • Other suitable detergent ingredients that can be added are enzyme oxidation scavengers. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme materials and means for their inco ⁇ oration into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694 to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their inco ⁇ oration into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques.
  • Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 to Novo.
  • Enzymes can also be used to control certain types of malodor, especially malodor from urine and other types of excretions, including regurgitated materials. Proteases are especially desirable. The activity of commercial enzymes depends very much on the type and purity of the enzyme being considered. Enzymes that are water soluble proteases like pepsin, tripsin, ficin, bromelin, papain, rennin, and mixtures thereof are particularly useful.
  • enzymes are normally inco ⁇ orated at levels sufficient to provide up to about 5 mg by weight, preferably from about 0.001 mg to about 3 mg, more preferably from about 0.002 mg to about 1 mg, of active enzyme per gram of the aqueous compositions.
  • the aqueous compositions herein can comprise from about 0.0001% to about 0.5%, preferably from about 0.001% to about 0.3%>, more preferably from about 0.005%> to about 0.2%> by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.0005 to 0.1 Anson units (AU) of activity per gram of aqueous composition.
  • Nonlimiting examples of suitable, commercially available, water soluble proteases are pepsin, tripsin, ficin, bromelin, papain, rennin, and mixtures thereof.
  • Papain can be isolated, e.g., from papaya latex, and is available commercially in the purified form of up to, e.g., about 80% protein, or cruder, technical grade of much lower activity.
  • Other suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms .
  • Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE .
  • proteases suitable for removing protein-based stains include those sold under the trade names ALCALASE® and SAVINASE® by Novo Industries A/S (Denmark) and MAXATASE® by International Bio-Synthetics, Inc. (The Netherlands).
  • Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985); Protease B (see European Patent Application Serial No.
  • Patent 3,600,319 issued August 17, 1971 to Gedge, et al., European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas, and in U.S. Patent 3,519,570. All of the above patents and applications are inco ⁇ orated herein, at least in pertinent part.
  • Enzyme-polyethylene glycol conjugates are also preferred.
  • Such polyethylene glycol (PEG) derivatives of enzymes wherein the PEG or alkoxy-PEG moieties are coupled to the protein molecule through, e.g., secondary amine linkages. Suitable derivatization decreases immunogenicity, thus minimizes allergic reactions, while still maintaining some enzymatic activity.
  • PEG polyethylene glycol
  • An example of protease-PEG's is PEG-subtilisin Carlsberg from B. lichenniformis coupled to methoxy-PEGs through secondary amine linkage, and is available from Sigma-Aldrich Co ⁇ ., St. Louis, Missouri.
  • the wash-added fabric care compositions herein can also optionally contain one or more iron and/or manganese chelating agents.
  • Suitable chelating agents is selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally- substituted aromatic chelating agents and mixtures thereof.
  • the chelating agents disclosed in said U. S. Pat. No. 5,759,990 at column 26, line 29 through column 27, line 38 are suitable.
  • Other examples of suitable chelating agents are disclosed in U.S. Patent No. 5,728,671.
  • EDDS ethylenediamine- N,N'-disuccinate
  • compositions herein can also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.
  • MGDA water-soluble methyl glycine diacetic acid
  • these chelating agents will generally comprise from about 0.1% to about 15%) by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • preferred metal chelating agents For rinse-added compositions, preferred metal chelating agents contain amine and especially tertiary amine moieties since these tend to be fabric substantive and very effectively chelate copper and iron as well as other metals.
  • a preferred amine-based metal chelating compound for use in compositions of the present invention has the following general structure:
  • Rl (Rl)(R 2 )N(CX2) n N(R3)(R 4 )
  • X is selected from the group consisting of hydrogen, linear or branched, substituted or unsubstituted alkyl having from 1 to 10 carbons atoms and substituted or unsubstituted aryl having at least 6 carbon atoms
  • n is an integer from 0 to 6
  • Ri , R2, R3, and R4 are independently selected from the group consisting of alkyl; aryl; alkaryl; arylalkyl; hydroxyalkyl; polyhydroxyalkyl; polyalkylether having the formula - ((CH2)yO) z R7 where R7 is hydrogen or a linear, branched, substituted or unsubstituted alkyl chain having from 1 to 10 carbon atoms and where y is an integer from 2 to 10 and z is an integer from 1 to 30; alkoxy; polyalkoxy having the formula: -(O(CH2)y)
  • Preferred chelating agents include those where R ⁇ , R2, R3, and R4 are independently selected from the group consisting of alkyl groups having from 1 to 10 carbon atoms and hydroxyalkyl groups having from 1 to 5 carbon atoms, preferably ethyl, methyl, hydroxyethyl, hydroxypropyl and isohydroxypropyl.
