EP3247833A1 - Procédé de traitement de tissu amélioré pour l'élimination des taches - Google Patents

Procédé de traitement de tissu amélioré pour l'élimination des taches

Info

Publication number
EP3247833A1
EP3247833A1 EP16737925.4A EP16737925A EP3247833A1 EP 3247833 A1 EP3247833 A1 EP 3247833A1 EP 16737925 A EP16737925 A EP 16737925A EP 3247833 A1 EP3247833 A1 EP 3247833A1
Authority
EP
European Patent Office
Prior art keywords
fabric
salts
composition
treatment
zeta potential
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16737925.4A
Other languages
German (de)
English (en)
Other versions
EP3247833A4 (fr
Inventor
Gregory Van Buskirk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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
Priority claimed from US14/716,871 external-priority patent/US10577743B2/en
Application filed by Individual filed Critical Individual
Publication of EP3247833A1 publication Critical patent/EP3247833A1/fr
Publication of EP3247833A4 publication Critical patent/EP3247833A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F35/00—Washing machines, apparatus, or methods not otherwise provided for

Definitions

  • the instant disclosure relates to a fabric treatment composition for imparting fabric protection benefits to a textile, such as stain and soil resistance, oil repellency, water repellency, softness, wrinkle and damage resistance, and improved hand-feel.
  • the composition can be used or applied as a pretreatment prior to washing, through soaking or direct spray application, or added to a treatment cycle, such as the wash or rinse cycle of an automatic washing machine.
  • Application of the fabric treatment is complete when a treated fabric is cured by drying and/or heating.
  • the textile agent comprises, in addition to the fluorochemical, a urethane latex, a compatible acrylate latex and a cross-linking resin.
  • the first composition is a low-solids latex having a glass transition temperature from 10 °C to 35 °C.
  • the second composition includes a high solids latex having the consistency of wood glue or wallpaper paste and a glass transition temperature from -40 °C to -10 °C and is applied to one side of the fabric. This combined commercial treatment system purportedly produces a fabric that is liquid repellent, stain resistant, and is easy to handle.
  • U.S. Patent No. 5,047,065 to Vogel, et al. describes a combination of a perfluoroaliphatic group-bearing water/oil repellent agent dispersion, an emulsifiable polyethylene dispersion, and a soft-hand extender based on a modified hydrogen alkyl polysiloxane.
  • the composition is padded onto fabric at a concentration of 70-150 g/L and then cured at 150 °C.
  • compositions are intended for commercial application to nylon yarns.
  • ethylene/vinyl acetate waxes such as those materials cited in U.S. Patent No. 4,027,062 to Englebrecht, et al., and U.S. Patent No. 4,833,006 to McKinney, et al. It is also possible to make fabrics resistant to stains caused by spilled liquid by using silicone materials, as is commonly known in the art.
  • An additional drawback of direct application products is that they cannot be used on fabrics that are already stained or soiled because they lock in stains and soils. That is, they seal over a stain or soil already on a textile, rather than first dislodging it from the textile.
  • U.S. Patent No. 6,180,740 to Fitzgerald describes an aqueous emulsion containing a fluorochemical copolymer composition that provides oil-and water-repellency to textiles.
  • the emulsion is apparently stable under conditions of high alkalinity, high anionic concentration, and/or high shear conditions.
  • Fabric treatment requires drying at relative high temperatures of between 110 °C to 190 °C.
  • U.S. Patent No. 4,724,095 to Gresser describes a detergent composition comprising an effective amount of at least one hydrophobic/hydrophilic anti-redeposition copolymer that comprises at least one of the recurring units ethylene oxide and alkylene oxide.
  • the purpose for the copolymer is to reduce the zeta potential of the fibers of the textile substrate to a value of 0.5 times, or less, of the zeta potential of the bare fiber. Close examination of the patent reveals that the zeta potential is determined solely for the bare and treated fabrics, that is, neither for the liquid composition nor the wash liquor, and that while the zeta potential becomes less negative, it never attains a positive charge value.
  • Gresser labeled Test No. 2
  • a soiling composition that includes a hydrophobic compound such as paraffin.
  • the paraffin is used to discolor a test fabric. It is noted that Gresser' s goal is to completely remove the soil—and therefore the paraffin—from the fabric.
  • U.S. Patent No. 6,379,753 to Soane, et al. describes methods for modifying textile materials to render them water repellant, among other things, by covalently bonding multifunctional molecules to the textile material.
  • the multifunctional molecules are polymers with plural functional groups or regions, such as binding groups, hydrophobic groups, and hydrophilic groups and oleophobic groups.
  • U.S. Ser. No. 14/549,555 relate to a fabric treatment composition for imparting fabric protection benefits, such as stain and soil resistance, oil repellency, water repellency, softness, wrinkle and damage resistance, and improved hand-feel.
  • the composition can be used as a pretreatment prior to washing, through soaking or direct spray application, or added to a treatment cycle, such as the wash or rinse cycle of an automatic washing machine.
  • the fabric treatment is complete when the fabric has been cured by drying and/or heating. None of the foregoing, however, has addressed the use of high-efficiency, low-water usage type washing machines that have been gaining in popularity with consumers in recent years.
  • the present disclosure provides non-limiting examples of fabric treatment compositions and methods for providing protective properties to a fabric or garment, especially when introduced in a high-efficiency or HE type consumer washing machine.
  • a product and method that combines the controlled and even coating of commercial fabric treatment operations with the convenience and ease of home use that is compatible with use in low-water or HE machines.
  • the coating should be curable at temperatures that are readily attainable in a residential clothes dryer. This is because curing at high temperatures can make coatings excessively durable, owing to excessive buildup over numerous treatment cycles. This, in turn, typically results in an unfavorable hand-feel.
  • Reduced temperature curing results in improved hand-feel, and also allows for an easily reversible and/or removable coating, if desired.
  • Such non-permanent or transient coatings reduce total coating buildup over multiple applications or treatments, and also reduce the possibility of leaving a visible residue or other undesirable change in appearance on fabrics, such as yellowing or discoloration of white or lighted-colored fabrics.
  • a desired textile treatment product should also not lock in pre-existing stains or soils and thereby ruin fabrics.
  • household dryers typically attain average temperatures of at least 175 °C, and under normal usage reach much higher temperatures.
  • Green discloses treating a blended fabric of cotton, nylon and heat-resistant fibers with a surrogate cleaning solution, i.e., aqueous sodium hydroxide, then rinsing the fabric and drying it in a conventional home dryer to a maximum dryness at 71 °C. Green does not state that 71 °C is the maximum temperature to which a fabric should be subjected, nor that 71°C is the maximum temperature achieved in a conventional home dryer, but rather states that 71 °C was the maximum temperature that was used.
  • a surrogate cleaning solution i.e., aqueous sodium hydroxide
  • the concentration of added fabric treatment compositions are therefore increased 3-4 fold relative to conventional top-loading washing machines, and it would be expected that more of the fabric treatment composition would therefore deposit on treated textiles Rather unexpectedly, however, such is not the case.
  • the amount of fabric treatment composition that is introduced or applied to textiles in low water, high-efficiency washing machines is significantly reduced as compared to the amount of fabric treatment composition that is introduced to a textile in a low-water or HE rinse cycle directly after low-water or HE wash cycle.
  • FIG. 1. is a flow chart illustrating an exemplary method of controlling a washing machine according to exemplary embodiments of the present disclosure.
  • the present disclosure therefore concerns the surprising discovery that the successful treatment of fabrics to impart stain repellency, particularly when using HE washing machines, includes introducing a fabric treatment composition into a rinse cycle that is essentially devoid of added surfactant-containing additives.
  • agitator-type or “top-loading” or “top-loader” washing machines are understood to refer to conventional or non-HE type washing machines.
  • dry cycle or “drying cycle” is understood to refer to that portion of a fabric care procedure during which heat is applied to a fabric or the fabric is left to dry in ambient air.
  • the application of heat may occur either in a conventional home laundry dryer, or via any other technique for driving off water such as by ironing the fabric, through the use of an air blower or hot air gun, etc.
  • fabric protective benefits or “fabric protection benefits” is understood to refer to at least one of: stain resistance, oil repellency, water repellency, softness, wrinkle and damage resistance, improved hand-feel, as well as combinations of any of the foregoing. Fabric protection benefits are also understood to include reduction of fiber wear, i.e., retention of fiber tensile strength, maintenance of fabric appearance by reduction of fiber pilling, reduction of color loss or fading, inhibition of the deposition of fugitive dyes onto a fabric during a washing cycle or overall laundering process, fabric shape retention and/or fabric shrinkage reduction.
  • HE washer refers to washing machines that are designed to be more efficient than traditional washing machines in their energy and water use. See American Cleaning Institute, "High Efficiency Washers and Detergents", Washington D.C., 2010, available in print and on-line at http://www.cleaninginstitute.0rg/assets/l/page/he.pdf HE washers use only about 20% to 66% of the amount of water by volume that is typically used in traditional agitator-type washers in the United States. Because there is much less water to heat, energy use in HE washers can be as little as 20 to 50 percent of the amount of energy typically required to heart water in traditional agitator washers.
  • laundering process As used herein, the term "laundering process,” “laundry process,” or “laundry cycle” is understood to refer to any and all washing, rinsing, spinning and drying to which a fabric may be subjected during a fabric treatment and/or fabric cleaning procedure.
  • washing cycle or “wash cycle” refers only to that portion of a laundering process or fabric cleaning procedure in which a detergent is combined with a fabric, garment or textile in aqueous solution for the purpose of cleaning the item.
  • spin cycle or “spinning cycle” is understood to refer to that portion of a fabric cleaning procedure during which residual water or aqueous solutions are removed from the fabric through wringing, centrifugal force or any combination thereof.
  • dry cycle or “drying cycle” is understood to refer to that portion of a fabric care procedure during which heat is applied to a fabric or the fabric is left to dry in ambient air.
  • the application of heat may occur either in a conventional home laundry dryer, or via any other technique to drive off water such as ironing the fabric, through use of an air blower or hot air gun, etc.
  • FIG. 1 at 100 illustrates an exemplary method for introducing a fabric treatment composition to a fabric.
  • the process begins when a user first introduces laundry into the washing machine at step 102 and adds water to the machine according to the desired machine operation at water addition step 104. If a user decides that the fabrics are soiled and/or stained at decision point 106, the user adds laundry detergent to the wash load as shown in detergent addition step 108.
  • the user can allow the laundry to soak, but eventually the laundry is agitated in the wash liquor at agitation step 110, and after a period determined either automatically by washing machine controls or manually by a user, the wash water is exhausted from the machine, and the laundry is spun via centrifugal force as shown in exhaust water, spin step 112.
  • an intermediate rinse cycle is initiated at decision step 114.
  • Water is added to the machine according to desired machine operation as shown at water addition step 116.
  • the user can again allow the laundry to soak in the rinse water, but eventually the laundry is agitated in the rinse liquor at agitation step 118, and after a period determined automatically by the washing machine controls or manually by a user, the rinse water is exhausted from the machine, and the laundry is spun via centrifugal force in exhaust water, spin step 120.
  • a fabric treatment cycle is initiated. This latter process becomes the same for regular as well as high-efficiency machines.
  • water is added to the machine according to desired machine operation at 104.
  • a suitable dose of fabric treatment composition as described herein is added along with the water or added subsequent thereto as shown at treatment composition addition step
  • the user can again allow the laundry to soak in the treatment liquor, but eventually the laundry is agitated in the treatment liquor at agitation step 124, and after a period determined automatically by the washing machine controls or via manual override, the treatment water is exhausted from the machine, and the laundry is spun via centrifugal force as shown at exhaust water, spin step 126.
  • the laundry is then dried in a conventional dryer, whereby the process is ended.
  • a method for treating fabrics in a low-water, high-efficiency washing machine to provide at least one fabric protective property to a fabric includes the steps of:
  • washing the fabric with a detergent composition comprising at least one surfactant as shown at 108, 110 and 112 of FIG. 1;
  • first fabric treatment composition onto the fabric in a second rinse cycle as shown at 122, 124 and 126 of FIG. 1, wherein the first fabric treatment composition comprises:
  • a hydrophobic agent that does not cause significant color change nor impart discoloration to a fabric, characterized as having a melting point or glass transition temperature of less than 100 °C;
  • a zeta potential modifier such that the first treatment liquor has a zeta potential that is positive and greater than zero millivolts
  • the fabric protective property is selected from the group comprising: increased water repellency, increased oil repellency, increased soil and stain release, improved hand-feel, improved softness, improved resistance to damage, and any combination thereof;
  • the hydrophobic agent is not a fluoropolymer
  • the zeta potential modifier comprises a cationic or cationically modified
  • the ratio of hydrophobic agent to zeta potential modifier is at least 1 :3.
  • a fabric may be treated numerous times with a fabric treatment composition during any one laundering process, with the proviso that at least one intermediate rinsing step essentially devoid of surfactant-containing additives is included after any washing cycle, but prior to any fabric treatment step or steps. Once the fabric becomes dry or has been heated to dryness, any one particular laundering process is understood to be at an end.
  • a textile may be exposed to the same or a different fabric treatment composition numerous times during any one laundering procedure, with the proviso that at least one rinsing step essentially devoid of a detergent or surfactant composition occurs prior to any fabric treatment or depositing step or steps. Accordingly, a method for treating fabrics in a washing machine to provide at least one fabric protective property to a fabric comprises the first method described above, wherein the step of depositing a fabric treatment composition onto the fabric is repeated at least once.
  • a fabric, garment or textile that has been treated with a first fabric treatment composition that may have been applied during a laundering process can be re-treated with either the same first fabric treatment composition during a subsequent laundering process or treated with a second fabric treatment composition during a subsequent laundering process, with the proviso that an intermediate rinsing step essentially devoid of added surfactant-containing additives takes place subsequent to the washing step and prior to the fabric treatment step.
  • the second fabric treatment composition may comprise the same hydrophobic agent, fluoropolymer and zeta potential modifier as in the first fabric treatment composition, or they may be different.
  • the second fabric treatment composition may independently contain either the same, more or less weight % amounts of each of the active components of the first fabric treatment composition.
  • a method for treating a fabric in a washing machine to provide at least one fabric protective property to the fabric comprises the steps of:
  • washing the fabric with a detergent composition comprising at least one surfactant as shown at 108, 110 and 112 of FIG. 1;
  • first fabric treatment composition onto the fabric in a second rinse cycle that comprises a first treatment liquor as shown at 122, 124 and 126 of FIG. 1, wherein the first fabric treatment composition comprises:
  • a first amount of a fluoropolymer b. a first amount of a fluoropolymer; and c. a first effective amount of a zeta potential modifier, such that the first treatment liquor has a zeta potential that is positive and greater than zero millivolts;
  • the fabric protective property is selected from the group comprising: increased water repellency, increased oil repellency, increased soil and stain release, improved hand-feel, improved softness, improved resistance to damage, and any combination thereof;
  • the hydrophobic agent is not a fluoropolymer
  • the zeta potential modifier comprises a cationic or cationically
  • the ratio of hydrophobic agent to zeta potential modifier is at least 1 :3.
  • the first fabric treatment composition may be the same as or different from the second fabric treatment composition; and vi. the second amounts of hydrophobic agent, fluoropolymer and zeta potential modifier, respectively, are independently equal to or not equal to the first amounts of hydrophobic agent, fluoropolymer and zeta potential modifier, respectively.
  • both depositing steps 3. and 4. above, or independently either depositing step 3. or depositing step 4. above may be repeated at least once prior to curing or drying step 5.
  • a method for treating a fabric to impart at least one fabric protective property to the fabric includes the steps of:
  • washing the fabric with a detergent composition comprising at least one surfactant as shown at steps 108, 110 and 112 of FIG. 1;
  • first fabric treatment composition onto the fabric in a second rinse cycle that comprises a first treatment liquor as shown at steps 122, 124 and 126 of FIG 1, wherein the first fabric treatment composition comprises:
  • a first effective amount of a zeta potential modifier such that the first treatment liquor has a zeta potential that is positive and greater than zero millivolts
  • the second fabric treatment composition comprises:
  • a second amount of a fluoropolymer e. a second amount of a fluoropolymer; and f. a second effective amount of a zeta potential modifier, such that the second treatment liquor has a zeta potential that is positive and greater than zero millivolts;
  • the first fabric treatment composition may be the same as or different from the second fabric treatment composition
  • the second amounts of hydrophobic agent, fluoropolymer and zeta potential modifier, respectively are independently equal to or not equal to the first amounts of hydrophobic agent, fluoropolymer and zeta potential modifier, respectively;
  • the fabric protective property is selected from the group comprising: increased water repellency, increased oil repellency, increased soil and stain release, improved hand-feel, improved softness, improved resistance to damage, and any combination thereof;
  • the hydrophobic agent is not a fluoropolymer
  • the zeta potential modifier comprises a cationic or cationically modified
  • the ratio of hydrophobic agent to zeta potential modifier is at least 1 :3.
  • steps 3 and 4 above may independently be performed more than once prior to steps 5 and 6, respectively.
  • a method for imparting a fabric protective property to a fabric may be practiced according to the above, wherein step 5, and any repetitions thereof, together with step 6 occur after the completion of step 3, and any repetitions thereof, together with step 4.
  • the drying temperatures used in the above method in curing steps 4 and 6 is less than about 70 °C.
  • the fluoropolymer emulsions that are suitable for use with the fabric treatment formulations described herein may contain a discrete amount of surfactants, especially mixtures of cationic and nonionic surfactants, but such amounts, if present at all, are usually small.
  • a generally suitable range for fluoropolymers in a first fabric treatment compositions presented herein is 0.5 to 60%, more preferred is 1 to 40%, and further preferred is 5 to 30%.
  • the amount of fluoropolymer that may be acceptable for use in a second fabric treatment composition can be somewhat less.
  • a second fabric treatment composition may contain from 0.1 - 30 weight % fluoropolymer.
  • the fluoropolymers employed in the fabric treatment compositions of the instant disclosure can be water insoluble oily soil repellents and may have one or more fluoroaliphatic radicals, and/or one or more perfluoroalkyl radicals and/or partially or fully fluorinated radical substituents. They can be nonionic in that they do not contain an ionized functional group such as a quaternary ammonium group. They can be cationic in that they contain an ionized or ionizable functional group, such as a quaternary ammonium group in the first instance, or a tertiary amine, which is protonatable to provide for a positive charge center.
  • fluoropolymers can be zwitterionic in that they have both cationic and anionic groups present, suitably with the number of cationic and anionic groups present being essentially equivalent in number to provide an overall net nonionic property to the fluoropolymer, and also suitably with the number of cationic and anionic groups present being essentially non-equivalent in number to provide an overall net positive or cationic charge to the fluoropolymer. It is especially preferred that the fluoropolymers be at least slightly cationic, that is that, carry a net positive charge.
  • Useful classes of the fluoropolymers are the fluorocarbonylimino biurets, the fluoroesters, the fluoroester carbamates, and the fluoropolymers.
  • the class of fluorocarbonyliminobiurets is represented by U.S. Pat. No. 4,958,039 to Pechhold, which is incorporated herein by reference.
  • the class of fluorocarbonylimino biurets is particularly useful because of the outstanding anti-soilant protection it provides.
  • the class of fluoroesters is represented by U.S. Pat. No. 3,923, 715 to Dettre, et al, and U.S. Pat. No. 4,029,585 to Dettre, et al, which are incorporated herein by reference.
  • the foregoing patents disclose perfluoroalkyl esters of carboxylic acids of 3 to 30 carbon atoms.
  • An example is the citric acid ester of perfluoroalkyl aliphatic alcohols such as a mixture of 2-perfluoroalkyl ethanols containing 8 to 16 carbon atoms.
  • the class of fluoroester carbamates is also disclosed in aforementioned U.S. Pat. No. 4,029,585.
  • the class of fluoropolymers is represented by U.S. Pat. No. 3,645, 989 to Tandy and U.S. Pat. No. 3,645,990 to Raynolds, which are incorporated herein by reference.
  • the patents describe, respectively, fluorinated polymers from acrylic and methacrylic derived fluoro- substituted monomers and methyl acrylate or ethylacrylate, optionally with small amounts of other monomers.
  • a useful fluoropolymer is the terpolymer formed by polymerization of an aliphatic or aromatic alpha olefin or an alkyl vinyl ether, a non-hydrolyzable perfluoroalkyl substituted monomer and maleic anhydride as described in U.S. Pat. No. 6,245,116 to Pechhold, et al, which is incorporated herein by reference.
  • Useful fluoropolymers are ZONYL 8412 and ZONYL RN available from E. I.
  • SCOTCHGARD FC 255 SCOTCHGARD FC 214-230, FLUORAD series, such as FLUORAD FC 129, available from the 3M Corporation, Minnesota Mining and Manufacturing Company, St. Paul, MN; and TEFLON RN, TEFLON 8070, and TEFLON 8787, available from E. I. du Pont de Nemours and Company.
  • Additional useful fluoropolymers include ZONYL 7950, ZONYL 5180, ZONYL 6885, ZONYL 7910, ZONYL 6700, ZONYL 8300, ZONYL 6991, ZONYL 310 and ZONYL NWG, all from E. I.
  • Useful fluoropolymers also include fluoropolymers available from Archroma, Arkema, Asahi Glass, Daikin, Goldschmidt, Hoechst Celanese, Mitsubishi, Peach State Laboratories, Shaw Industries and Trichromatic Carpet. Examples include the FOMBLIN FE-20 series of aqueous based perfluoro polyether microemulsions available from Solvay Specialty Polymers, Brussels, Belgium; fluoropolymer emulsion 3310, 3311 and Unidyne® TG-532, available from Noveon Inc.
  • NUVA FT and NUVA N2116 both fluorochemical acrylate polymers available from Archroma Corporation
  • SHAWGUARD 353 fluoroalkyl acrylate copolymer available from Shaw Industries, Inc.
  • BARTEX Til, BARTEX MAC both fluoroalkylacrylate polymers, available from Trichromatic Carpets, Inc., Quebec, Canada.
  • Highly preferred materials of this class of fluoropolymers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/ or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • a preferred range for hydrophobic agents in the fabric treatment compositions discussed herein is 0.5 to 60 weight %, more preferably 1 to 40 weight % and most preferably 5 to 30 weight % of the fabric treatment composition.
  • the hydrophobic agents suitable for use herein include those which are at least partly insoluble in water at a temperature of 20 °C, and which have a melting point or glass transition temperature below 100 °C and preferably between about 45 °C to about 100 °C.
  • Suitable hydrophobic agents include hydrophobic polymers, copolymers, and copolymers containing hydrophobic monomers.
  • Suitable hydrophobic agents include hydrophobic waxes, including, but not limited to paraffin waxes.
  • paraffin waxes suitable for use in accordance with the instant disclosure are generally complex mixtures without a clear-cut melting point. For characterization purposes, their melting range is normally determined by differential thermo analysis or DTA, as described in "The Analyst” 87 (1962), p. 420, and/or by their solidification point.
  • the glass transition temperature is understood to be the temperature at which wax changes from a liquid into a solid state through slow cooling.
  • paraffins can be completely liquid at room temperature, i.e., those with a solidification point below 25 °C, and paraffins that are solid at room temperature may both be used.
  • the paraffin wax is preferably solid at room temperature and can be present in completely liquid form at 100 °C. Suitable paraffin waxes for use in accordance with the instant disclosure may be obtained, for example, under the name of LUNAFLEX available from Fuller and under the name of DEAWAX from DEA Mineralol AG.
  • Suitable hydrophobic agents are produced from ethylenically unsatu- rated monomers.
  • monomers are styrene, acrylic acid or methacrylic acid esters of aliphatic C 1 to C 18 alcohols, acrylonitrile, vinyl acetate, acrylic acid and methacrylic acid.
  • polymers that contain 1 to 30 parts by weight of monomers containing carboxylic acid groups; 30 to 70 parts by weight of monomers which form homopolymers having glass temperatures below 20 °C, preferably esters of acrylic acid with C 1 to C 18 alcohols and/or methacrylic acid with C 1 to C 18 alcohols; and 30 to 70 parts by weight of monomers which form homopolymers having glass transition temperatures above room temperature, preferably methacrylic acid esters of C 1 to C 3 alcohols or styrene.
  • examples of such polymers include the following commercial products that are available as dispersions: SYNTRAN 1501, available from Interpolymer, PRIMAL 644, available from Dow Chemical, NEOCRYL A 1049, available from DSM Coating Resins, LLC.
  • polystyrene resin examples include low molecular weight (i.e., less than 500,000 Daltons) polyethylene, low density polyethylene, polypropylene, polyolefin, polyurethane, ethylvinyl acetate, polyvinyl chloride, and copolymers.
  • emulsifiable waxes capable of forming wax emulsions, include, for example, oxidized polyethylene, ethylene acrylic acid copolymers, and montanic acid and ester waxes available as LUWAX.
  • polyolefin waxes maleic grafted polyolefin waxes, paraffin, other hydrocarbon waxes and vegetable waxes such as carnauba and candelillia.
  • Preferred emulsifiable waxes include polyethylene, polypropylene, oxidized polyethylene, oxidized polypropylene, ethylene acrylic copolymers, and maleic grafted polyolefins.
  • Preferred emulsifiable waxes include polyolefins that are partially modified to contain functional groups improving dispersibility of the waxes, such functional groups include alkoxyl, carboxyl, amide, alkylamide, sulfonic, phosphonic or mixtures thereof.
  • Suitable emulsifiable waxes also include waxes containing chemical groups that facilitate emulsification, such as carboxylic or related groups.
  • emulsifiable waxes include oxygen-containing wax or oxidized waxes as illustrated by those described in the following patents: natural waxes such as candelillia, carnauba, beeswax, coconut wax, montan wax, as well as oxidized petroleum waxes as illustrated by U.S. Pat. No. 2,879,237 to Groote, et al, U.S. Pat. No. 2,879,238 to Groote, et al., U.S. Pat.
  • the low melting point wax is selected from microcrystalline Multiwax W145A available from Witco, paraffin Altafin 140/145 from Astor-Durachem, and micro- crystalline Rosswax 1365 from Frank B. Ross.
  • Highly preferred materials of this class of hydrophobic agents are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment, after drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight.
  • the hydrophobic agents can be delivered in emulsions that are nonionic, in that they do not contain an ionized functional group such as a quaternary ammonium group. They can be cationic in that they contain an ionized or ionizable functional group, such as a quaternary ammonium group in the first instance, or a tertiary amine, which is protonatable to provide for a positive charge center.
  • They can be zwitterionic in that they have both cationic and anionic groups present, suitably with the number of cationic and anionic groups present being essentially equivalent in number to provide an overall net nonionic property to the fluoropolymer, and also suitably with the number of cationic and anionic groups present being essentially non-equivalent in number to provide an overall net positive or cationic charge to the fluoropolymer. It is especially preferred that the hydrophobic agent ingredient be at least slightly cationic, that is that carry a net positive charge.
  • the liquid carrier is preferably an aqueous system.
  • the carrier can also con- tain a low molecular weight organic solvent that is highly soluble in water, e. g., C 1 to C 4 monohydric alcohols, C 2 to C 6 polyhydric alcohols, such as alkylene glycols and polyalkyl- ene glycols, alkylene carbonates, and mixtures thereof.
  • these water-soluble solvents include ethanol, propanol and isopropanol.
  • Water is a preferred liquid carrier due to its low cost, availability, safety, and environmental compatibility.
  • the water can be distilled, deionized, or tap water.
  • liquid carriers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the level of liquid carrier can typically be from about 20% to about 80% of the composition, preferably from about 30% to about 70%, and more preferably from about 40% to about 60%) of the composition.
  • the amount of liquid carrier can be greater.
  • the liquid carrier may typically range from about 50%> to about 99%) of the composition, preferably from about 60%> to about 98%>, and more preferably from about 80%> to about 95%> of the composition.
  • the liquid carrier can typically range from about70%> to about 99.9%), by weight of the composition, preferably from about 80%> to about 99.5%>, and more preferably from about 90%> to about 99%> of the composition.
  • levels of the inventive composition are necessarily reduced to the required level for effectiveness.
  • compositions of the present disclosure include fluoropolymers and
  • hydrophobic agents that become covalently and/or non-covalently attached to the surface of fabrics upon being cured at elevated temperatures.
  • electrokinetics One of these factors is the electrokinetics.
  • the term zeta potential applies to the electrical charges existing in fine dispersions. Specifically, a solid particle, e.g., insoluble polymer, which is suspended in an aqueous system is surrounded by a dense layer of ions having a specific electrical charge. This layer is surrounded by another layer, more diffuse than the first, that has an electrical charge of its own. The bulk of the suspended liquid also has its own electrical charge. The difference in electrical charge between the dense layer of ions surrounding the particle and the bulk of the suspended liquid is the zeta potential, usually measured in millivolts.
  • the zeta potential, ⁇ is defined by Equation (I):
  • ⁇ 4nbq/D (I) where q is the charge on the particle, ⁇ is the thickness of the zone of influence of the charge on the particle, and D is the dielectric constant of the liquid.
  • the fluoropolymers are attracted to the fabric surface owing to a combination of van der Waals attractive forces and electrostatic interactions.
  • the surface of the fabric is negatively charged due to the presence of the carboxylic groups of the cellulose.
  • adsorbed materials such as negative compounds or negatively charged surface active materials, e.g., anionic surface- tants found in detergents, can result in the surface of the fabric becoming negatively charged due the presence of these materials on the fabric surface.
  • adsorbed materials such as negative compounds or negatively charged surface active materials, e.g., anionic surface- tants found in detergents, can result in the surface of the fabric becoming negatively charged due the presence of these materials on the fabric surface.
  • the existence of negatively charged groups or adsorbed negatively charged materials on the fabric surface may inhibit the attraction of the fluoropolymers to the fabric surface to at least to some extent.
  • any negative surface charge present on fabrics to be treated can be reduced or avoided by introducing an appropriate amount of zeta potential modifier to adjust the zeta potential of the treatment liquor to a positive value greater than zero.
  • zeta potential modifier is added so that the zeta potential of the treatment liquor is positive and greater than zero millivolts.
  • the zeta potential of the treatment liquor ranges from a positive value of zero to about + 150 millivolts and preferably is less than about +100 millivolts.
  • at least one zeta potential modifier it will typically range from 0.1 to 30% of the composition.
  • Suitable zeta potential modifiers are cationic agents including, for example, cationic monomers, polymers, and copolymers comprising cationic monomers, wherein the cationic monomer is present at least to an extent sufficient to provide an overall net cationic nature, i.e. overall positive charge, to the copolymer.
  • Preferred cationic agents include cationic surfactants, including, but not limited to, mono and di-methyl fatty amines, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl amine acetates, trialkylammonium acetates, alkyldimethylbenzyl ammonium salts, dialkymethylbenzyl ammonium salts, alkylpyridinium halide and alkyl (alkyl substituted) pyridinium salts, alkylthiomethyl pyridinium salts, alkylamidomethyl pyridinium salts, alkylquinolinium salts, alkylisoquinolinium salts, ⁇ , ⁇ -alkylmethyl pyrollidonium salts, 1,1-dialkylpiperidinium salts, 4,4-dialkylthiamorpholinium salts, 4,4-dialkylthiamorpholinium-l-oxide salts, methyl bis(alkylethyl)-2
  • Suitable zeta potential modifiers further include cationic (i.e. bearing one or more positive charges) and cationically modified materials, including, for example, cationic and cationically modified organic polymers, cationic and cationically modified biopolymers, and cationic and cationically modified inorganic materials, including, for example, cationic and cationically modified clays, cationic and cationically modified silicas, cationic and cationically modified metal oxides and cationic and cationically modified composite materials.
  • cationic and cationically modified materials including, for example, cationic and cationically modified organic polymers, cationic and cationically modified biopolymers, and cationic and cationically modified inorganic materials, including, for example, cationic and cationically modified clays, cationic and cationically modified silicas, cationic and cationically modified metal oxides and cationic and cationically modified composite materials.
  • Suitable organic cationic polymers include, but are not limited to, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose which is available under the name UCARE Polymer JR 400® from Dow Chemical, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized
  • vinylpyrrolidone/vinylimidazole polymers such as, for example, Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat® L from BASF), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amodimethicones, copolymers of adipic acid and
  • dimethylaminohydroxypropyldiethylene triamine (Cartaretins® from Archroma), copolymers of acryamide with dimethyldiallylammonium chloride (Merquat 550 from Lubrizol), polyaminopolyamides, as described, for example, in FR 2252840 A, and their crosslinked water-soluble polymers, condensation products of dihaloalkyls, such as, for example, dibromobutane with bisdialkylamines, such as, for example, bisdimethylamino-1, 3 -propane, cationic guar gum, such as guarhydroxypropyltrimethylammonium chloride (for example, Jaguar® C-16 and Jaguar® C-17 from Solvay Rhodia; Cosmedia Guar C 261 from BASF), quaternized ammonium salt polymers, such as, for example, Mirapol®A-15, Mirapol®AD-l, Mirapol® AZ-1 from Solvay Rhodia, and cationically
  • Additional cationic compounds suitable for use as zeta potential modifiers include amine acid salts; polyacryamidopropyltrimmonium chloride; betaines, such as but not limited to, alkyl betaines, alkyl amido betaines, imidazolinium betaines; quaternized poly(vinylpyridine); amidoamine acid salts; poly(imine) acid salts; polyethylene imine acid salts; cationic polyacryamides; poly(vinylamine) acid salts; cationic ionene polymers;
  • poly(vinylimidazolinium salts) such as but not limited to, the diquatemary polydimethyl siloxanes; poly(vinyl alcohol) quaternary materials;
  • polydimethyldiallylammonium chloride cationic exchange resins; anionic exchange resins; copolymers of vinylpyrrolidone and methyacrylamidopropyltrimethylammonium chloride; acidified polyvinylpolypyrrolidones; acidified copolymers of vinylpyrrolidone and vinylacetate; acidified copolymers of vinylpyrrolidone and dimethylaminoethylmetacrylate; copolymers of vinylpyrrolidone and methacrylamidopropyl trimethylammonium chloride; copolymers of quaternized vinylpyrrolidone and dimethylaminoethyl methacrylate; acidified copolymers of vinylpyrrolidone and styrene; acidified copolymers of vinylpyrrolidone and acrylic acid, and cationic polyelectrolyte polymers.
  • Suitable organic cationic inorganic materials suitable for use as zeta potential modifiers include, but are not limited to cationic clay, such as for example, sodium mont- morillonite, hydrotalcite, vermiculite, kaolinite; clays reacted with quaternary compounds, such as, tetramethylammonium chloride; polyquarternized amines; acidified n-alkyl-2-pyr- rolidones; polyacrylic acid polymers; alkyl C 8 to alkyl C 24 organic acids, such as but not limited to, lauric acid, satiric acid; and combinations thereof.
  • cationic clay such as for example, sodium mont- morillonite, hydrotalcite, vermiculite, kaolinite
  • clays reacted with quaternary compounds such as, tetramethylammonium chloride
  • polyquarternized amines such as, acidified n-alkyl-2-pyr- rolidones
  • polyacrylic acid polymers alkyl
  • Suitable metal oxides and composites include cationically modified metal oxides and layered metal oxide composites, for example, but not limited to, oxides of silicon, germanium, selenium, chromium, titanium, aluminum, gallium, nickel, iron, copper, silver, gold, platinum, magnesium and calcium, and mixtures and/or layered composites thereof.