  • the preferred chelating agent has more than about 1%> nitrogen by weight of the compound, and preferably more than 7%>.
  • a preferred chelating agent is tetrakis-(2-hydroxylpropyl) ethylenediamine (TPED).
  • the rinse-added composition contains at least about 0.01%o, preferably at least about 0.05%, more preferably at least about 0.10%> and less than about 10%>, preferably less than about 5%> and more preferably less than about 1%> of chelating agent, by weight of the composition.
  • Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • 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.
  • Aqueous Carrier exemplified by silicones, and silica-silicone mixtures.
  • the preferred carrier of the present invention is water.
  • the water which is used can be distilled, deionized, or tap water. Water is the main liquid carrier due to its low cost, availability, safety, and environmental compatibility. Aqueous solutions are preferred for wrinkle control and odor control.
  • Water is very useful for fabric wrinkle removal or reduction. Not to be bound by theory, it is believed that water breaks many intrafiber and interfiber hydrogen bonds that keep the fabric in a wrinkle state. It also swells, lubricates and relaxes the fibers to help the wrinkle removal process.
  • Water serves as the liquid carrier for the fabric care branched polysaccharide and other soluble and/or dispersible optional ingredients.
  • Water also serves as the liquid carrier for the cyclodextrins, and facilitates the complexation reaction between the cyclodextrin molecules and any malodorous molecules that are on the fabric when it is treated.
  • the dilute aqueous solution also provides the maximum separation of cyclodextrin molecules on the fabric and thereby maximizes the chance that an odor molecule will interact with a cyclodextrin molecule.
  • water has an unexpected odor controlling effect of its own. It has been discovered that the intensity of the odor generated by some polar, low molecular weight organic amines, acids, and mercaptans is reduced when the odor- contaminated fabrics are treated with an aqueous solution. Not to be bound by theory, it is believed that water solubilizes and depresses the vapor pressure of these polar, low molecular weight organic molecules, thus reducing their odor intensity.
  • the level of liquid carrier in the compositions of the present invention is typically greater than about 80%, preferably greater than about 90%, more preferably greater than about 95% ⁇ , by weight of the composition.
  • the level of liquid carrier is typically from about 2% to about 98%>, by weight of the composition, preferably from about 35% to about 97%, more preferably from about 60% to about 95%o, by weight of the composition.
  • the carrier in addition to water, can contain a low molecular weight organic solvent that is highly soluble in water, e.g., ethanol, propanol, isopropanol, and the like, and mixtures thereof.
  • Low molecular weight alcohols can help the treated fabric to dry faster.
  • the optional solvent is also useful in the solubilization of some adjunct shape retention polymers described hereinbefore.
  • the optional water soluble low molecular weight solvent can be used at a level of up to about 50%>, typically from about 0.1%) to about 25%o, preferably from about 2%> to about 15%>, more preferably from about 5%> to about 10%, by weight of the total composition.
  • Factors that need to consider when a high level of solvent is used in the composition are odor, flammability, and environment impact.
  • the present invention also relates to an article of manufacture comprising the fabric care composition in a package, in association with instructions for how to use the composition to treat fabrics correctly, in order to obtain the desirable fabric care results, viz, wrinkle removal and/or reduction, wrinkle resistance, fiber strengthening/anti-wear, fabric wear reduction, fabric shrinkage prevention and/or reduction, fabric pill prevention and/or reduction, shrinkage prevention and/or reduction, fabric color maintenance, fabric color fading reduction, soiling prevention and/or reduction, and/or fabric shape retention, and mixtures thereof.
  • a preferred article of manufacture comprises said composition in a spray dispenser, in association with instructions for how to use the composition to treat fabrics correctly, including, e.g., the manner and/or amount of composition to spray, and the preferred ways of stretching and/or smoothing of the fabrics to remove wrinkles, as will be described with more detailed herein below. It is important that the instructions be as simple and clear as possible, so that using pictures and/or icons is desirable.
  • SPRAY DISPENSER An article of manufacture herein comprises a spray dispenser. The fabric care composition is placed into a spray dispenser in order to be distributed onto the fabric.
  • Said spray dispenser for producing a spray of liquid droplets can be any of the manually activated means as is known in the art, e.g.
  • the spray dispenser herein does not normally include those that will substantially foam the clear, aqueous fabric care composition. It has been found that the performance is increased by providing smaller particle droplets. Desirably, the Sauter mean particle diameter is from about 10 ⁇ m to about 120 ⁇ m, more preferably, from about 20 ⁇ m to about 100 ⁇ m. Dewrinkling benefits for example are improved by providing small particles (droplets), especially when the surfactant is present.