  • Suitable zeta potential modifiers further include cationically modified silicas, such as those disclosed in U.S. App. No. 20030157804, which is incorporated herein by reference.
  • Suitable zeta potential modifiers further include chitosans, which are cationic biopolymers under the pH conditions, and cationic chitin derivatives, such as, for example, quaternized chitosan, optionally in microcrystalline distribution. Examples are disclosed in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, p. 231-232, which is incorporated herein by reference.
  • Preferred forms of the zeta potential modifiers described herein include water soluble, water dispersible and water insoluble suspensions, dispersions or emulsions of these zeta potential modifiers.
  • Preferred forms of the inorganic and polymeric based zeta potential modifiers include fine particulates for improved dispersibility in the compositions discussed herein.
  • Preferred forms of the inorganic and polymeric zeta potential modifiers include particulates having particle sizes in the micron and nanometer size ranges. Preferred sizes of particulates, for example, include particle sizes of about 1 nanometer to about 100 microns, most preferred being particle sizes in the range of about 1 nanometer to about 1 micron.
  • fabric softeners that include cationic surfactants can be employed as a source of zeta potential modifiers.
  • the fabric softener serves multiple functions including facilitating the attachment of the fluoropolymers and hydrophobic agents to the fabric surface.
  • multivalent cationic salts including cations of the alkaline earth metals (Group IIA), transition metals (Groups IIIB, IVB, VB, VIB, Vim, VIIIB, IB, IIB) and non-metal elements (Groups IIIA, IV A, VA) may be appropriate for use as zeta potential modifiers alone, combined together, or in combination with other zeta potential modifiers described herein.
  • the zeta potential modifiers are included as optional ingredients of the fabric treatment composition as discussed herein.
  • the zeta potential modifiers are deemed optional in that they are not needed to counteract the negatively charged species, such as anionic surfactants found in commercial detergents, that might otherwise interfere to some extent with the attraction of the fluoropolymer to the fabric surface.
  • Highly preferred materials of this class of zeta potential modifiers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • a suitable range for zeta potential modifiers in the fabric treatment compositions presented herein is 0.1 to 30 weight %, more preferably 0.1 to 20 weight % and most preferably 0.1 to 5 weight % of the fabric treatment composition.
  • the amount of zeta potential modifier that may be acceptable for use in a second fabric treatment composition remains about the same, in order to maintain the zeta potential in the treatment liquor.
  • the above fluoropolymers and hydrophobic agents may require the use of emulsifiers, such as ethoxylated fatty alcohols, fatty amides, fatty acids and alkylphenols and fatty amines or salts thereof.
  • emulsifiers include quaternary ammonium or protonated amine cationic surfactants such as trimethyl-dodecylammonium chloride, tri- methyl-hexadecylammonium chloride, dimethyl-dicocoammonium chloride, and dimethyl- octadecylammonium acetate.
  • Preferred nonionic emulsifiers include the etherifi cation products of ethylene oxide and/or propylene oxide with glycerol monooleate, oleic acid, cetyl alcohol, pelargonic acid, stearyl alcohol, sorbitan monooleate, sorbitan monostearate.
  • Highly preferred materials of this class of emulsifiers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying, or after the drying step followed by normal exposure to the elements, such as air, moisture or sunlight exposure
  • the pH of the resulting aqueous solution should be in the range from about 2 to about 11. Adjustment of pH can be carried out by including a small quantity of an acid in the fabric treatment composition. Because no strong pH buffers need be present, only small amounts of acid may be required.
  • the pH may be adjusted with inorganic or organic acids, for example hydrochloric acid or alternatively with monobasic or dibasic organic acids, such as acetic acid, maleic acid or in particular glycolic acid. Additional acids that can be used include, but are not limited to, methyl sulfonic, hydrochloric, sulfuric, phosphoric, citric, maleic, and succinic acids.
  • Adjustment of pH may be carried out by including a small quantity of a base in the formulation. Because no strong pH buffers need be present, only small amounts of base may be required.
  • the pH may be adjusted with inorganic bases, including, but not limited to, alkali metal or alkaline earth metal salts of hydroxides, carbonates, bicarbonates, borates, sulfonates, phosphates, phosphonates and silicates.
  • the pH may be adjusted with organic bases, including, but not limited to, salts of monocarboxylic acids, salts of dicarboxylic acids, salts of citric acid and other suitable organic acids with water soluble conjugate bases presented previously herein.
  • the pH may be adjusted with organic bases such as the alkanolamines including methanol, ethanol and propanol amines, including dimethanol, diethanol and dipropanol amines, and including trimethanol, triethanol and tripropanol amines.
  • organic bases such as the alkanolamines including methanol, ethanol and propanol amines, including dimethanol, diethanol and dipropanol amines, and including trimethanol, triethanol and tripropanol amines.
  • Highly preferred materials for pH adjusters are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • An optional silicone component can be used in an amount from about 0.1% to about 6% of the composition, preferably from 0.1 to 3% of the total fabric treatment composition, in order to assist in imparting water repellency to a textile.
  • Both silicones and organopolysiloxanes may be used.
  • hydrophilizing silicones such as dimethylpolysiloxanes which contain incorporated epoxy groups and/or polyethoxy or polypropoxy or polyethoxy/propoxy groups.
  • Preferred siloxanes include aminoethylaminopropyl dimethyl siloxane, hydroxy terminated dimethyl siloxane (dimethiconol), and modified hydrogen alkyl polysiloxanes.
  • Preferred silicones comprise cationic and amphoteric silicones, polysiloxanes, and polysiloxanes having hydrogen-bonding functional groups consisting of amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups.
  • Such polysiloxanes include, but are not limited to, polyether-modified polysiloxanes, amino-modified polysiloxanes, epoxy-modified polysiloxanes, polyhydrido-modified polysiloxanes, phenol derivative-modified polysiloxanes, ABA-type polysiloxanes, including those available from OSi Specialties, Inc. (a division of Witco Corporation), under the SILWET, NUWET, NUDRY, NUSOF, MAGNASOFT trade names.
  • Preferred silicones may include polydi- methylsiloxanes of viscosity from about 100 centistokes (cs) to about 100,000 cs, and preferably from about 200 cs to about 60,000 cs and/or silicone gums. These silicones can be used in emulsified form, which can be conveniently obtained directly from the suppliers. Examples of these pre-emulsified silicones are the 60% emulsion of polydimethylsiloxane (350 cs) sold by Dow Corning Corporation under the trade name DOW CORNING 1157 Fluid and the 50% emulsion of poly dimethyl siloxane (10,000 cs) sold by General Electric Company under the trade name GENERAL ELECTRIC 2140 silicones. Silicone foam suppressants can also be used.
  • Highly preferred materials of this class of silicones are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the composition can contain a nonionic surfactant.
  • a nonionic surfactant When a nonionic surfactant is added to the composition, it can typically be added at a level from about 0.05% to about 30%), preferably from about 0.05% to about 20%, and more preferably from about 0.1 % to about 10%) of the composition.
  • Suitable nonionic surfactants include addition products of alkoxylating agents such as ethylene oxide (EO), propylene oxide (PO), isopropylene oxide (IPO), or butylene oxide (BO), or a mixture thereof, with fatty alcohols, fatty acids, and fatty amines. Any of the alkoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant.
  • the nonionic surfactant is selected from the group consisting of alkylether carboxylate, alcohol ethoxylate or secondary alcohol ethoxylate, and alkyl phenyl ethoxylate or alkyl aryl ethoxylate.
  • nonionic surfactants may also contain a mixture of ethoxylate and propoxylate.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent No. 4,565,647 to Llenado and incorporated herein by reference, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group.
  • Further examples of suitable surfactants are described in McCutcheon's Vol. 1 : Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC Publishing Co., 1995, which is incorporated herein by reference.
  • Highly preferred materials of this class of nonionic surfactants are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • compositions discussed herein can contain a cationic surfactant.
  • a cationic surfactant When a cationic surfactant is added to the fabric treatment compositions of the instant disclosure, it can typically be added at a level from about 0.05% to about 30%, preferably from about 0.05%) to about 20%, and more preferably from about 0.1%> to about 10%> of the composition.
  • the cationic surfactant can optionally be one or more fabric softener actives.
  • Preferred fabric softening actives include amines and quaternized amines.
  • N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride where the tallow chains are at least partially unsaturated and N,N- di(canoloyl-oxy-ethyl)-N,N- dimethyl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N- methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N- methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.
  • Additional fabric softening agents useful herein are described in U.S. Patent No. 5,643,865 to
  • Suitable cationic surfactants include ethoxylated quaternary ammonium surfactants.
  • Some preferred ethoxylated quaternary ammonium surfactants include PEG-5 cocoammonium methosulfate; PEG- 15 cocoammonium chloride; PEG- 15 oleoammonium chloride; and bis(polyethoxyethanol) tallow ammonium chloride.
  • Further examples of suitable surfactants are described in McCutcheon's Vol. 1 : Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC Publishing Co., 1995, which is incorporated herein by reference.
  • the counterion to these cationic surfactants may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like.
  • Highly preferred materials of this class of cationic surfactants and their counterions are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the fabric treatment compositions of the instant disclosure can contain amphoteric and/or zwitterionic surfactants.
  • an amphoteric or zwitterionic surfactant When an amphoteric or zwitterionic surfactant is added to the fabric treatment compositions discussed herein, it can typically be added at a level from about 0.05% to about 30%, preferably from about 0.05% to about 20%, and more preferably from about 0.1% to about 10% of the composition.
  • Suitable amphoteric surfactants include amine oxides having the formula ( R 1 )(R 2 )(R 3 )NO wherein each of R 1 , R 2 and R 3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chains of from 1 to 30 carbon atoms.
  • Preferred amine oxide surfactants to be used according to the present disclosure include amine oxides having the formula (R 1 )(R 2 )(R 3 )NO wherein R 1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, further preferably from 8 to 12, and wherein R 2 and R 3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups.
  • R 1 may be a saturated substituted or unsubstituted, linear or branched hydrocarbon chain.
  • Suitable amine oxides for use herein are, for instance, naturally derived hydrocarbon blends of C 8 -C 10 amine oxides as well as C 12 -C 16 amine oxides commercially available from Hoechst.
  • Suitable zwitterionic surfactants may contain both cationic and anionic hydrophilic groups on the same molecule at a relatively wide pH range.
  • a typical cationic group is a quaternary ammonium group, although other positively charged groups like phosphonium, imidazolium and sulfonium groups can be used.
  • Typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
  • R 1 -N'(R 2 )(R 3 )R 4 X- wherein R 1 is a hydrophobic group; R 2 and R 3 are each C 1 - C 4 alkyl, hydroxy alkyl or other substituted alkyl group which can also be joined to form ring structures with the N; R 4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is preferably a carboxylate or sulfonate group.
  • Preferred hydrophobic groups R 1 are alkyl groups containing from 1 to 24, preferably less than 18, and more preferably less than 16 carbon atoms.
  • the hydrophobic group can contain unsaturation and/or substituents and/or linking groups such as aryl groups, amido groups, ester groups and the like.
  • the simple alkyl groups are preferred for cost and stability reasons.
  • amphoteric surfactants include alkylampho glycinates, and alkyl imino propionate.
  • Highly preferred zwitterionic surfactants include betaine and sulphobetaine surfactants, derivatives thereof or mixtures thereof.
  • betaine or sulphobetaine surfactants are preferred herein as they are particularly suitable for the cleaning of delicate materials, including fine fabrics such as silk, wool and other naturally derived textile materials. Betaine and sulphobetaine surfactants are also extremely mild to the skin and/or fabrics to be treated that come in contact with the user's skin.
  • Suitable betaine and sulphobetaine surfactants to be used herein include the betaine/sulphobetaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values.
  • Some common examples of these detergents are described in U.S. Patent No. 2,082,275 to Daimler, et al, U.S. Patent No. 2,702,279 to Funderburk, et al, and U.S. Patent No. 2,255,082 to Orthner, et al, which are incorporated herein by reference.
  • Further examples of suitable surfactants are described in McCutcheon's Vol. 1 : Emulsifiers and Detergents, North American Ed., McCutcheon
  • Highly preferred materials of this class of amphoteric and zwitterionic surfactants are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the fabric treatment compositions disclosed herein can contain an anionic surfactant.
  • an anionic surfactant When an anionic surfactant is included in the fabric treatment composition, it can typically be added at a level from about 0.05% to about 15%, preferably from about 0.05% to about 5%), and more preferably from about 0.1% to about 1% of the composition.
  • Suitable anionic surfactants include C 8 -C 18 alkyl sulfonates, C 10 -C 14 linear or branched alkyl benzene sulfonates, C 10 -C 14 alkyl sulfates and ethoxysulfates (e.g.,
  • McCutcheon's Vol. 1 Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC Publishing Co., 1995, which is incorporated herein by reference.
  • Highly preferred materials of this class of anionic surfactants are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the composition can include a soil release agent that is present from about 0% to about 5%, preferably from about 0.05% to about 3%, and more preferably from about 0.1% to about 2% of the composition.
  • a soil release agent that is present from about 0% to about 5%, preferably from about 0.05% to about 3%, and more preferably from about 0.1% to about 2% of the composition.
  • Polymeric soil release agents useful with the fabric treatment compositions of the instant disclosure include copolymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like.
  • a preferred soil release agent is a copolymer having blocks of terephthalate and polyethylene oxide.
  • these polymers may be comprised of repeating units of ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units from about 25:75 to about 35:65, and the polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights from about 300 to about 2000.
  • the molecular weight of this type of polymeric soil release agent can be in the range from about 5,000 to about 55,000. Suitable soil release agents are disclosed in U.S. Patent Nos.
  • 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 may preferably comprise ethylene and/or propylene groups.
  • soil release polymers are nonionic, for example, the nonionic soil release polymer described in U.S. Patent No. 4,849,257 to Borcher, Sr., et al., which is incorporated herein by reference.
  • the polymeric soil release agents useful in the instant disclosure can include anionic and cationic polymeric soil release agents. Suitable anionic polymeric or oligomeric soil release agents are disclosed in U.S. Patent No. 4,018,569 to Chang, which is incorporated herein by reference. Other suitable polymers are disclosed in U.S. Patent No. 4, 808,086 to Evans, et al., which is incorporated herein by reference.
  • Highly preferred materials of this class of soil release polymers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the composition can include antistatic agents, which can be present at a level from about 0% to about 5%, preferably from about 0.005% to about 5%, more preferably from about 0.05% to about 2%, and further preferably from about 0.2% to about 1% of the composition.
  • Preferred antistatic agents include cationic surfactants, including quaternary ammonium compounds such as alkyl benzyl dimethyl ammonium chloride; dicoco quarter- nary ammonium chloride; coco dimethyl benzyl ammonium chloride; soya trimethyl quaternary ammonium chloride; hydrogenated tallow dimethyl benzyl ammonium chloride; and methyl dihydrogenated tallow benzyl ammonium chloride.
  • alkyl imidazolinium salts are alkyl imidazolinium salts.
  • Other preferred antistatic agents are the ion pairs of, e.g., anionic detergent surfactants and fatty amines, or quaternary ammonium derivatives thereof, e.g., those disclosed in U.S. Patent No. 4,756,850 to Nayar, which is incorporated herein by reference.
  • Other preferred antistatic agents are ethoxylated and/or propoxylated sugar derivatives.
  • Preferred antistatic agents include monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride (available from Henkel
  • ethyl bis(polyethoxyethanol) alkyl ammonium ethyl sulfate available from Witco Corporation under the trade name VARIQUAT 66
  • polyethylene glycols polymeric quaternary ammonium salts (such as those available from Rhone- Poulenc Corporation under the MIRAPOL trade name)
  • quaternized polyethyleneimines vinylpyrrolidone/ methacrylamidopropyl trimethylammonium chloride copolymer (available from GAF Corporation under the trade name GAFQUAT HS-100), triethonium hydrolyzed collagen ethosulfate (available from Maybrook Inc. under the trade name QUAT-PRO E), and mixtures thereof.
  • Highly preferred materials of this class of antistatic agents are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Perfumes or fragrance materials may be added to the composition.
  • the selection of the perfume or perfumes maybe based upon the application, the desired effect on the consumer, and preferences of the formulator.
  • the perfume selected for use with the compositions and formulations of the fabric treatment compositions presented herein may contain ingredients with odor characteristics which are preferred in order to provide a fresh impress- sion on the surface to which the composition is directed, for example, those which provide a fresh impression for fabrics.
  • Such perfume may be preferably present at a level from about 0.01 % to about 5%, preferably from about 0.05% to about 3%, and more preferably from about 0.1 % to about 2% of the total composition.
  • the perfume may be composed of fragrance materials selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohols having molecular weights from about 90 to about 240; aliphatic ketones having molecular weights from about 150 to about 260; aromatic ketones having molecular weights from about 150 to about 270; aromatic and aliphatic lactones having molecular weights from about 130 to about 290; aliphatic aldehydes having molecular weights from about 140 to about 200; aromatic aldehydes having molecular weights from about 90 to about 230; aliphatic and aromatic ethers having molecular weights from about 150 to about 270; and condensation products of aldehydes and amines having molecular weights from about 180 to about 320; and mixtures thereof.
  • fragrance materials selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohol
  • perfumes or fragrance materials include, but are not limited to: adoxal (2,6,10-trimethyl-9- undecen-l-al), allyl amyl glycolate, allyl cyclohexane (allyl-3-cyclohexylpropionate), amyl acetate (3 -methyl- 1-butanol), amyl salicylate, anisic aldehyde (4-methoxybenzaldehyde), aurantiol (condensation product of methyl anthranilate and hydroxycitronellal), bacdanol (2- ethyl-4-(2,2,3-trimethyl-3-cyclopenten-l-yl)-2-buten-l-ol), benzaldehyde, benzophenone, benzyl acetate, benzyl salicylate, damascone (l-(2,6,6-trimethyl-l- cyclohexen-l-yl)-2-buten-
  • cyclopentadecanolide flor acetate (dihydronorcyclopentadienyl acetate), florhydral (3-(3- isopropylphenyl)butanal), frutene (dihydronorcyclopentadienyl propionate), galaxolide (l,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopent-gamma-2-benzopyrane), gamma- decalactone (4-N-heptyl-4-hydroaldehyde), cinnamic aldehyde, hexyl salicylate,
  • perfumes and fragrance materials are well-known to those of skill in the art, both for desired scent and appropriate scent impact.
  • a perfume containing perfume ingredients that are not too hydrophobic.
  • the degree of hydrophobicity of a perfume ingredient can be correlated with its octanol/water partitioning coefficient P, the ratio between its equilibrium concentration in octanol and in water.
  • P octanol/water partitioning coefficient
  • a perfume ingredient with a greater partitioning coefficient P is more hydrophobic and a perfume ingredient with a smaller partitioning coefficient P is more hydrophilic; a selection based on the application and intended effect may be made accordingly.
  • the preferred perfume ingredients may have an octanol/water partitioning coefficient P of about 1,000 or smaller.
  • Highly preferred materials of this class of fragrances and perfumes are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • ANTEVIICROB IAL S AND PRESERVATIVES can be added tothe fabric treatment compositions of the instant disclosure.
  • Typical concentrations for biocidal effectiveness of these compounds may range from about 0.001% to about 0.8%, preferably from about 0.005%) to about 0.3%>, and more preferably from about 0.01%> to 0.2% 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%> of the concentrated compositions.
  • Preservatives are especially preferred when organic compounds that are subject to microorganisms are added to the fabric treatment compositions disclosed herein, especially when they are used in aqueous compositions. When such compounds are present, long term and even short-term storage stability of the compositions and formulations becomes an important issue since contamination by certain microorganisms with subsequent microbial growth often results in an unsightly and/or malodorous solution.
  • compositions and formulations are highly objectionable when it occurs, it is preferable to include a solubilized water-soluble, antimicrobial presser- vative, which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear and often aqueous compositions and formulations discussed and disclosed herein.
  • Typical microorganisms that can be found in laundry products include bacteria, for example, Bacillus thurigensis (cereus group) and Bacillus sphaericus, and fungi, for example, Aspergillus ustus.
  • Bacillus sphaericus is one of the most numerous members of Bacillus species in soils.
  • microorganisms such as Escherichia coli and
  • Pseudomonas aeruginosa are found in some water sources, and can be introduced during the preparation of aqueous solutions of the fabric treatment compositions discussed herein. It is preferable to use a broad spectrum preservative, for example, one that is effective on both bacteria (both Gram positive and Gram negative) and fungi.
  • a limited spectrum preservative for example, one that is only effective on a single group of microorganisms, for example, 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.
  • Antimicrobial preservatives useful in the present fabric treatment compositions discussed herein can be biocidal compounds, that is, substances that kill microorganisms, or biostatic compounds, that is, substances that inhibit and/or regulate the growth of microorganisms.
  • Preferred antimicrobial preservatives include those that are water-soluble and are effective at low levels.
  • the water- soluble preservatives that may be used include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary compounds, dehydroacetic acid, phenyl and phenoxy compounds, and mixtures thereof.
  • preservatives useful in the instant fabric treatment compositions include, but are not limited to, the short chain alkyl esters of p-hydroxybenzoic acid (commonly known as parabens); N-(4-chlorophenyl)-N-(3,4-dichlorophenyl) urea (also known as 3,4,4-trichloro- carbanilide or triclocarban); 2,4,4-trichloro-2'-hydroxydiphenyl ether, commonly known as Triclosan®); a mixture of about 77% 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available from The Dow Chemical Company as a 1.5% aqueous solution under the trade name KATHON CG; 5- bromo-5-nitro-l,3-dioxane, available from BASF Corporation under the trade name
  • BRONIDOX L 2-bromo-2-nitropropane-l,3-diol, available from The Dow Chemical Company under the trade name BRONOPOL; l,l-hexamethylenebis(5-p-(chlorophenyl)- biguanide) (commonly known as chlorhexidine) and its salts, for example, with acetic and digluconic acids; a 95:5 mixture of 1,3- bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidine- dione and 3-butyl-2- iodopropynyl carbamate, available from Lonza Inc.
  • the preservative can be any organic preservative material that is appropriate for applying to a fabric. With respect to the embodiments presented herein, such preservative(s) will preferably not cause damage to a fabric appearance, for example, through discoloration, coloration, or bleaching of the fabric.
  • the antimicrobial preservative is included in the fabric treatment compositions disclosed herein, it is preferably present in an effective amount, wherein an "effective amount” means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time.
  • an "effective amount” means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time.
  • Preferred levels of preservative are from about 0.0001% to about 0.5%), more preferably from about 0.0002%) to about 0.2%, further preferably from about 0.0003%) to about 0.1%>, of the composition.
  • the preservative can be used at a level that provides an antimicrobial effect on the treated fabrics.
  • the composition may also include a solubilized, water-soluble antimicrobial active, useful in providing protection against organisms that become attached to the treated material.
  • a solubilized, water-soluble antimicrobial active useful in providing protection against organisms that become attached to the treated material.
  • the free, uncomplexed antimicrobial, e.g., antibacterial, active provides an optimum antibacterial performance. Sanitization of fabrics can be achieved by the compositions of the present disclosure containing antimicrobial materials, e.g., antibacterial halogenated compounds, quaternary compounds, and phenolic compounds.
  • Some of the more robust antimicrobial halogenated compounds which can function as disinfectants/sanitizers as well as finish product preservatives, and are useful in the compositions of the instant disclosure include 1, 1--hexam ethylene bis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, and its salts, e.g., with hydrochloric, acetic and gluconic acids.
  • the digluco- nate 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 with the fabric treatment compositions disclosed herein, it can typically be present at a level from about 0.001%> to about 1.0%, preferably from about 0. 002%> to about 0.3%, and more preferably from about 0.01%) to about 0. 1%, by weight of the usage composition. In some cases, a level 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, phenyl sulfonates such as p-methylphenyl sulfonates, nitrates, acetates, gluconates, and the like.
  • Non- limiting examples of 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 HY AMINE (available from Lonza); (2) dialkyl quaternary such as BARD AC products of Lonza, (3) N- (3- chloroallyl) hexaminium chlorides such as DOWICIDE and DOWICIL available from Dow; (4) benzethonium chloride such as HY AMINE 1622 from Rohm & Haas; (5) methylbenzethonium chloride represented by HY AMINE 10X supplied by Rohm & Haas, (6) cetylpyridinium chloride such as Cepacol chloride available from of Merrell Labs.
  • BARQUAT available from Lonza
  • MAQUAT available from Mason
  • VARIQUAT available from Witco/Sherex
  • Preferred antimicrobial compounds for use herein include quaternary ammonium compounds containing alkyl or substituted alkyl groups, alkyl amide and carboxylic acid groups, ether groups, unsaturated alkyl groups, and cyclic quaternary ammonium compounds, which can be chlorides, dichlorides, bromides, methyl sulphates, chlorophenates, cylcohexyl sulphamates or salts of the other acids.
  • alkylpyridinium chlorides and/or sulphates the alkyl group being preferably cetyl, dodecyl or hexadecyl group
  • -alkylisoquinolyl chlorides and/or bromides the alkyl group being preferably dodecyl group.
  • Particularly suitable quaternary ammonium compounds for use herein include alkyldimethylbenzyl ammonium chloride, octyl decyl dimethylammonium chloride, dioctyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, alkyl dimethyl ammonium saccharinate,
  • cetylpyridinium and mixtures thereof.
  • Highly preferred materials of this class of antimicrobials and preservatives are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • dyes and colorants can be added to fabric treatment compositions of the instant disclosure.
  • Typical concentrations of these compounds may range from about 0.001 % to about 0.8%, preferably from about 0.005% to about 0.3%, and more preferably from about 0.01 % to 0.2% of the usage composition.
  • Colorants and dyes, especially bluing agents, can be optionally added to the compositions of the instant disclosure for visual appeal and performance impression. When colorants are used, they may be used at extremely low levels to avoid fabric staining.
  • Preferred colorants for use with the fabric treatment compositions discussed herein include highly water-soluble dyes, for example, LIQUITINT dyes available from Milliken Chemical Company.
  • 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 II, and mixtures thereof.
  • Any dye can be used in the compositions of the instant disclosure, but nonionic dyes are preferred in order to decrease interaction with the zeta potential modifier and/or with the dye transfer inhibitor.
  • Useful acid dyes include: Polar Brilliant Blue and D&C Yellow #10, both supplied by Hilton Davis Chemical Company. Nonionic LIQUITINT dyes supplied by Milliken Chemical Company are also useful.
  • Suitable colors include, but are not limited to, Acid Black 1, Acid Blue 3, Acid Blue 9 Aluminum Lake, Acid Blue 74, Acid Green 1, Acid Orange 6, Acid Red 14 Aluminum Lake, Acid Red 27, Acid Red 27 Aluminum Lake, Acid Red 51, Acid Violet 9, Acid Yellow 3, Acid Yellow 3 Aluminum Lake, Acid Yellow 73, Aluminum Powder, Basic Blue 6, Basic Yellow 11, Carotene, Brilliant Black 1, Bromocresol Green, Chromium Oxide Greens, Curry Red, D&C Blue No. 1 Aluminum Lake, D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 3 Aluminum Lake, D&C Green No. 5, D&C Orange No. 4 Aluminum Lake, D&C Red No. 6, D&C Red No. 6 Aluminum Lake, D&C Violet No. 2, D&C Yellow No.
  • D&C Yellow No. 11 D&C Blue No. 1
  • FD&C Yellow No. 5 Aluminum Lake, iron oxides, Pigment Orange 5, Pigment Red 83, Pigment Yellow 73, Solvent Orange 1, Solvent Yellow 18, ultramarines, and zinc stearate.
  • Highly preferred dyes and colorants for use herein are those that do not effectively bind to or permanently dye or color fabrics treated by use of the fabric treatment compositions disclosed herein, nor cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Optionally added viscosity control agents can be organic or inorganic in nature and may either lower or raise the viscosity of the formulation.
  • organic viscosity modifiers to lower viscosity are aryl carboxylates and sulfonates (for example including, but not limited to benzoate, 2-hydroxybenzoate, 2-aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate), fatty acids and esters, fatty alcohols, and water-miscible solvents such as short chain alcohols.
  • inorganic viscosity control agents are water-soluble ionizable salts.
  • ionizable salts can be used.
  • suitable salts are the halides and acetates of ammonium ion and the group IA and IIA metals of the Periodic Table of the Elements, for example, calcium chloride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, ammonium iodide, sodium acetate, potassium acetate, or mixtures thereof.
  • Calcium chloride is preferred.
  • the ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity.
  • the amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desire of the formulator. Typical levels of salts used to control the composition viscosity are from 0 to about 10%, preferably from about 0.01% to about 6%, and more preferably from about 0.02% to about 3% of the composition.
  • Viscosity modifiers or thickening agents can be added to increase the ability of the compositions to stably suspend water-insoluble articles, for example, perfume microcapsules.
  • Such materials include hydroxypropyl substituted guar gum (such as that available from Rhone-Poulenc Corporation under the trade name JAGUAR HP200), polyethylene glycol (such as that available from Union Carbide Corporation under the trade name CARBOWAX 20M), hydrophobically modified hydroxy ethylcellulose (such as that available from the Aqualon Company under the trade name NATROSOL Plus), and/or organophilic clays (for example, hectorite and/or bentonite clays such as those available from Rheox Company under the name BENTONE 27, 34 and 38 or from Southern Clay Products under the trade name BENTOLITE L; and those described in U.S.
  • Highly preferred materials of this class of thickeners and viscosity control and viscosity modifiers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • pearlizing or opacifying agents examples include, but are not restricted to, glycol distearate, propylene glycol distearate, and glycol stearate. Some of these products are available from Witco Corporation under the KEMESTER trade name.
  • Highly preferred materials of this class of pearlizing and opacifying agents are those that do bind to treated fabrics, nor cause any significant color change nor impart any discoloration, such as whitening, graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • antioxidants examples include propyl gallate, available from Eastman Chemical Products, Inc. under the trade names TENOX PG and TENOX S-l, and dibutylated hydroxytoluene, available from UOP Inc. under the trade name SUSTANE BHT. Also preferred are antioxidants for providing sun-fade protection for textiles treated with the fabric treatment compositions of the instant disclosure, such antioxidants being described in EP0773982, and incorporated herein by reference.
  • Preferred antioxidants include 2-(N-methyl-N- cocoamino)ethyl-3',5'-di-tert-butyl-4'-hydroxybenzoate; 2-(N, N-dimethyl-amino)ethyl-3',5'- di-tert-butyl-4'-hydroxybenzoate; 2-(N- methyl-N-cocoamino)ethyl-3',4',5'-trihydrox- ybenzoate; and mixtures thereof, more preferably 2-(N-methyl-N-cocoamino)ethyl-3',5'-di- tert-butyl-4'-hydroxy benzoate.
  • the butylated derivatives are preferred in the compositions disclosed herein, because tri-hydroxybenzoates have a tendency to discolor upon exposure to light.
  • the antioxidant compounds of the instant disclosure demonstrate light stability in the fabric treatment compositions discussed herein. "Light stable” as used herein is understood to mean that the antioxidant compounds used in the fabric treatment compositions disclosed herein do not discolor when exposed to either sunlight or simulated sunlight for approximately 2 to 60 hours at a temperature of from about 25°C to about 45°C.
  • Antioxidant compounds and free radical scavengers can generally protect dyes from degradation by first preventing the generation of single oxygen and peroxy radicals, and thereafter terminating the degradation pathways.
  • compositions of the instant disclosure may comprise an organic sunscreen.
  • Suitable sunscreens can have UVA absorbing properties, UVB absorbing properties, or a combination of both.
  • the compositions of the present disclosure may preferably comprise a UVA absorbing sunscreen actives that absorb UV radiation having a wavelength from about 320 nm to about 400 nm.
  • Suitable UVA absorbing sunscreen actives include
  • dibenzoylmethane derivatives examples include anthranilate derivatives such as methylanthranilate and homomethyl-l-N-acetylanthranilate, and mixtures thereof.
  • dibenzoylmethane sunscreen actives are described in U.S. Patent No 4,387,089 to De Polo; and in Sunscreens: Development, Evaluation, and Regulatory Aspects edited by N. J. Lowe and N. A. Shaath, Marcel Dekker, Inc. (1990), which are incorporated herein by reference.
  • the UVA absorbing sunscreen active is preferably present in an amount to provide broad-spectrum UVA protection either independently, or in combination with, other UV protective actives that may be present in the composition.
  • Preferred UVA sunscreen actives include dibenzoylmethane sunscreen actives and their derivatives. They include, but are not limited to, those selected from 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4- isopropyl- dibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2, 5- dimethyldibenzoylmethane, 4,4'- diisopropylbenzoylmethane,4-(l, l-dimethylethyl)-4'- methoxy dibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxy dibenzoylmethane, 2-methyl-5- tert-butyl-4'-methoxy dibenzoylmethane, 2,4-dimethyl-4'-methoxy dibenzoylmethane, 2,6- dimethyl-4'-tert-
  • Preferred diben- zoyl sunscreen actives include those selected from 4-( 1,1 -dimethylethyl)-4'-methoxy dibenzoylmethane, 4-isopropyldibenzoylmethane, and mixtures thereof.
  • a more preferred sunscreen active is 4-(l,l-dimethylethyl)-4'-methoxy dibenzoylmethane, which is also known as butylethoxydibenzoylmethane or Avobenzone, is commercially available under the names of PARSOL 1789 from Givaudan Roure (International) S. A. (Basel, Switzerland) and EUSOLEX 9020 from Merck & Co., Inc. (Whitehouse Station, N.J.).
  • the sunscreen 4- isopropyldibenzoylmethane which is also known as isopropyldibenzoylmethane, is commercially available from Merck under the name of EUSOLEX 8020.
  • the fabric treatment compositions disclosed herein may preferably further comprise a UVB sunscreen active that absorbs UV radiation having a wavelength of from about 290 nm to about 320 nm.
  • the compositions may preferably comprise an amount of the UVB sunscreen active that is safe and effective to provide UVB protection either independently, or in combination with, other UV protective actives that may be present in the compositions.
  • compositions preferably comprise from about 0.1% to about 16%, more preferably from about 0.1% to about 12%), and further preferably from about 0.5% to about 8%> by weight, of UVB absorbing organic sunscreen.
  • UVB sunscreen actives are suitable for use herein. Non-limiting examples of such organic sunscreen actives are described in U.S. Patent No 5,087,372 to Toyomot and U.S. Patent Nos. 5,073,371 and 5,073,372 both to Turner, et al., which are incorporated herein by reference.
  • Preferred UVB sunscreen actives are selected from 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (referred to as octocrylene), 2- phenyl-benzimidazole-5-sulphonic acid (PBSA), cinnamates and their derivatives such as 2- ethylhexyl-p-methoxycinnamate and octyl-p-methoxycinnamate, TEA salicylate, octyldi- methyl PAB A, camphor derivatives and their derivatives, and mixtures thereof.
  • octocrylene 2-ethylhexyl-2-cyano-3,3-diphenylacrylate
  • PBSA 2- phenyl-benzimidazole-5-sulphonic acid
  • cinnamates and their derivatives such as 2- ethylhexyl-p-methoxycinnamate and octyl-p-methoxyc
  • Preferred organic sunscreen actives include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (commonly named octocrylene), 2-phenyl-benzimidazole-5-sulphonic acid (PBSA), octyl-p-methoxycinnamate, and mixtures thereof. Salt and acid neutralized forms of the acidic sunscreens are also useful.
  • An agent may also be added to any of the compositions useful in the instant disclosure to stabilize the UVA sunscreen and to prevent it from photo-degrading on exposure to UW radiation and thereby maintaining its UVA protection efficacy.
  • Wide ranges of compounds have been cited as providing these stabilizing properties and should be chosen to compliment both the UVA sunscreen and the composition as a whole.
  • Suitable stabilizing agents include, but are not limited to, those described in U.S. Pat. No. 5,972,316 to Robinson; U.S. Pat. No. 5,968,485 to Robinson; U.S. Pat. No.5,935,556 to Tanner, et al. ; and U.S. Pat. 5,827,508 Tanner, et al., which are incorporated herein by reference.