  • the spray dispenser can be an aerosol dispenser.
  • Said aerosol dispenser comprises a container which can be constructed of any of the conventional materials employed in fabricating 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.i.g.
  • the one important requirement concerning the dispenser is that it be provided with a valve member which will permit the clear, aqueous fabric care composition contained in the dispenser to be dispensed in the form of a spray of very fine, or finely divided, particles or droplets.
  • the aerosol dispenser utilizes a pressurized sealed container from which the clear, aqueous fabric care composition is dispensed through a special actuator/valve assembly under pressure.
  • the aerosol dispenser is pressurized by inco ⁇ orating therein a gaseous component generally known as a propellant.
  • a gaseous component generally known as a propellant.
  • a propellant e.g., gaseous hydrocarbons such as isobutane, and mixed halogenated hydrocarbons
  • Halogenated hydrocarbon propellants such as chlorofluoro hydrocarbons have been alleged to contribute to environmental problems, and are not preferred.
  • hydrocarbon propellants are not preferred, because they can form complexes with the cyclodextrin molecules thereby reducing the availability of uncomplexed cyclodextrin molecules for odor abso ⁇ tion.
  • Preferred propellants are compressed air, nitrogen, inert gases, carbon dioxide, etc.
  • the spray dispenser can be a self-pressurized non-aerosol container having a convoluted liner and an elastomeric sleeve.
  • Said self-pressurized dispenser comprises a liner/sleeve assembly containing a thin, flexible radially expandable convoluted plastic liner of from about 0.010 to about 0.020 inch thick, inside an essentially cylindrical elastomeric sleeve.
  • the liner/sleeve is capable of holding a substantial quantity of fabric care composition and of causing said composition to be dispensed.
  • a more complete description of self-pressurized spray dispensers can be found in U.S. Pat. Nos. 5,111,971, Winer, issued May 12, 1992, and 5,232,126, Winer, issued Aug. 3, 1993; both of said references are herein inco ⁇ orated by reference.
  • Another type of aerosol spray dispenser is one wherein a barrier separates the fabric care composition from the propellant (preferably compressed air or nitrogen), as disclosed in U.S. Pat. No. 4,260,110, issued April 7, 1981, and inco ⁇ orated herein by reference.
  • a dispenser is available from EP Spray Systems, East Hanover, New Jersey.
  • the spray dispenser is a non-aerosol, manually activated, pump- spray dispenser.
  • Said pump-spray dispenser comprises a container and a pump mechanism which securely screws or snaps onto the container.
  • the container comprises a vessel for containing the aqueous fabric care composition to be dispensed.
  • the pump mechanism comprises a pump chamber of substantially fixed volume, having an opening at the inner end thereof.
  • a pump stem having a piston on the end thereof disposed for reciprocal motion in the pump chamber.
  • the pump stem has a passageway there through with a dispensing outlet at the outer end of the passageway and an axial inlet port located inwardly thereof.
  • the container and the pump mechanism can be constructed of any conventional material employed in fabricating pump-spray dispensers, including, but not limited to: polyethylene; polypropylene; polyethyleneterephthalate; blends of polyethylene, vinyl acetate, and rubber elastomer.
  • a preferred container is made of clear, e.g., polyethylene terephthalate. Other materials can include stainless steel.
  • the spray dispenser is a manually activated trigger-spray dispenser.
  • Said trigger-spray dispenser comprises a container and a trigger both of which can be constructed of any of the conventional material employed in fabricating trigger- spray dispensers, including, but not limited to: polyethylene; polypropylene; polyacetal; polycarbonate; polyethyleneterephthalate; polyvinyl chloride; polystyrene; blends of polyethylene, vinyl acetate, and rubber elastomer. Other materials can include stainless steel and glass.
  • a preferred container is made of clear, e.g. polyethylene terephthalate.
  • the trigger-spray dispenser does not inco ⁇ orate a propellant gas into the odor-absorbing composition, and preferably it does not include those that will foam the fabric care composition.
  • the trigger-spray dispenser herein is typically one which acts upon a discrete amount of the fabric care composition itself, typically by means of a piston or a collapsing bellows that displaces the composition through a nozzle to create a spray of thin liquid.
  • Said trigger-spray dispenser typically comprises a pump chamber having either a piston or bellows which is movable through a limited stroke response to the trigger for varying the volume of said pump chamber. This pump chamber or bellows chamber collects and holds the product for dispensing.
  • the trigger spray dispenser typically has an outlet check valve for blocking communication and flow of fluid through the nozzle and is responsive to the pressure inside the chamber.
  • an outlet check valve for blocking communication and flow of fluid through the nozzle and is responsive to the pressure inside the chamber.
  • the trigger As the trigger is compressed, it acts on the fluid in the chamber and the spring, increasing the pressure on the fluid.
  • the bellows spray dispenser As the bellows is compressed, the pressure increases on the fluid. The increase in fluid pressure in either trigger spray dispenser acts to open the top outlet check valve. The top valve allows the product to be forced through the swirl chamber and out the nozzle to form a discharge pattern.
  • An adjustable nozzle cap can be used to vary the pattern of the fluid dispensed.
  • the spring acts on the piston to return it to its original position.
  • the bellows acts as the spring to return to its original position. This action causes a vacuum in the chamber.
  • the responding fluid acts to close the outlet valve while opening the inlet valve drawing product up to the chamber from the reservoir.
  • a broad array of trigger sprayers or finger pump sprayers are suitable for use with the compositions of this invention. These are readily available from suppliers such as
  • the preferred trigger sprayers are the blue inserted Guala sprayer, available from Berry Plastics Corp., or the Calmar TS800-1A® , TS1300®, and TS-800-2®, available from Calmar Inc., because of the fine uniform spray characteristics, spray volume, and pattern size. More preferred are sprayers with precompression features and finer spray characteristics and even distribution, such as Yoshino sprayers from Japan.
  • ® is a 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape to the Cinch bottle. It can be made of any materials such as high density polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, glass, or any other material that forms bottles. Preferably, it is made of high density polyethylene or clear polyethylene terephthalate.
  • a finger pump can be used with canister or cylindrical bottle.
  • the preferred pump for this application is the
  • the article of manufacture herein can also comprise a non-manually operated spray dispenser.
  • non-manually operated it is meant that the spray dispenser can be manually activated, but the force required to dispense the fabric care composition is provided by another, non-manual means.
  • Non-manually operated sprayers include, but are not limited to, powered sprayers, air aspirated sprayers, liquid aspirated sprayers, electrostatic sprayers, and nebulizer sprayers.
  • the fabric care composition is placed into a spray dispenser in order to be distributed onto the fabric.
  • Powered sprayers include self contained powered pumps that pressurize the aqueous fabric care composition and dispense it through a nozzle to produce a spray of liquid droplets.
  • Powered sprayers are attached directly or remotely through the use of piping/tubing to a reservoir (such as a bottle) to hold the aqueous fabric care composition.
  • Powered sprayers can include, but are not limited to, centrifugal or positive displacement designs. It is preferred that the powered sprayer be powered by a portable DC electrical current from either disposable batteries (such as commercially available alkaline batteries) or rechargeable battery units (such as commercially available nickel cadmium battery units).
  • Powered sprayers can also be powered by standard AC power supply available in most buildings.
  • the discharge nozzle design can be varied to create specific spray characteristics (such as spray diameter and particle size). It is also possible to have multiple spray nozzles for different spray characteristics.
  • the nozzle may or may not contain an adjustable nozzle shroud that would allow the spray characteristics to be altered.
  • Nonlimiting examples of commercially available powered sprayers are disclosed in U.S. Pat. Nos. 4,865,255, Luvisotto, issued Sep. 12, 1989 which is inco ⁇ orated herein by reference. Preferred powered sprayers are readily available from suppliers such as Solo, Newport News, Virginia (e.g., Solo Spraystar rechargeable sprayer, listed as manual part #: US 460 395) and Multi-sprayer Systems, Minneapolis, Minnesota (e.g., model: Spray 1).
  • Air aspirated sprayers include the classification of sprayers generically known as "air brushes”.
  • a stream of pressurized air draws up the aqueous fabric care composition and dispenses it through a nozzle to create a spray of liquid.
  • the fabric care composition can be supplied via separate piping/tubing or more commonly is contained in a jar to which the aspirating sprayer is attached.
  • Air aspirated sprayers are readily available from suppliers such as The Badger Air-Brush Co., Franklin Park, Illinois (e.g., model #: 155) and Wilton Air Brush Equipment, Woodridge, Illinois (e.g., stock #: 415-4000, 415-4001, 415-4100).
  • Liquid aspirated sprayers are typical of the variety in widespread use to spray garden chemicals.
  • the aqueous dewrinkling composition is drawn into a fluid stream by means of suction created by a Venturi effect.
  • the high turbulence serves to mix the aqueous fabric care composition with the fluid stream (typically water) in order to provide a uniform mixture/concentration. It is possible with this method of delivery to dispense the aqueous concentrated fabric care composition of the present invention and then dilute it to a selected concentration with the delivery stream.
  • Liquid aspirated sprayers are readily available from suppliers such as Chapin Manufacturing Works, Batavia, New York (e.g., model #: 6006).