  • Preferred examples of stabilizing agents for use herein include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (referred to as octocrylene), ethyl-2-cyano-3,3-diphenylacrylate,2-ethylhexyl-3,3-diphenylacrylate, ethyl-3,3-bis (4-methoxyphenyl)acrylate, and mixtures thereof.
  • Highly preferred materials of this class of antioxidants and sunscreen actives are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • compositions of the instant disclosure may preferably deposit from about
  • compositions disclosed herein can comprise from about 0.001% to about
  • compositions and formulations disclosed herein can contain ethoxylated amines, amphoterics, betaines, polymers such as polyvinylpyrrolidone, and other ingredients that inhibit dye transfer.
  • Optional dye fixing agents can be cationic, and based on quaternized nitrogen compounds or on nitrogen compounds having a strong cationic charge which is formed in situ under the conditions of usage.
  • Cationic fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) ex Crosfield; INDOSOL E- 50 (February 27, 1984, Ref. No. 6008.35.84; polyethyleneamine-based) ex Sandoz;
  • SANDOFIX TPS ex Sandoz
  • SANDOFIX SWE a cationic resinous compound
  • REWIN SRF REWIN SRF-0
  • REWIN DWR Crochet-Beitlich GMBH Tinofix ECO
  • Tinofix FRD Tinofix FRD
  • Solvent from Ciba-Geigy.
  • Other cationic dye fixing agents are described in "After treatments for Improving the Fastness of Dyes on Textile Fibres", Christopher C. Cook, Rev. Prog. Coloration, Vol. XH, (1982).
  • Dye fixing agents suitable for use with the fabric treatment compositions discussed herein include ammonium compounds such as fatty acid-diamine condensates, inter alia, the hydrochloride, acetate, methosulphate and benzyl hydrochloride salts of diamine esters.
  • ammonium compounds such as fatty acid-diamine condensates, inter alia, the hydrochloride, acetate, methosulphate and benzyl hydrochloride salts of diamine esters.
  • Non-limiting examples include oleyldiethyl aminoethylamide, oleylmethyl diethylenediamine methosulphate, and monostearylethylene diaminotrimethylammonium methosulphate.
  • N-oxides of tertiary amines are suitable for use as dye fixatives in the fabric treatment compositions of the instant disclosure.
  • discoloration such as graying or yellowing
  • the fabrics to which they are applied either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the fabric treatment compositions discussed herein may optionally comprise from about 0.01%, preferably from about 0.02%, more preferably from about 0.25% to about 15%), further preferably to about 10%, and yet more preferably to about 5% of a chlorine scavenger.
  • a chlorine scavenger In cases wherein the cation portion and the anion portion of the non-polymeric scavenger each react with chlorine, the amount of scavenger can be adjusted to fit the needs of the formulator.
  • Suitable chlorine scavengers include ammonium salts having the formula: [(R) RN]X wherein each R is independently hydrogen, C1-C4 alkyl, -C1-C4 substituted alkyl, and mixtures thereof; preferably R is hydrogen or methyl, more preferably hydrogen; R is hydrogen C1-C10 alkyl, C1-C10 substituted alkyl, and mixtures thereof.
  • R is hydrogen and X is a compatible anion.
  • Non-limiting examples include chloride, bromide, citrate, and sulfate; preferably X is chloride.
  • Non-limiting examples of preferred chlorine scavengers include ammonium chloride, ammonium sulfate, and mixtures thereof, preferably ammonium chloride.
  • Other chlorine scavengers include reducing agents such as thiosulfate.
  • Highly preferred materials of this class of chlorine scavengers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the compounds disclosed herein may contain from about 0.005% to about
  • Such wetting agents may be selected from polyhydroxy compounds.
  • water soluble polyhydroxy compounds that can be used as wetting agents in the fabric treatment compositions discussed herein include glycerol, polyglycerols having a weight-average molecular weight from about 150 to about 800, and poly oxy ethylene glycols and polyoxypropylene glycols having a weight-average molecular weight from about 200 to about 4000, preferably from about 200 to about 1000, and more preferably from about 200 to about 600.
  • Poly oxy ethylene glycols having a weight-average molecular weight from about 200 to about 600 are especially preferred.
  • Mixtures of the above-described polyhydroxy compounds may also be used.
  • a particularly preferred polyhydroxy compound is polyoxyethylene glycol having a weight- average molecular weight of about 400, available from Union Carbide Corporation under the trade name PEG-400.
  • Highly preferred materials of this class of wetting agents are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/ or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Suitable inorganic salts for use as an optional electrolyte in the present compo- sitions include Mgl 2 , 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 , Na 2 SO 3 , Na 2 SO 4 , NaNO 3 , Na 4 P 2 O 5 , sodium silicate, sodium metasilicate, sodium tetrachloroaluminate, sodium tripolyphosphate (STPP),
  • Na2S3O7, sodium zirconate CaF 2 , CaCl 2 , CaBr 2 , Cal 2 , CaSO 4 , Ca(NO 3 ) 2 , KI, KBr, KC1, KF, KNO 3 , KIO 3 , K 2 SO 4 , K 2 SO 3 , K 3 PO 4 , K 4 (P 2 O 7 ), potassium pyrosulfate, potassium pyrosulfite, Lil, LiBr, LiCl, LiF, LiNO 3 , A1F 3 , A1C1 3 , AlBr 3 , A1I 3 , A1 2 (SO 4 ) 3 , A1(PO 4 ), A1(NO 3 ) 3 , alu- minum silicate; including hydrates of these salts and including combinations of these salts or salts with mixed cations e.g.
  • potassium aluminum A1K(SO 4 ) 2 and salts with mixed anions e.g. potassium tetrachloroaluminate and sodium tetrafluoroaluminate.
  • Salts incorporating cations from groups Ilia, IVa, Va, Via, Vila, VIII, lb, and lib on the periodic chart with atomic numbers greater than 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 greater than 20 as well as salts with cations from the lanthanide 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.
  • quaternary ammonium salts quaternary alkyl ammonium salts, quaternary dialkyl ammonium salts, quaternary trialkyl ammonium salts and quaternary tetraalkyl ammonium salts wherein the alkyl substituent comprises a methyl, ethyl, propyl, butyl or higher C5-C12 linear alkane radical, or combinations thereof.
  • Organic salts useful herein 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, benzenedicarb oxylate, benzenetricarb oxylate.
  • Other useful organic salts include carbonate and/or hydrogen carbonate (HCO 3 "1 ) when the pH is suitable, alkyl and aromatic sulfates and sulfonates, e.g., sodium methyl sulfate, benzene sulfonates and derivatives such as xylene sulfonate, and amino acids when the pH is suitable.
  • 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.
  • 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 and organic electrolytes are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, rafter the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • 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 present compositions can be less than about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 2.5%, and further preferably from about 1 % to about 2% of the inventive composition.
  • Additional desirable adjuncts may be enzymes (although it may be preferred to also include an enzyme stabilizer), including, but not limited to hydrolases, hydroxylases, cellulases, peroxidases, laccases, mannases, amylases, lipases and proteases.
  • Proteases are one especially preferred class of enzymes. Typical examples of proteases include Maxatase and Maxacal from Genencor International, Alcalase, Savinase, and Esperase, all available from Novozymes North America, Inc. See also U.S. Pat. No. 4,511,490 to Stanislowski, et al., incorporated herein by reference.
  • amylases which are carbohydrate-hydrolyzing enzymes. It may also be preferred to include mixtures of amylases and proteases. Suitable amylases include Termamyl from Novozymes, North America Inc, and Maxamyl from Genencor International Co. Still other suitable enzymes are cellulases, such as those described in U.S. Pat. No. 4,479,881 to Tai; U.S. Pat. No. 4,443,355 to Murata, et al; U.S. Pat. No. 4,435,307 to Barbesgaard, et al; and U.S. Pat. No. 3,983,082 to Ohya, et al., incorporated herein by reference.
  • hydrolytic enzyme may be present in an amount of about 0. 01-5%, more preferably about 0.01-3%, and further preferably about 0.1-2%) by weight of the detergent. Mixtures of any of the foregoing hydrolases are desirable, especially protease/amylase blends.
  • Highly preferred materials of this class of enzymes are those that do not cause any significant residual odor or color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • BLEACHING AGENTS are those that do not cause any significant residual odor or color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the fabric treatment compositions of the instant disclosure may optionally comprise from about 0.01 %, preferably from about 0.02%, more preferably from about 0.25% to about 15%, further preferably to about 10%, and yet more preferably to about 5% of a bleaching agent.
  • Suitable bleaching agents include chlorine-releasing agents and peroxygen and peroxide-releasing compounds.
  • Alkali metal hypochlorites, including sodium or potassium hypochlorite, are preferred chlorine releasing agents.
  • Peroxygen compounds include alkali metal salts of percarbonate, perborate and peroxymonosulfate.
  • Peroxide compounds including hydrogen peroxide and compounds generating hydrogen peroxide in solution, peroxyacids and precursors to peroxyacids and peroxyimidic acids, and metal based oxidants are also suitable.
  • Suitable bleaching agents include preformed peracids and organic peroxides, including alkonyl and acyl peroxides such as tertiary butyl peroxide and benzoyl peroxide, and related alkonyl and acyl peroxide and superoxide derivatives of alkyls and arenes. Additionally, an appropriate bleach activator for the active oxygen source or peroxide may be present, such those found in Arbogast, et al., U.S. Pat. Nos.
  • Highly preferred materials of this class of bleaching agents are those that do not cause any significant fabric damage or color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Optical brighteners also referred to as fluorescent whitening agents or FWAs
  • FWAs fluorescent whitening agents
  • These fluorescent materials act by absorbing ultraviolet wavelength of light and emitting visible light, generally in the color blue wavelength ranges.
  • the FWAs settle out or deposit onto fabrics during the wash cycle. These include the stilbene, styrene, and naphthalene derivatives, which upon being impinged by ultraviolet light, emit or fluoresce light in the visible wavelength.
  • These FWAs or brighteners are useful for improving the appearance of fabrics, which have become dingy through repeated soilings and washings.
  • the FWAs are not be explicitly anionic but rather either nonionic; cationic; amphoteric; or neutralized, ion-paired moieties of anionic FWAs as described in Petrin, et at., U.S. Pat. No. 5,057,236.
  • Preferred anionic FWAs for ion-pairing according to Petrin, et al., '236 are Blankophor BBH, RKH and BHC, from Blankophor GmbH & Co. KG; and Tinopal 5BMX-C, CBS-X and RBS, from BASF.
  • Fluorescent whiteners most currently used in common laundry compositions generally fall into a category referred to in the art as diaminostilbene disulfonic acid-cyanuric chloride brighteners or DASC-brighteners. These compounds have the following general formula (I):
  • Examples of such DASC fluorescent whiteners include those sold by the Ciba- Geigy Corporation under the trade name "Tinopal", which are substituted stilbene 2,2'- disulfonic acid products, e.g., disodium 4,4'-bis-((4-anilino-6-inorpholino-l ,3,5 -triazin-2-yl) amino)stilbene-2,2' -disulfonate (sold as Tinopal AMS); disodium 4,4'-bis-(( 4-anilino-6-(N- 2-hydroxyethyl-N -methyl amino)- 1 ,3,5-triazm-2-yl)ammo)stilbene-2,2 , -disulfonate (sold as Tinopal 5BM); disodium 4,4'bis-((4-anilino-6-( bis (2-hydroxyethyl)amino)-l ,3,5-triazin-2- yl)
  • cationic, nonionic, and amphoteric FWAs such as those cited in U.S. Pat. Nos. 4,433,975, 4,432,886, 4,384,121, all to Meyer and U.S. Pat. No. 4,263,431 to Weber, et al, and incorporated herein by reference. Further examples of suitable FWAs are described in McCutcheon's Vol. 2: Functional Materials, North
  • Highly preferred materials of this class of brighteners are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the various components for the fabric treatment composition most preferred are those that do not cause any significant damage to treated fabrics or cause any significant color change, nor impart any discoloration, such as whitening, graying or yellowing, to the fabrics to which they are applied, either during treatment followed by curing and/or drying, or after the curing and/or drying step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • dye and colorants should not undergo any significant change from their original color and not stain or discolor the fabrics to which they are applied.
  • bleaching agents should also not interfere with the function of stain release and/or fabric treatment.
  • compositions of the present disclosure and/or products incorporating the compositions may be in any form known to those skilled in the art.
  • the compositions and/or products may be in the form of an aerosol, liquid, granular, powder, tablet, solid, paste, foam and/or bar compositional form, or their encapsulated or coated forms.
  • These compositions and/or products may be neat or releasably absorbed or adsorbed on to a substrate, such as a woven or non-woven filament substrate or packaged within a suitable article of manufacture for convenient handling and dispensing.
  • an article of manufacture comprises the inventive composition and a spray dispensing device, an aerosol dispensing device, a standard bottle, a device to release the composition into the rinse water, or a water soluble or water-insoluble sachet or package, or a water soluble or water-insoluble tablet or powder which enables release of the composition.
  • a suitable film coating or encapsulate may also be employed with either a liquid or solid form to provide for release of the composition.
  • the spray dispenser can be any of the manually activated means for producing a spray of liquid droplets as is known in the art, e.g., trigger-type, pump-type, electrostatic spray device, non-aerosol self-pressurized, and aerosol-type spray devices. Regardless of the specific spray means employed, it is preferred that at least about 70%, more preferably, at least about 80%, and further preferably at least about 90% of the droplets have a particle size smaller than about 200 microns. Generally in instances where the potential for inhalation by users may occur, it is most preferred that at least about 70%, more preferably, at least about 80%), and further preferably at least about 90% of the droplets have a particle size larger than about 5 microns.
  • the liquid composition can be divided in fine liquid droplets resulting in a spray that is directed onto the fabric surface to be treated.
  • Suitably fine droplet sizes are achieved in such spray-type dispensers owing to the mechanism of operation in which the composition contained in the body of the dispenser is directed through the spray-type dispenser bead via energy communicated to a pumping mechanism by the user as the composition is forced against an obstacle, such as a screen grid or a cone or the like, which provides sufficient shock to the stream of the ejected liquid composition to atomize the liquid composition and provide the formation of liquid droplets of sufficiently small size.
  • the aerosol-dispensing device of the instant disclosure can be any of the manually activated devices employing a pressurized propellant as known in the art.
  • the aerosol dispenser may comprise a container, which can be constructed of any of the conventional materials employed in fabricating aerosol containers.
  • the dispenser should be capable of withstanding internal pressure in the range of about 20 to about 120 psig, and preferably from about 20 to about 80 psig.
  • An important characteristic concerning the dispenser is that it be provided with a valve member, which can permit the fabric treatment composition disclosed herein 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 composition of the present disclosure can be dispensed through a special actuator/ valve assembly under pressure.
  • the aerosol dispenser is pressurized by incorporating therein a gaseous component generally known as a propellant.
  • a gaseous component generally known as a propellant.
  • gaseous hydrocarbons such as isobutane, mixed halogenated hydrocarbons, compressed air, nitrogen, inert gases, and carbon dioxide
  • Highly preferred are those propellants that do not present environmental concerns, such as compressed air, nitrogen, inert gases and carbon dioxide.
  • a more complete description of commercially available aerosol-spray dispensers appears in U.S. Pat. No. 3,436,772, to Stebbins and U.S. Pat. No. 3,600,325 to Kaufman, et al., which are incorporated herein by reference.
  • the spray dispenser can be a self-pressurized non-aerosol container having a convoluted liner and an elastomeric sleeve.
  • the self-pressurized dispenser can be comprised of an assembly containing a liner and a sleeve comprising a thin, flexible radially expandable convoluted plastic liner of about 0.010 (0.25 mm) to about 0.020 (0.50 mm) inch thick, inside an essentially cylindrical elastomeric sleeve.
  • the liner and sleeve assembly can be capable of holding a substantial quantity of the composition of the instant disclosure and of causing the product to be dispensed.
  • a description of such self-pressurized spray dispensers can be found in U.S. Pat.
  • Fabric treatment compositions such as those disclosed herein can be introduced into an automatic washing machine prior to or during the main wash cycle of the machine in any suitable form as described herein.
  • Some commercial washing machines provide a presoaking cycle into which compositions of the present disclosure can be introduced.
  • the presoaking or soaking cycle generally provides for treatment of clothing prior to introduction of a detergent or other additives prior to the main wash cycle.
  • the compositions disclosed herein may be employed alone as a sole treatment and may be employed in combination with other laundry additive products, such as liquid or powdered detergents, laundry additives or laundry booster products that are commonly in use.
  • the fabric treatment compositions disclosed herein can be introduced subsequent to a detergent using a delayed release packaging material or device or similar means.
  • Some commercial washing machines provide a means to automatically dispense an additive to the main wash water (the "wash liquor") after a short delay following the initiation of a wash cycle.
  • Other "drop in” dosing and dispensing devices known to the art can also be employed for releasing the inventive compositions into the main wash cycle.
  • Delayed release packaging can also be employed to hold and subsequently release the compositions of the present disclosure at a predetermined time during the wash cycle.
  • compositions disclosed herein When such delayed release packaging material is employed, it is desirable for the release of the compositions disclosed herein to be delayed in such a manner that sufficient time remains within the cycle time of the wash for the fabric treatment composition to act upon the clothing in order to provide effective treatment thereupon.
  • All of these approaches provide a means to treat articles, for example textiles, clothing, garments and the like, according to the methods disclosed herein.
  • Also suitable are methods in which articles are treated with the compositions and methods of the instant disclosure in an aqueous liquor, such as when washing by hand, washing in a tub, bucket or sink, as is commonly done with individual, so-called delicate articles and fine items of clothing and textiles that are not typically machine washed.
  • compositions can be formulated so as to assume the primary role of detergent in addition to imparting stain and soil resistance.
  • Such compositions are especially preferred, in that in practice the consumer needs to purchase and use only a single all-in-one product, which imparts cleaning, stain and soil resistance.
  • the composition used according to the methods disclosed herein would prefer- bly be formulated to include optional adjuncts such as surfactants, builders, fluorescent whitening agents, enzymes, and the like in appropriate levels to achieve the desired cleaning effect without having any effective impact on the hydrophobic agent, the zeta potential modifier or the optional fluoropolymer of the instant disclosure in regards to the inventive method for imparting stain and soil resistance to the desired materials.