  • Electrostatic sprayers impart energy to the aqueous fabric care composition via a high electrical potential. This energy serves to atomize and charge the aqueous fabric care composition, creating a spray of fine, charged particles. As the charged particles are carried away from the sprayer, their common charge causes them to repel one another. This has two effects before the spray reaches the target. First, it expands the total spray mist. This is especially important when spraying to fairly distant, large areas. The second effect is maintenance of original particle size. Because the particles repel one another, they resist collecting together into large, heavier particles like uncharged particles do. This lessens gravity's influence, and increases the charged particle reaching the target.
  • Nonlimiting examples of commercially available electrostatic sprayers appears in U.S. Pat. Nos. 5,222,664, Noakes, issued Jun. 29, 1993; 4,962,885, Coffee, issued Oct. 16, 1990; 2,695,002, Miller, issued Nov. 1954; 5,405,090, Greene, issued Apr. 11, 1995; 4,752,034, Kuhn, issued Jun. 21, 1988; 2,989,241, Badger, issued Jun. 1961; all of said patents are inco ⁇ orated herein by reference.
  • Electrostatic sprayers are readily available from suppliers such as Tae In Tech Co, South Korea and Spectrum, Houston, Texas.
  • Nebulizer sprayers impart energy to the aqueous dewrinkling composition via ultrasonic energy supplied via a transducer. This energy results in the aqueous fabric care composition to be atomized.
  • Various types of nebulizers include, but are not limited to, heated, ultrasonic, gas, venturi, and refillable nebulizers.
  • Nonlimiting examples of commercially available nebulizer sprayers appears in U.S. Pat. Nos. 3,901,443, Mitsui, issued Aug. 26, 1975; 2,847,248, Schmitt, issued Aug. 1958; 5,511,726, Greenspan, issued Apr. 30, 1996; all of said patents are inco ⁇ orated herein by reference.
  • Nebulizer sprayers are readily available from suppliers such as A&D Engineering, Inc., Milpitas, California (e.g., model A&D Un-231 ultrasonic handy nebulizer) and Amici, Inc., Spring City, Pennsylvania (model: swirler nebulizer).
  • the preferred article of manufacture herein comprises a non-manually operated sprayer, such as a battery-powered sprayer, containing the aqueous fabric care composition. More preferably the article of manufacture comprises a combination of a non-manually operated sprayer and a separate container of the aqueous fabric care composition, to be added to the sprayer before use and/or to be separated for filling/refilling.
  • the separate container can contain an usage composition, or a concentrated composition to be diluted before use, and/or to be used with a diluting sprayer, such as with a liquid aspirated sprayer, as described herein above.
  • the separate container should have structure that mates with the rest of the sprayer to ensure a solid fit without leakage, even after motion, impact, etc. and when handled by inexperienced consumers.
  • the sprayer desirably can also have an attachment system that is safe and preferably designed to allow for the liquid container to be replaced by another container that is filled.
  • the fluid reservoir can be replaced by a filled container.
  • the sprayer can contain a shroud to ensure proper alignment and/or to permit the use of thinner walls on the replacement container. This minimizes the amount of material to be recycled and/or discarded.
  • the package sealing or mating system can be a threaded closure (sprayer) which replaces the existing closure on the filled and threaded container.
  • a gasket is desirably added to provide additional seal security and minimize leakage. The gasket can be broken by action of the sprayer closure.
  • These threaded sealing systems can be based on industry standards. However, it is highly desirable to use a threaded sealing system that has non-standard dimensions to ensure that the proper sprayer/bottle combination is always used. This helps prevent the use of fluids that are toxic, which could then be dispensed when the sprayer is used for its intended pu ⁇ ose.
  • An alternative sealing system can be based on one or more interlocking lugs and channels. Such systems are commonly referred to as “bayonet” systems. Such systems can be made in a variety of configurations, thus better ensuring that the proper replacement fluid is used. For convenience, the locking system can also be one that enables the provision of a "child-proof cap on the refill bottle. This "lock-and-key" type of system thus provides highly desirable safety features. There are a variety of ways to design such lock and key sealing systems.
  • the lock and key can be integral to the sealing mechanism.
  • the interlocking pieces can be separate from the sealing system.
  • the shroud and the container could be designed for compatibility. In this way, the unique design of the container alone could provide the requisite assurance that the proper recharge/refill is used.
  • the present invention also relates to an article of manufacture comprising a fabric care composition for use in spraying and/or misting an entire garment in a manner such that excessive amounts of the fabric/garment care composition are prevented from being released to the open environment, provided in association with instructions for use to ensure that the consumer applies at least an effective amount of fabric care polysaccharied with globular structure and/or fabric care composition, to provide the desired garment care benefit, typically from about 0.001% to about 0.5%, preferably from about 0.01%) to about 0.2%, more preferably from about 0.02% to about 0.05%, by weight of the garment.
  • compositions of the present invention for use to treat fabrics in different steps of the laundry process, e.g., pre-wash, wash cycle, rinse cycle, and drying cycle, can be packaged in association with instructions for how to use the composition to treat fabrics correctly, in order to obtain the desirable fabric care results, viz, wrinkle removal and/or reduction, wrinkle resistance, fiber strengthening/anti-wear, fabric wear reduction, fabric shrinkage prevention and/or reduction, fabric pill prevention and/or reduction, shrinkage prevention and/or reduction, fabric color maintenance, fabric color fading reduction, soiling prevention and/or reduction, and/or fabric shape retention, and mixtures thereof.
  • the fabric care composition which contains a fabric care polysaccharide with globular structure, and optionally, e.g., adjunct fabric care oligosaccharides, perfume, fiber lubricant, adjunct fabric shape retention polymer, lithium salt, hydrophilic plasticizer, odor control agent including cyclodextrin, antimicrobial actives and/or preservative, surfactant, enzyme, antioxidant, metal chelating agent including aminocarboxylate chelating agent, antistatic agent, insect and moth repelling agent, fabric softener active, electrolyte, chlorine scavenging agent, dye transfer inhibiting agent, dye fixing agent, phase stabilizer, colorant, brightener, soil release agent, builder, dispersant, suds suppressor, etc., and mixtures thereof, can be used by distributing, e.g., by placing, an effective amount of the aqueous solution onto the fabric surface or fabric article to be treated.
  • odor control agent including cyclodextrin, antimicrobial actives and/or preservative
  • an effective amount means an amount sufficient to remove or noticeably reduce the appearance of wrinkles on fabric.
  • the amount of fabric care solution is not so much as to saturate or create a pool of liquid on said article or surface and so that when dry there is no visual deposit readily discernible.
  • compositions and articles of the present invention which contain a fabric care polysaccharide with globular structure can be used to treat fabrics, garments, and the like, to provide at least one of the following fabric care benefits: wrinkle removal, wrinkle reduction, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric soiling reduction, fabric shape retention, and/or fabric shrinkage reduction.
  • An effective amount of the liquid composition of the present invention is preferably sprayed onto fabric and/or fabric articles include, but are not limited to, clothes, curtains, drapes, upholstered furniture, ca ⁇ eting, bed linens, bath linens, tablecloths, sleeping bags, tents, car interiors, etc.
  • an effective amount should be deposited onto the fabric, with the fabric becoming damp or totally saturated with the composition, typically from about 5% to about 150%, preferably from about 10% to about 100%, more preferably from about 20% to about 75%, by weight of the fabric.
  • the treated fabric typically has from about 0.005% to about 4%, preferably from about 0.01%> to about 2%, more preferably from about 0.05% to about 1%), by weight of the fabric of said fabric care polysaccharide with globular structure.
  • the fabric is optionally, but preferably stretched.
  • the fabric is typically stretched pe ⁇ endicular to the wrinkle.
  • the fabric can also be smoothed by hand after it has been sprayed. The smoothing movement works particularly well on areas of clothing that have an interface sewn into them, or on the hems of clothing. Once the fabric has been sprayed and optionally, but preferably, stretched, it is hung until dry. It is preferable that the treatment is performed in accordance with the instructions for use, to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • the spraying means should be capable of providing droplets with a weight average diameter of from about 5 ⁇ m to about 250 ⁇ m, preferably from about 8 ⁇ m to about 120 ⁇ m, more preferably from about 10 ⁇ m to about 80 ⁇ m.
  • a weight average diameter of from about 5 ⁇ m to about 250 ⁇ m, preferably from about 8 ⁇ m to about 120 ⁇ m, more preferably from about 10 ⁇ m to about 80 ⁇ m.
  • the fabric care composition can also be applied to fabric via a dipping and/or soaking process followed by a drying step.
  • the application can be done industrially by large scale processes on textiles and/or finished garments and clothings, or in consumer's home by the use of commercial product.
  • the present invention also comprises a method of using concentrated liquid or solid fabric care compositions, which are diluted to form compositions with the usage concentrations, as given hereinabove, for use in the "usage conditions".
  • Concentrated compositions comprise a higher level of fabric care polysaccharide with globular structure, typically from about 1% to about 99%, preferably from about 2% to about 65%o, more preferably from about 3% to about 25%, by weight of the concentrated fabric care composition.
  • Concentrated compositions are used in order to provide a less expensive product.
  • the concentrated product is preferably diluted with about 50% to about 10,000%, more preferably from about 50% to about 8,000%, and even more preferably from about 50% to about 5,000%, by weight of the composition, of water.