  • Fabric treatment compositions of the instant disclosure can be introduced into an automatic washing machine during the rinse cycle of the machine using rinse water additive dispensers that are well known in the art. Examples include U.S. Pat. No. 5,768,918 to McKibben; U.S. Pat. No. 5,267,671 to Baginski, et al..; U.S. Pat. No. 4,835,804 to Arnau- Munoz, et al ; U.S. Pat. No. 3,888,391 to Merz; and U.S. Pat. No. 3, 108, 722 to Torongo, Jr., et al.
  • Centrifugal force applied to a weight inside the dispenser during a spin cycle of an automatic clothes washer can cause a dispenser valve to become unseated so that additive from the dispenser may spill out of the dispenser and mix with rinse water that is added to the washer after the spin cycle.
  • the dispenser can be normally inserted into the washer before the wash cycle begins. It should remain closed during the agitation of the wash cycle, yet reliably open during the first spin cycle at the conclusion of the wash cycle in order to deliver the composition of the instant disclosure at a point in time at which it will be most effective.
  • compositions of the present disclosure may be packaged in sachet form for convenient dosing and handling by the user.
  • the sachet may be of any suitable shape and construction. Highly convenient shapes from the viewpoints of both manufacture and packing are square and rectangular, but any other desired shape is also suitable.
  • Preferred sachets may contain one, two, or more compartments.
  • the compartments may, for example, be side-by-side, joined by a common seal, or back-to-back, joined by a common wall.
  • the former arrangement is more suitable if the two compartments are to be very different in size, and is also easier to make.
  • Other multi-compartment arrangements are disclosed in EP 236136A, which is incorporated herein by reference.
  • the relative sizes of a single or multi-compartment sachet can be tailored to match the proportions of the total contents to be accommodated in each, and the optimum shape of the sachet chosen accordingly.
  • a single compartment or first compartment of a two-compartment sachet can contain a relatively larger dosage of the composition of the current disclosure for first treatment purposes, while the second compartment of a two-compartment sachet can contain a relatively smaller dosage for second or subsequent treatments, e.g., maintenance treatment purposes.
  • the individual compartments of a two or multi-compartment sachet can be easily separated from one another by the user for dosage control when the contents comprise the same composition, enabling one, two or multiple compartments of the sachet to be used simultaneously, depending on the quantity of composition required.
  • the second compartment of a two-compartment sachet may also contain ingredients other than the fabric treatment compositions disclosed herein such as typical adjuncts, e.g., other non-interfering ingredients being packed together with the composition of the current disclosure to provide a secondary benefit.
  • the total amount of a composition of the current disclosure to be packaged in the sachet product may vary, for example, from 10 to 150 g for a half dose (20 to 300 g for a single dose), depending on the type and size of washing machine in which it is intended to be used, and the amount of fabric that is intended to be treated.
  • the sachet system be designed such that the contents will be released at or very shortly after the time of addition to the wash liquor or the rinse water (the "rinse liquor"), depending upon which cycle of the wash the sachet containing the composition is added.
  • substantially complete delivery of the contents is delayed to occur after at most 30 minutes, and more preferably at most 25 minutes from the time of addition to the wash liquor so that the contents of the sachet, which is introduced during the wash cycle of the washing machine, are not substantially released until at least the beginning of the rinse cycle of the washing machine.
  • the sachet systems may be designed such that at least one compartment or sachet thereof gives a delayed or controlled release of the contents.
  • Suitable sachet structures are described in EP236136A, Anderson, et al., which is incorporated herein by reference.
  • a water-insoluble sachet may be employed to hold the fabric treatment composition.
  • Such a water-insoluble sachet for delivery of the composition may be of the closed, water-permeable type that relies on leaching out by the wash liquor for release of its contents.
  • the sachet may be provided with a seal that will open under washing machine conditions, by the action of water or of mechanical agitation or both; for example, as disclosed in EP312277A, Newbold, et al, which is incorporated herein by reference.
  • Opening sachets may be of either water-permeable or water-impermeable material, with water-permeable material being preferred. Suitable materials include paper, woven and non-woven fabrics, films of natural or synthetic origin, or combinations thereof having a base weight between 1 and 100 g/m2.
  • EP246897A Newbold, et al., which is incorporated herein by reference, and include polyamide, polyester, polyacrylate, cellulose acetate, poly-ethylene, polyvinyl chloride, polypropylene, cellulosic fibers, regenerated cellulosic fibers, and mixtures thereof.
  • Preferred materials include cellulose/polyester mix fabrics, and Manila/viscose non-woven paper. It is especially preferred that the seals are composed of a water-labile component and a heat-sealable component, as described in the before referenced EP246897A.
  • sachet substrate itself to be one that dis-solves or disintegrates in the wash or rinse liquor.
  • sachets of water-soluble film are well-known in the art and include polyvinyl alcohols and partially hydrolyzed polyvinyl acetates, alginates, cellulose ethers such as carboxymethylcellulose and methyl cellulose, polyacrylates, polyethylene oxide, and combinations of these.
  • compositions including granular, powder and tablet forms of delivery, which may comprise the present composition and a suitable inert carrier in which the composition is reversibly compounded such that the composition can be effectively released to the water when the granular, powder or tablet delivery means is brought into contact with water, e.g., introduced into the wash water.
  • granular compositions in accordance with the present disclosure can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation. Tablets suitable for delivery of the fabric treatment compositions disclosed herein are well known in the art. Preferred are tablets of a size that are convenient for dosing in a washing machine.
  • a preferred size is from 5 g to 200 g, more preferably from 5 g to 100 g, and the size can be selected in accordance with the intended wash load and the design of the washing machine, which is to be used.
  • tablets containing two or more compositional zones in which one zone may comprise materials of the present disclosure and a second zone may comprise a carrier comprising, but not limited to, adjunct materials described herein as suitable optional additives.
  • fabric treatment compositions disclosed herein can be deposited onto fabrics by a number of methods. Regardless of the technique employed, the critical feature is that the hydrophobic agent and fluoropolymer become deposited on the fabric surface. Subsequent heating above ambient temperatures but below 100 °C, preferably below 70 °C, reversibly cures the composition onto the fabric. However, excessive heating above 100 °C is to be avoided, as the resulting coating is then bound to the fabric too tenaciously, leading to decreased overall performance of the coating. Without being bound by theory, it is believed that the coating should be reversibly bound to effect release of stains and soils during subsequent laundering of the fabric.
  • composition during home laundering of soiled garments in traditional home washing machines that have a 25 to 90 liter capacity when filled.
  • Such machines typically have a fill or wash cycle of about 12 to 18 minutes' duration, during which time the initial volume of water is added, followed by a rinse cycle of about 2 to 5 minutes, during which time sufficient water is added to disperse the soil, detergent, and any other laundry additives.
  • the rinse cycle is typically followed by a spin cycle of about 10 to 20 minutes.
  • the user of such traditional washing machines had the flexibility of using higher doses of the formulations described herein for larger loads, as well as pausing a cycle to allow for greater deposition of fabric-treatment actives. Between the wash, rinse and spin cycles, the introduced water is drained.
  • HE washers use less water than traditional washers.
  • HE washers typically only use from 20% to 66% of the water used by traditional agitator washers.
  • energy use can be as little as 20 to 50 % of the energy used by traditional agitator washers because there is much less water to heat.
  • the time of exposing the fabrics to compositions disclosed herein must be efficiently executed within a period of no more than 10 minutes, preferably less than 5 minutes, and most preferably less than 3 minutes.
  • the inventive fabric treatment composition preferably includes at least one zeta potential modifier.
  • a fabric treatment composition containing a fluoropolymer, hydrophobic agent, and zeta potential modifier is added to a fabric any time during the wash cycle, that is, the period in which a detergent is added during the overall laundering process.
  • the fabric treatment composition may be added whenever a fabric softener is added to the washing machine, as during a rinse cycle.
  • a laundry product may be formulated that includes a detergent in addition to the hydrophobic agent, fluoropolymer and zeta potential modifier of the instant fabric treatment compositions, to provide a method for imparting stain and soil resistance to a fabric.
  • a formulated product may also contain additional adjuncts such as surfactants, builders, fluorescent whitening agents, enzymes and the like. Such adjuncts should be selected such they have minimal impact on the active ingredients that impart fabric protective properties such as stain and soil resistance.
  • Such a formulated composition can be added during the initial fill/wash cycle of a washing machine in which the cleaning and protective methods discussed herein may be practiced. This method is especially preferred, as the consumer does not need to further intervene during the automated laundering process.
  • an effective amount of the fabric treatment compositions disclosed herein can be sprayed or applied directly onto fabrics, particularly clothing.
  • an effective amount that can be deposited onto the fabric without causing saturation of the fabric is typically from about 10 to about 85 weight %, preferably from about 15 to about 65 wt. %, and more preferably from about 20 to about 50 wt. % of the fabric.
  • the amount of active that can be typically sprayed or applied directly onto the fabric is from about 0.1 to about 4 weight %, preferably from about 0.2 to about 3 weight %, and more preferably from about 0.3 to about 2 weight % of the fabric.
  • a fabric treated with a fabric treatment composition described herein can be tumble-dried in a standard household clothes dryer and/or be ironed at normal ironing temperatures to effect curing of the fabric treatment composition onto the fabric. Inadvertent excessive curing or heating of a fabric that has been treated with the fabric treatment composition is to be avoided, especially where absorbency of the fabric is desired. Excessive heating of a treated fabric as during a drying or curing cycle could cause semi-permanent affixing of the treatment to the fabric. Accordingly, the temperature of the dryer should be set to a range of lower drying temperatures.
  • drying temperatures that should be use to effect curing of the inventive fabric treatment compositions are less than 150 °C, more preferably less than 125 °C, even more preferably less than 100 °C and most preferably less than 70 °C. For sensitive fabrics, drying temperatures less than about 70 °C are also preferred.
  • treated fabrics can be allowed to dry at ambient temperature, and the curing effected subsequently by a post-dry heating in a standard clothes dryer and/or by ironing at temperatures preferably less than 150 °C, more preferably less than 125 °C and even more preferably less than 100 °C, and most preferabl less than 70 °C.
  • the treated fabric can be subjected to radiant energy, such as from the sun, or infrared generating heat source, or exposure to microwave energy such as from a microwave dryer or microwave generating device, to effect curing of the applied fabric treatment composition.
  • radiant energy such as from the sun, or infrared generating heat source
  • microwave energy such as from a microwave dryer or microwave generating device
  • the treated fabric may simultaneously be dried and heated in one step to effect curing of the composition on the fabric, or these operations may optionally be conducted in sequence, providing that the heating step is performed subsequent to the drying step.
  • an effective amount of the composition can be aerosolized and applied onto fabrics, particularly clothing, by means of a clothes revitalizing device, such as the Whirlpool PERSONAL VALET system distributed by the Whirlpool Corporation of Benton Harbor, Michigan, or via a system that delivers a sprayed or aerosolized composition into the dryer itself.
  • a clothes revitalizing device such as the Whirlpool PERSONAL VALET system distributed by the Whirlpool Corporation of Benton Harbor, Michigan, or via a system that delivers a sprayed or aerosolized composition into the dryer itself.
  • the instant fabric treatment compositions can be combined with the revitalizing solution normally employed in the device, being combined in any desired ratio by volume, or substituted entirely in place of a revitalizing or other treatment solution in order to effect fabric treatment.
  • An effective amount of the composition can be automatically metered and aerosolized to cause its deposition onto the clothes or textiles contained within the devices.
  • a textile can also be soaked in an effective amount of fabric treatment composition and then washed before tumble drying, ironing or tumble-drying with optional ironing.
  • an acceptable method of delivery is to add the composition to a separate soak or treatment cycle performed in a washing machine or other suitable container with or without agitation, such as hand-soaking of fabrics performed in a sink, bucket or other such container, in which the composition of the present disclosure is added to water with sufficient agitation to uniformly mix the composition with the water to insure effective dispersal or dissolution of the composition to create a uniform dispersion or solution for subsequent treatment of the fabrics.
  • the order of mixing can be in any order, that is, the composition can be added to water to effect dilution or water can be added to the composition to effect dilution after the composition is first introduced into a washing machine or other suitable container. Either way, it is preferable that the composition is first admixed with water to effect dilution before fabrics are exposed to the diluted composition, in order to effect the most uniform treatment possible. Subsequent agitation of the fabrics in the diluted composition is not generally required, although if preformed in a washing machine, such agitation is generally provided during the wash cycle. Some newer washing machines, however, provide for a timed soaking cycle with no agitation or with intermittent agitation.
  • fabrics can be drained of excess fluid and then dried at a temperature less than 100 °C or optionally ironed at appropriate heat settings.
  • An available option is to rinse with fresh water and/or wash the soaked fabrics, followed by tumble drying below 100 °C, preferably below 70 °C, or optionally ironing at appropriate heat settings.
  • an effective amount of the composition can be added to the standard wash cycle of an automatic washing machine and/or tumble-dried with optional ironing. It is also a further option to add the fabric treatment compositions described herein to the standard wash cycle and optionally rinse the fabrics prior to drying at less than 100 °C, preferably less than 70 °C, with optional ironing. Accordingly, the fabric treatment compositions described herein may be combined with any laundry additive, a detergent, completely substitute the detergent, or additional surfactant and builders added to replace the detergent. In still another aspect, an effective amount of the composition can be added to the standard rinse or separate part of the rinse cycle and/or tumble-dried with optional ironing.
  • the fabric treatment composition may be combined with fabric softener or other rinse additive.
  • a variety of addition devices may also be used. Many washing machines contain additive dispensers for laundry additives such as bleach or fabric softener. Other devices are known in the art to add liquids to the wash cycle and/or to release them into the rinse cycle. In addition, water soluble pouches, nonwoven pouches, powders and tablets may be used.
  • Another method for using the fabric treatment compositions disclosed herein is to treat a non-woven and/or woven carrier article with the composition.
  • a further embodiment of this method is to add a fragrance to the carrier article. The carrier article is maintained in a moist state until added to the dryer with articles to be treated.
  • the carrier article remain moist to facilitate the transfer of the composition to the treated garments.
  • This method is especially effective on delicate articles including, but not limited to, silk, wool, linen where excessive heat may cause unwanted effects. Furthermore, this method allows for the economical treatment of limited article loads or those containing articles that should not be immersed or exposed to large volumes of liquid.
  • an effective amount can be present to effect deposition of the composition onto the fabric.
  • the effective amount for a first treatment operation performed on a previously untreated fabric is typically from about 0.01 % to about 10%, preferably from about 0.1 % to about 5%), and more preferably from about 0.1 % to about 2% of the composition to weight of the fabric present, wherein the ratio of the weight of dry fabric to the weight of water can be within a value between a ratio of 1 : 100 and 1 : 1, respectively, of the ratio of the dry fabric weight to water weight present.
  • a curing step is employed to complete treatment according to the methods of the present disclosure.
  • Suitable curing step includes drying the articles treated with fabric treatment compositions at a temperature above ambient, but less than about 100 °C, and preferably less than about 70 °C. Even lower temperatures, such as less than 60 °C and even less than 50 °C may also be used.
  • heated drying that is heating the article above ambient temperatures, by such means including, but not limited to ironing, steaming, blow drying, drying under a heat lamp, drying near a radiative source of heat, or machine drying in a dryer of the treated articles following treatment with compositions disclosed herein.
  • Curing may also be effected by drying, following by a heating step wherein the treated dried articles are subsequently heated above ambient temperature for a time sufficient to effect treatment according to the methods described herein.
  • a subsequent or further treatment of the fabric at a later time may be carried out by applying a second fabric treatment composition.
  • the dosage amount of the second fabric treatment composition may be less than, the same as or greater than the dosage amount that was used during the first treatment.
  • any one or several of the components of the second fabric treatment composition may differ in amount relative to the amount of the analogous component in the first fabric treatment composition. That is, at any time after an initial treatment event, it is possible to again treat a fabric at the first treatment level, at a higher level or a lower level.
  • the second fabric treatment composition may have varying amounts of components as compared to the amount of active components in a first fabric treatment composition. A smaller dosing of fabric treatment actives may be desirable in subsequent wash treatments following a first fabric treatment, for example, to replenish the total amount of fabric treatment composition on the fabric.
  • Some amount of a first fabric treatment composition that was initially deposited on a fabric may become lost due to wear or subsequent untreated washing of the fabric with the passage of time.
  • Replenishment of fabric protective properties on such a fabric by subsequently re-treating a fabric with a second fabric treatment composition is understood to refer to a maintenance level of the composition.
  • the amount of fabric treatment composition that is required to effectively treat a fabric in order to impart desirable fabric protective properties such as stain repellency, etc. will in general be greater for a first treatment than for fabrics that have previously been treated.
  • subsequent, repeated treatments may generally require significantly lower amounts of fabric treatment composition in order to effectively replenish a fabric treatment composition on the fabric and to maintain a desired level of repellency benefits.
  • Higher or lower, maintenance, levels of a fabric treatment composition may be used in subsequent wash treatments in order to maintain a consistent level of benefits.
  • subsequent laundering of the fabric can be carried out with amounts of fabric treatment composition to water that are typically from about 0.001 % to about 5%, preferably from about 0.01 % to about 2%, and more preferably from about 0.01 % to about 1 %, by weight of the composition to weight of the water present, wherein the ratio of the weight of dry fabric to the weight of water is preferably within a value between a ratio of 1 : 100 and 1 : 1, respectively, of the ratio of the dry fabric weight to water weight present.
  • an effective amount of the composition can be added to a standard tumble dryer, with optional ironing.
  • the composition may be used alone in any dryer delivery device, such as a nonwoven or sponge, or combined with fabric softener sheets, home dry cleaning devices, or other dryer device.
  • a fabric treatment composition such as a paste, suitable for coating onto, and delivery from, a substrate e.g. a flexible sheet or sponge or a suitable dispenser, such as a container having apertures therein, during a tumble dryer cycle.
  • a method for using the fabric treatment composition is to add or release the composition into the rinse water.
  • an effective amount of active of the composition disclosed herein may contain fabric softener actives, perfume, electrolytes, chlorine scavenging agents, dye transfer inhibiting agents, dye fixative 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.
  • textiles treated with the fabric treatment compositions described herein particularly delicate fabrics, fabrics composed of natural fibers including, but not limited to fur, wool or silks, fabrics comprising inclusions, panels, or mixed woven or non-woven compositions of heat sensitive natural or synthetic fibers including, but not limited to elastomeric materials such as rubber, SPANDEX, polyacetate, vinyl and nylon, may be so treated by any of the means described herein and allowed to dry under ambient conditions without the application of heat in order to prevent shrinking, dimensional distortion, wrinkling, creasing or other such deleterious effects that may be the result of applying heat to the wet textiles or heating the wet textiles sufficiently and for sufficient time to reduce them to an essentially dry state.
  • elastomeric materials such as rubber, SPANDEX, polyacetate, vinyl and nylon
  • such fabrics treated by the compositions disclosed herein and allowed to dry under ambient conditions may subsequently be exposed to a heat source to effect curing of the composition in order to obtain the full benefits of the treatment.
  • a heat source including, but not limited to heating in an automatic dryer, or contact with steam, an iron, heated air from a blow dryer or other heat source, will not suffer from the deleterious effects noted herein that are commonly seen when such delicate fabrics are dried by heating to dryness starting from a substantially wet state.
  • the time of exposure to a heat source required by textiles treated by the composition of disclosed herein and allowed to dry under ambient conditions may be substantially reduced compared to the time of exposure to a heat source required if such textiles treated with the composition are brought to dryness directly from a wet state.
  • Such reduced time of exposure to a heat source is beneficial to reduce any deleterious effects noted above for many textiles, particularly those labeled as delicate or dry-clean only textiles.
  • Drying is a function of both temperature and time. Effective drying can be achieved either by exposing treated garments to effectively higher drying temperatures for a shorter time, or exposing treated garments to effectively longer drying times with correspondingly lower drying temperatures. Preferred temperature and drying times are typically provided by selected cycles of commercially available automatic dryers under normal, permanent press and delicate cycle selections. Highly preferred are cycle selections that provide a short cooling down period with continued tumbling to provide for reduced wrinkling of tumbled fabrics, although this is not a requirement for treating fabrics with the compositions disclosed herein. Drying the fabric at a temperature above 45 °C is preferred.
  • compositions and articles of the present invention which contain a fabric improving active can be used to treat fabrics, garments, and the like to provide at least one of the following fabric care benefits: wrinkle removal and/or reduction, fabric wear reduction, fabric pilling reduction, fabric color fading reduction, fabric soiling reduction, fabric shape retention, and/or fabric shrinkage reduction.
  • the inventive composition can be applied by any of the above methods.
  • a first composition can be first applied at a high effective amount of the requisite actives to give untreated fabrics the beneficial properties.
  • Subsequent treatment of the same fabrics can be applied at a lower maintenance effective amount employing a second composition having requisite actives at a lower level, and therefore more economical usage benefit, but still effective at maintaining the beneficial protective properties provided to the treated fabrics in a first treatment step augmented by treatment in the second treatment step.
  • a kit consisting of the two treatment compositions as in the preceding embodiment may be employed, a first treatment composition with a first effective level of a hydrophobic agent, a fluoropolymer, and a zeta potential modifier, and optionally one or more additives; and a second treatment composition employed for subsequent and/or repeated treatment(s) to maintain the fabric protective properties provided in the first treatment step, where the second treatment composition has a second effective level of a hydrophobic agent, a fluoropolymer, a zeta potential modifier, and optionally one or more additives.
  • a kit having a first fabric treatment composition and a second fabric treatment composition is employed, the kit having a first protective fabric treatment consisting of an aqueous composition having: (a) about 5 to 10 weight % hydrophobic agent; (b) about 5 to 30 weight % fluoropolymer; (c) about 0.1 to 5 weight % zeta potential modifier; (d) optionally, about 0.01 to 10 weight % bleaching agent; (e) optionally, about 0.1 to 10 weight % surfactant; and (f) optionally, an additive; the kit also providing a second protective fabric treatment consisting of a second aqueous composition having (g) about 5 to 10 weight % hydrophobic agent; (h) about 5 to 30 weight% fluoropolymer; and (i) about 0.1 to 5 weight % zeta potential modifier; (j) optionally, 5 to 30 weight % of fluoropolymer; (k) optionally, about 0.01 to 10 weight % bleaching agent; (1)
  • the kit is employed in a first operation to first treat a fabric article, and then in a second operation to restore a fabric protective benefit provided by first use of the first fabric protective treatment.
  • the kit is employed in a first operation to first treat, and then in a second operation to maintain the first fabric protective treatment benefit by a second and/or subsequent series of second treatment steps employing the second treatment composition of the kit.
  • the second and/or subsequent series of second treatment operations may provide an enhanced or different second fabric benefit differing from the first fabric protective benefit provided in a first treatment operation.
  • a first treatment composition has a hydrophobic agent, a fluoropolymer, a zeta potential modifier and a compatible bleaching agent and surfactant to effect deep cleaning and stain removal of residue on a soiled fabric article during a first treatment operation, which provides a first fabric protective benefit having stain and soil release characteristics of reduced soiling; and in a second operation employing a second treatment composition, providing cleaning and maintenance of the protective benefit provided by the first treatment composition.
  • the kit includes instructions for use of the first and second compositions for treating fabrics according to the inventive methods described herein to deliver and maintain the desired fabric protective properties, including wrinkle removal and/or reduction, fabric wear reduction, fabric pilling reduction, fabric color fading reduction, fabric soiling reduction, fabric shape retention, and/or fabric shrinkage reduction.
  • concentrated compositions can be employed, and used as is or further diluted prior to use.
  • Concentrated compositions comprise a higher level of fabric active, typically from about 1 % to about 99%, preferably from about 2% to about 65%, and 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 can be used undiluted or diluted by about 1,000,000%), more preferably by about 25,000%), and even more preferably by about 5000%) of the composition, by addition by weight of water.
  • compositions can also be used as ironing aids.
  • An effective amount of the composition can be sprayed onto fabric and the fabric can be ironed at the normal ironing temperature recommended by the fabric label instruction guide.
  • the fabric can be sprayed with an effective amount of the composition, allowed to dry and then ironed, or sprayed and ironed immediately to effect curing.
  • the instant fabric treatment compositions 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 improving active 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 textiles.
  • One distribution of the treatment composition can be achieved using a fog form.
  • the mean particulate diameter size of the fabric care composition fog can be from about 5 microns to about 200 microns, preferably from about 5 microns to about 100 microns, and more preferably from about 10 microns to about 50 microns.
  • the wash or rinse water should contain typically from 0.01 to 1 g of fluoropolymer per liter of wash water and from 0.01 to 1 g of hydrophobic agent per liter of wash water.
  • the especially preferred levels of the inventive composition are from 0.01 to 0.5 g of fluoropolymer per liter of wash water and from 0.01 to 0.5 g of hydrophobic agent per liter of wash water. After treatment with an initial level of the composition, a maintenance level of present composition may be sufficient to maintain the properties.
  • Desirable maintenance levels of the inventive composition can be from 0.01 to 0.2 g of fluoropolymer per liter of wash water and from 0.01 to 0.2 g of hydrophobic agent per liter of wash water.
  • Especially preferred levels of the inventive composition might be from 0.01 to 0.1 g of fluoropolymer per liter of wash water and from 0.01 to 0.1 g of hydrophobic agent per liter of wash water.
  • the present disclosure also relates to a method for using an aqueous or solid, preferably powder or granular, composition to treat fabrics in a wash cycle, with such compositions comprising the fabric protecting actives, and optionally, surfactants, builders, perfume, chlorine scavenging agents, dye transfer inhibiting agents, dye fixative 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.
  • the present 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 be 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 disclosure also concerns a method for treating fabric in a home laundry drying step, comprising applying an effective amount of the fabric protecting actives of the present invention and, optionally, fabric softener actives, distributing agent, perfume, fiber lubricants, fabric shape retention polymers, lithium salts, potassium salts, phase stabilizers, chlorine scavenging agents, dye transfer inhibiting agents, dye fixative 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 present composition can take a variety of physical forms including liquid, foams, gel and solid forms such as solid particulate forms.
  • One method for treating a textile comprises treating a 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 method for imparting fabric protective properties to a textile comprises treating fabrics with a fabric protection composition that is dispensed from a sprayer at the beginning of and/or during a drying cycle. It is preferable that the treating step be performed in accordance with a set of instructions for use, to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • the set of instructions in combination with an amount of fabric treatment composition may together constitute a fabric treatment kit.
  • the present disclosure also relates to a fabric care method for dipping and/or soaking fabrics before the fabrics are laundered, with a pre-wash fabric care composition as discussed herein, that contains an effective amount of fabric protecting active and, optionally, surfactants, builders, perfume, chlorine scavenging agents, dye transfer inhibiting agents, dye fixative 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 be performed in accordance with instructions for use, to ensure that the consumer knows what benefits can be achieved, and how best to obtain these benefits.
  • compositions each having the same amounts of fluoropolymers and hydrophobic agent, but different amounts of zeta potential modifier (e.g., cationic surfactant in the form of a quaternary ammonium compound) were prepared.
  • the compositions were diluted using water to effective use levels equivalent to 5% by weight of the undiluted compositions.
  • the zeta potential of each composition was measured using two instruments, a Beckman Coulter DelsaTMNano C instrument and from Particle Sizing
  • a goniometer manufactured by Rame Hart, Inc. was used, having an illuminated specimen stage assembly and clamping system allowing a test fabric swatch to be positioned horizontally and clamped with sufficient tension to flatten the swatch to prevent sagging but without causing any substantial stretching or deformation of the swatch.
  • the goniometer has an integral eye piece having both horizontal axis line indicator and an adjustable rotating cross line indicator and angle scale, both independently adjustable by separate veniers.
  • test fabric swatch of approximate dimensions of 2.5 cm by 2.5 cm is clamped into place and the vertical venier adjusted to align the horizontal line (axis) of the eye piece coincident to the horizontal plane of the fabric swatch, and the horizontal position of the stage relative to the eye piece positioned so as to view one side of the test fluid droplet interface region at the swatch surface.
  • Test fabric swatches are preferably cut from larger test fabrics at a variety of randomly selected areas of the test fabric to provide multiple samples for testing.
  • approximately one drop of test fluid in an amount between about 0.010 and about 0.012 g is dispensed onto the swatch using a small syringe fitted with a stainless steel needle and a micrometer drive screw to displace a calibrated amount of the test fluid.
  • purified water either deionized or distilled
  • oil measurements such as soybean oil, available from Bunge North America, St. Louis, Missouri, is suitably employed.
  • the rotatable venier is adjustment to align the cross line and cross position, that is the intersection of the rotatable cross line and the fixed horizontal line, coincident with the edge of the test fluid droplet and the swatch, and the cross line angle (rotation) then positioned coincident with the tangent to the edge of the test droplet surface, as imaged by the eye piece.
  • the contact angle is then read from the angle scale, which is equivalent to the tangent angle.
  • Initial contact angles above 30 degrees are indicators of effective water or oil repellency. Also suitable are contact angles above 30 degrees that persist over relatively significant contact times, for example around 30 seconds to about 2 minutes. Higher initial contact angles of about 30 degrees and greater and persistent contact angles of about 30 degrees and greater are good indicators of effective water or oil repellency.
  • Cotton weave swatches also referred to as "flags" were treated with different concentrations of ZONYL 6700 for 12 min in 1500 grams of water at 25 °C in the Terg-O-Tometer, then squeezed and dried in the dryer for 40 min at 150 °F (65.5 °C). The 5% treatment of fluoropolymer solution is 5% as is based on the weight of cotton fabric in the treatment. This corresponds to a rinse cycle concentration of 1.23 grams per liter of rinse water. The contact angle was measured by putting a drop of water on the flags and measuring after 30 sec and 2 min.
  • the formulation containing no zeta potential modifier provided no repellency enhancement.
  • Optimum repellency occurred where the level of this particular zeta potential modifier was between 2-6%; the water repellency decreased when the zeta potential level reached 8% or higher which suggests that too much of the zeta potential modifier may have an adverse effect as well.
  • the pH of the compositions were carefully adjusted to 3.60 ⁇ 0.05 for these experiments to minimize experimental variations in the measurement of zeta potential measurement.
  • the compositions described herein may be adjusted to any desired pH as generally formulated for the intended usage and method of application desired for treating textiles and the like.
  • the suitable operating pH range includes from about pH 1 to about pH 13, although the pH may optimally be adjusted to some value within this range to accommodate the stability and functionality of any optional adjuncts, such as surfactants or enzymes, for example, that perform best at some selected pH.
  • the pH of the neat inventive composition ranged from 4.6-5.3;
  • the fabrics tested in each case included a combination comprising 70% cotton material and 30% of a cotton/synthetic blend, which is designated p/c.
  • the detergent when employed, was added in the wash cycle.
  • the treatment composition was added in the rinse cycle and, in one case, fabric softener, which included cationic surfactants, was also added in the rinse cycle.
  • compositions containing 6% zeta potential modifier performed well in terms of repellency in the absence of added washing detergent, but Sample Nos. 18a and 18b performed poorly when detergent was added in the wash cycle.
  • the same formulation exhibited good repellency performance when a fabric softener was added to the rinse cycle, as shown in Sample No. 18c, to increase the amount of cationic surfactant, i.e., zeta potential modifier.
  • the Extra Rinse option was selected: following the wash cycle, an intermediate rinse is effected with no added laundry product, followed by a final rinse containing the inventive treatment.
  • the detergent Liquid Tide
  • 100 mL of the inventive treatment was added to the fabric softener compartment of the laundry dispenser. The results are shown in Trial No. 3 in TABLE 6 below.
  • the foregoing examples demonstrate the manner in which the methods of the present disclosure provide for increased fabric protective benefits, including, but not limited to improved repellency against water and oil. It is further noted that the benefits with respect to improved repellency against water and oil also pertain to water-base, oil-based stains, respectively, and to particulate stains, and mixtures thereof. The foregoing examples further demonstrate the manner in which the methods of the present disclosure provide for improved hand-feel to treated fabrics. The foregoing examples also demonstrate the manner in which the methods disclosed herein provide improved fabric protective benefits without effectively reducing the breathability of treated fabrics with respect to water or moisture transmission.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)