  • compositions of the present invention can also be used as ironing aids.
  • An effective amount of the composition can be sprayed onto fabric and the fabric is ironed at the normal temperature at which it should be ironed.
  • the fabric can either be sprayed with an effective amount of the composition, allowed to dry and then ironed, or sprayed and ironed immediately.
  • the composition can be sprayed and/or misted onto fabrics and or entire garments in need of de-wrinkling and/or other fabric care benefits in a manner such that excessive amounts of the fabric/garment care composition are prevented from being released to the open environment, provided in association with instructions for use to ensure that the consumer applies at least an effective amount of fabric care polysaccharide with globular structure and/or fabric care composition, to provide the desired garment care benefit.
  • Any spraying mechanism and/or misting mechanism can be used to apply the fabric care composition to fabrics and/or garments.
  • a preferred distribution of the garment care composition is achieved by using a fog form.
  • the mean particulate diameter size of the fabric care composition fog is preferably from about 3 microns to about 50 microns, more preferably from about 5 microns to about 30 microns, and most preferably from about 10 microns to about 20 microns.
  • Another aspect of the present invention is the method of using an aqueous or solid, preferably powder, fabric care composition for treating fabric in the rinse step, comprising an effective amount of said fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharides, fabric softener actives, perfume, electrolytes, chlorine scavenging agents, dye transfer inhibiting agents, dye fixing agents, phase stabilizers, chemical stabilizers including antioxidants, silicones, antimicrobial actives and/or preservatives, chelating agents, aminocarboxylate chelating agents, colorants, enzymes, brighteners, soil release agents, or mixtures thereof.
  • the rinse water should contain typically from about 0.0005%> to about 1%, preferably from about 0.0008%) to about 0.1%, more preferably from about 0.001% to about 0.02% of the fabric care polysaccharides.
  • the present invention also relates to a method of using an aqueous or solid, preferably powder or granular, fabric care composition to treat the fabrics in the wash cycle, said compositions comprise fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharides, surfactants, builders, perfume, chlorine scavenging agents, dye transfer inhibiting agents, dye fixing agents, dispersants, detergent enzymes, heavy metal chelating agents, suds suppressors, fabric softener actives, chemical stabilizers including antioxidants, silicones, antimicrobial actives and/or preservatives, soil suspending agents, soil release agents, optical brighteners, colorants, and the like, or mixtures thereof.
  • aqueous or solid, preferably powder or granular, fabric care composition to treat the fabrics in the wash cycle
  • said compositions comprise fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharides, surfactants, builders, perfume, chlorine scavenging agents,
  • the wash-added fabric care composition can be used as a wash additive composition (when the surfactant level is low) or as a laundry detergent which also has additional fabric care benefits. It is preferable that the treatment is performed in accordance with the instructions for use, to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • the present invention also relates to a method for treating fabric in the drying step, comprising an effective amount of said fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharides, fabric softener actives, distributing agent, perfume, fiber lubricants, fabric shape retention polymers, lithium salts, phase stabilizers, chlorine scavenging agents, dye transfer inhibiting agents, dye fixing agents, chemical stabilizers including antioxidants, silicones, antimicrobial actives and/or preservatives, heavy metal chelating agents, aminocarboxylate chelating agents, enzymes, brighteners, soil release agents, and mixtures thereof.
  • the fabric care composition can take a variety of physical forms including liquid, foams, gel and solid forms such as solid particulate forms.
  • a preferred method comprises the treatment of fabric with a dryer-added fabric care composition in combination with a dispensing means such as a flexible substrate which effectively releases the fabric care composition in an automatic tumble clothes dryer.
  • a dispensing means such as a flexible substrate which effectively releases the fabric care composition in an automatic tumble clothes dryer.
  • Such dispensing means can be designed for single usage or for multiple uses.
  • the composition is applied onto a sheet substrate to form a dryer sheet product.
  • Another preferred method comprises the treatment of fabrics with a fabric care composition dispensed from a a sprayer at the beginning and/or during the drying cycle. It is preferable that the treatment is performed in accordance with the instructions for use, to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • the present invention also relates to a fabric care method of dipping and/or soaking fabrics before the fabrics is laundered, with a pre-wash fabric care composition containing an effective amount of fabric care polysaccharide with globular structure, and optionally, adjunct fabric care oligosaccharides, surfactants, builders, perfume, chlorine scavenging agents, dye transfer inhibiting agents, dye fixing agents, dispersants, detergent enzymes, heavy metal chelating agents, fabric softener actives, chemical stabilizers including antioxidants, silicones, antimicrobial actives and/or preservatives, soil suspending agents, soil release agents, optical brighteners, colorants, and the like, or mixtures thereof. It is preferable that the treatment is performed in accordance with the instructions for use, to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • Illustrative examples of fabric care polysaccharides with globular structure and with 1,3- ⁇ -linked backbone to be used in the following Examples are as follows: Arabinogalactan A: arabinogalactan fraction that has the average molecular weight of from about 16,000 to about 20,000. Arabinogalactan B: arabinogalactan fraction that has the average molecular weight of about 100,000. Arabinogalactan C: arabinogalactan fraction that has the average molecular weight of from about 10,000 to about 150,000.
  • adjunct fabric care oligosaccharide mixtures to be used in the following Examples are as follows: Isomaltooligosaccharide (LMO) Mixture A
  • Trisaccharides (maltotriose, panose, isomaltotriose) 40%>
  • Trisaccharides (maltotriose, panose, isomaltotriose) 25 %>
  • Tetrasaccharides stachyose 32% Trisaccharides (raffmose) 6%>
  • Trisaccharides (maltotriose, panose, isomaltotriose) 62%>
  • compositions are prepared by mixing and dissolving the ingredients into clear or translucent solutions,, in accord with the present invention:
  • Concentrated compositions of Examples III and IV are diluted with water to obtain usage compositions for, e.g., spraying, soaking and/or dipping fabric articles. They can also be used undiluted to treat fabric as wash additive and/or rinse additive compositions.

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Abstract

La présente invention se rapporte à des compositions d'entretien des textiles, à des procédés et à des produits manufacturés pour le traitement des textiles. Lesdites compositions contiennent une quantité efficace de polysaccharides destinés à l'entretien des textiles et dotés d'une structure globulaire. Elles peuvent également contenir d'autres ingrédients permettant d'améliorer leur performance et leur aptitude à la formulation. On peut appliquer ces compositions à un textile par pulvérisation, trempage ou immersion et également les utiliser en tant que compositions de traitement de prélavage, ou les ajouter au cycle de lavage, au cycle de rinçage et ou au cycle de séchage. De préférence, on applique ces compositions au moyen d'atomiseurs qui sont de préférence associés à des instructions d'utilisation.
PCT/US1999/024942 1998-10-23 1999-10-22 Composition d'entretien des textiles et procede correspondant WO2000024856A1 (fr)

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EP99956654A EP1123374B1 (fr) 1998-10-23 1999-10-22 Composition d'entretien des textiles et procede correspondant
US09/807,367 US7012053B1 (en) 1999-10-22 1999-10-22 Fabric care composition and method comprising a fabric care polysaccharide and wrinkle control agent
DE69929233T DE69929233T2 (de) 1998-10-23 1999-10-22 Zusammensetzung und verfahren zur textilpflege
JP2000578411A JP4873781B2 (ja) 1998-10-23 1999-10-22 布地保護組成物および方法
AT99956654T ATE314451T1 (de) 1998-10-23 1999-10-22 Zusammensetzung und verfahren zur textilpflege
BR9915536-2A BR9915536A (pt) 1998-10-23 1999-10-22 Composição e método para cuidados com o tecido
AU13211/00A AU1321100A (en) 1998-10-23 1999-10-22 Fabric care composition and method
CA2346771A CA2346771C (fr) 1998-10-23 1999-10-22 Composition d'entretien des textiles et procede correspondant

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CZ20011366A3 (cs) 2002-06-12
EP1123374B1 (fr) 2005-12-28
AU1133000A (en) 2000-05-15
CA2346771A1 (fr) 2000-05-04
CN1332787A (zh) 2002-01-23
JP2002528653A (ja) 2002-09-03
ATE314451T1 (de) 2006-01-15
BR9914747A (pt) 2001-10-02
CA2346691A1 (fr) 2000-05-04
JP2002528652A (ja) 2002-09-03
EP1144572A2 (fr) 2001-10-17
EP1123374A1 (fr) 2001-08-16
AU1223100A (en) 2000-05-15
WO2000024851A3 (fr) 2001-12-13
CA2346771C (fr) 2012-04-10
CN1331739A (zh) 2002-01-16
DE69929233D1 (de) 2006-02-02
BR9915536A (pt) 2001-10-16
EP1124924A1 (fr) 2001-08-22
DE69929233T2 (de) 2006-09-07
WO2000024858A1 (fr) 2000-05-04
JP2002528654A (ja) 2002-09-03
JP4873781B2 (ja) 2012-02-08
KR20010090799A (ko) 2001-10-19
AU1321100A (en) 2000-05-15
WO2000024851A2 (fr) 2000-05-04
CA2346805A1 (fr) 2000-05-04

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