Abstract

L'invention concerne une composition de traitement de tissu qui comprend au moins un modificateur du potentiel zêta, un fluoropolymère et un agent hydrophobe présentant un point de fusion ou une température de transition vitreuse inférieurs à 100 °C, pour conférer des avantages de protection de tissu à un tissu, notamment une meilleure résistance aux taches et aux salissures, un caractère oléofuge, un caractère hydrofuge, une souplesse, une résistance aux plis et aux dommages, et une meilleure sensation au toucher. Les compositions de traitement de tissu peuvent être utilisées en tant que prétraitement avant le lavage, par le biais d'un trempage, ou ajoutées à la lessive de traitement, à savoir, soit le cycle de lavage, soit celui de rinçage d'une machine à laver automatique, pour fournir d'abord puis conserver et renouveler les avantages de protection de tissu conférés à ce tissu, à condition qu'une étape de rinçage intermédiaire sensiblement exempte d'agent tensioactif soit utilisée après le cycle de lavage et avant l'étape de traitement de tissu. Après l'utilisation d'une première composition de traitement, des avantages de protection sont conservés et renouvelés au moyen d'une seconde opération de traitement mettant en œuvre une seconde composition de traitement. La seconde composition de traitement peut présenter des niveaux actifs inférieurs des agents de protection afin de pouvoir conserver et renouveler de façon économique et périodique les avantages de protection du tissu.
EP16737925.4A 2015-01-14 2016-01-14 Procédé de traitement de tissu amélioré pour l'élimination des taches Withdrawn EP3247833A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201562103192P 2015-01-14 2015-01-14
US14/716,871 US10577743B2 (en) 2002-04-09 2015-05-19 Laundry additive for providing antimicrobial effects to fabrics and interior surfaces of washing machine
PCT/US2016/013493 WO2016115408A1 (fr) 2015-01-14 2016-01-14 Procédé de traitement de tissu amélioré pour l'élimination des taches

Publications (2)

Publication Number Publication Date
EP3247833A1 true EP3247833A1 (fr) 2017-11-29
EP3247833A4 EP3247833A4 (fr) 2018-09-19

Family

ID=56406417

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16737925.4A Withdrawn EP3247833A4 (fr) 2015-01-14 2016-01-14 Procédé de traitement de tissu amélioré pour l'élimination des taches

Country Status (5)

Country Link
EP (1) EP3247833A4 (fr)
JP (2) JP2018505320A (fr)
KR (1) KR20170105074A (fr)
AU (1) AU2016206650A1 (fr)
WO (1) WO2016115408A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10822577B2 (en) 2002-04-09 2020-11-03 Gregory van Buskirk Fabric treatment method for stain release
IT201600094671A1 (it) 2016-09-21 2018-03-21 Bolton Manitoba S P A Metodo ottimizzato di lavaggio in lavatrice
JP6991081B2 (ja) * 2018-03-14 2022-01-12 第一工業製薬株式会社 水溶性袋体を用いた洗濯方法
GB2595918A (en) * 2020-06-11 2021-12-15 Reckitt & Colman Overseas Hygiene Home Ltd Novel composition
CN114606071B (zh) * 2022-03-15 2023-11-24 广州立白企业集团有限公司 一种漂洗剂组合物及其应用

Family Cites Families (142)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US715A (en) 1838-04-28 Improvement in water-wheels
US2702279A (en) 1955-02-15 Detergent compositions having
US989A (en) 1838-10-26 Smith cram
US3645A (en) 1844-07-01 Method of securing boring-machines to the article to be bored
US3923A (en) 1845-02-24 Mode of preventing the explosion oe steam-boilebs
US2082275A (en) 1934-04-26 1937-06-01 Gen Aniline Works Inc Substituted betaines
US2255082A (en) 1938-01-17 1941-09-09 Gen Aniline & Film Corp Capillary active compounds and process of preparing them
US2879238A (en) 1955-03-10 1959-03-24 Petrolite Corp Process of oxidizing mixture of microcrystalline wax, monocarboxylated polyethylene and polyethylene, and product produced thereby
US2879240A (en) 1955-03-10 1959-03-24 Petrolite Corp Process of oxidizing mixture of microcrystalline wax, an ester of hydroxylated polyethylene and polyethylene, and product produced thereby
US2879237A (en) 1955-03-10 1959-03-24 Petrolite Corp Process of oxidizing mixture of microcrystalline wax, hydroxylated polyethylene and polyethylene, and product produced thereby
US2879241A (en) 1955-03-10 1959-03-24 Petrolite Corp Process of oxidizing mixture of microcrystalline wax, an ester of monocarboxylated polyethylene and polyethylene, and product produced thereby
US2879239A (en) 1955-03-10 1959-03-24 Petrolite Corp Process of oxidizing mixture of microcrystalline wax and two polyethylenes of different molecular weight, and product produced thereby
US3163548A (en) 1961-05-22 1964-12-29 Petrolite Corp Carbon paper ink containing an isocyanate modified, amine treated, oxidized non-benzenoid hydrocarbon wax
US3108722A (en) 1961-09-19 1963-10-29 Procter & Gamble Dispenser for fabric softener
US3951960A (en) 1966-02-10 1976-04-20 Sterling Drug Inc. Novel crystalline forms of optical brighteners
US3436772A (en) 1966-10-14 1969-04-08 David T Stebbins Method for relaxing wrinkles in fabrics
CH554848A (de) 1967-10-03 1974-10-15 Ciba Geigy Ag Verfahren zur herstellung neuer stilben-derivate.
CH508692A (de) 1968-01-15 1971-06-15 Ciba Geigy Ag Verwendung von Styryl-naphthalin-Derivaten als optische Aufhellmittel ausserhalb der Textilindustrie
US3600325A (en) 1968-07-02 1971-08-17 Cpc International Inc Aerosol fabric de-wrinkler
US3645990A (en) 1970-01-29 1972-02-29 Du Pont Fluorinated oil- and water-repellent and dry soil resistant polymers
US3933511A (en) 1970-08-17 1976-01-20 Petrolite Corporation Polishes containing wax-anhydride compounds
US3933512A (en) 1970-08-17 1976-01-20 Petrolite Corporation Carbon paper inks containing wax-anhydride compounds
US3993659A (en) 1971-08-10 1976-11-23 Ciba-Geigy Corporation Bis-benzoxazolyl-naphthalenes as optical brighteners
JPS5510633B2 (fr) 1972-05-19 1980-03-18
CH583668A5 (fr) 1972-06-30 1977-01-14 Ciba Geigy Ag
US3954632A (en) 1973-02-16 1976-05-04 The Procter & Gamble Company Softening additive and detergent composition
US3861870A (en) 1973-05-04 1975-01-21 Procter & Gamble Fabric softening compositions containing water-insoluble particulate material and method
US4027062A (en) 1973-06-18 1977-05-31 Kellwood Company Composition and method for imparting fire resistance and water repellency to fabric
US3950277A (en) 1973-07-25 1976-04-13 The Procter & Gamble Company Laundry pre-soak compositions
LU68901A1 (fr) 1973-11-30 1975-08-20
US3974076A (en) 1974-01-11 1976-08-10 The Procter & Gamble Company Fabric softener
US4022938A (en) 1974-04-16 1977-05-10 The Procter & Gamble Company Fabric treatment compositions
US3888391A (en) 1974-09-12 1975-06-10 Procter & Gamble Dispenser for rinse-water additive
US4004932A (en) 1974-12-20 1977-01-25 Petrolite Corporation Isocyanated polyvalent metal salts of oxidized waxes
US4018569A (en) 1975-02-13 1977-04-19 General Electric Company Metal of improved environmental resistance
US3983082A (en) 1975-02-19 1976-09-28 General Electric Company Intumescent fire retardant material and article
US4045361A (en) 1975-05-21 1977-08-30 The Procter & Gamble Company Fabric conditioning compositions
US4029585A (en) 1975-07-26 1977-06-14 E. I. Du Pont De Nemours And Company Aqueous dispersions of perfluoroalkyl esters for treating textiles
US4161288A (en) 1976-10-05 1979-07-17 Creative Dispensing Systems, Inc. Fluid dispenser method and apparatus
US4260110A (en) 1977-02-18 1981-04-07 Winfried Werding Spray nozzle, devices containing the same and apparatus for making such devices
US4237016A (en) 1977-11-21 1980-12-02 The Procter & Gamble Company Textile conditioning compositions with low content of cationic materials
CH634077A5 (de) 1978-05-29 1983-01-14 Ciba Geigy Ag Kationische aufheller.
US4364845A (en) 1978-07-17 1982-12-21 Ciba-Geigy Corporation Concentrated aqueous solutions of sulfo group-containing fluorescent brighteners which are stable on storage
DE2928052A1 (de) 1978-07-17 1980-01-31 Ciba Geigy Ag Stabile stilbenaufhellerloesungen
NL190101C (nl) 1978-11-13 1993-11-01 Givaudan & Cie Sa Dibenzoylmethaanverbinding en tegen licht beschermend preparaat.
ATE4334T1 (de) 1979-01-11 1983-08-15 The Procter & Gamble Company Konzentrierte textilweichmachungszusammensetzung.
US4233164A (en) 1979-06-05 1980-11-11 The Proctor & Gamble Company Liquid fabric softener
EP0029003B1 (fr) 1979-11-01 1984-12-05 Ciba-Geigy Ag Sels d'agents de blanchiment optique cationiques, leur préparation et leur utilisation sur des matières organiques ainsi que leurs solutions aqueuses concentrées
DK187280A (da) 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
US4308151A (en) 1980-05-12 1981-12-29 The Procter & Gamble Company Detergent-compatible fabric softening and antistatic compositions
GB2076011A (en) 1980-05-19 1981-11-25 Procter & Gamble Coated white diphenyl and stilbene fabric brighteners
US4298290A (en) 1980-06-16 1981-11-03 International Business Machines Corporation System and printer justification system
US4434917A (en) 1981-05-26 1984-03-06 Yoshino Kogyosho Co., Ltd. Trigger-actuated atomizer
US4439335A (en) 1981-11-17 1984-03-27 The Procter & Gamble Company Concentrated fabric softening compositions
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
JPS591598A (ja) 1982-06-25 1984-01-06 花王株式会社 洗浄剤組成物
US4558821A (en) 1983-03-03 1985-12-17 Canyon Corporation Trigger-type sprayer with integrally formed housing, trigger, nozzle and cylinder
GB8306645D0 (en) 1983-03-10 1983-04-13 Unilever Plc Detergent compositions
US4511490A (en) 1983-06-27 1985-04-16 The Clorox Company Cooperative enzymes comprising alkaline or mixtures of alkaline and neutral proteases without stabilizers
DE3568455D1 (en) 1984-05-23 1989-04-06 Rhone Poulenc Chimie Detergent compositions containing copolymers based on polyoxyethylene and polyoxyalkylene used as antisoil redeposition agents, and process for their preparation
US4958039A (en) 1984-08-24 1990-09-18 E. I. Du Pont De Nemours And Company Modified fluorocarbonylimino biurets
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
GB2170403B (en) 1984-12-24 1989-08-09 Wakamoto Pharma Co Ltd Medicament for treatment of asthma and preparation thereof
US4808086A (en) 1985-03-06 1989-02-28 The Procter & Gamble Company Articles and methods for treating fabrics
US4661269A (en) 1985-03-28 1987-04-28 The Procter & Gamble Company Liquid fabric softener
GB8514707D0 (en) 1985-06-11 1985-07-10 Unilever Plc Enzymatic detergent composition
US4900468A (en) 1985-06-17 1990-02-13 The Clorox Company Stabilized liquid hydrogen peroxide bleach compositions
US4749596A (en) 1985-08-22 1988-06-07 The Procter & Gamble Company Articles and methods for treating fabrics
GB8605734D0 (en) 1986-03-07 1986-04-16 Unilever Plc Dispensing treatment agents
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
US4713194A (en) 1986-04-15 1987-12-15 The Procter & Gamble Company Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions
GB8612706D0 (en) 1986-05-23 1986-07-02 Unilever Plc Sealable container
US5296161A (en) 1986-06-09 1994-03-22 The Clorox Company Enzymatic perhydrolysis system and method of use for bleaching
US5030240A (en) 1986-06-09 1991-07-09 The Clorox Company Enzymatic peracid bleaching system
EP0254505B1 (fr) 1986-07-21 1992-04-22 Yoshino Kogyosho Co., Ltd. Distributeur de liquide du type à gâchette
US5002691A (en) 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5112514A (en) 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
US4959187A (en) 1986-11-06 1990-09-25 The Clorox Company Glycolate ester peracid precursors
US5108457A (en) 1986-11-19 1992-04-28 The Clorox Company Enzymatic peracid bleaching system with modified enzyme
US4756850A (en) 1987-06-10 1988-07-12 The Procter & Gamble Company Articles and methods for treating fabrics
US4877896A (en) 1987-10-05 1989-10-31 The Procter & Gamble Company Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
GB8724025D0 (en) 1987-10-13 1987-11-18 Unilever Plc Sealable sachets
US5130044A (en) 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US5234616A (en) 1987-10-30 1993-08-10 The Clorox Company Method of laundering clothes using a delayed onset active oxygen bleach composition
US5130045A (en) 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
DE3737753A1 (de) 1987-11-06 1989-06-15 Pfersee Chem Fab Waessriges ausruestungsmittel und verfahren zur weichen hydrophob/oleophob-behandlung von fasermaterialien
US4849257A (en) 1987-12-01 1989-07-18 The Procter & Gamble Company Articles and methods for treating fabrics in dryer
US4833006A (en) 1988-02-08 1989-05-23 Graniteville Company Flake proof fabric
US4835804A (en) 1988-03-25 1989-06-06 The Procter & Gamble Company Multiple compartment container laundering method
US5269962A (en) 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
DE3842571A1 (de) 1988-12-17 1990-06-21 Pfersee Chem Fab Hydrophile weichgriffmittel fuer faserige materialien und deren verwendung
US5087372A (en) 1989-03-24 1992-02-11 Asahi Kasei Kogyo Kabushiki Kaisha Method for removing heavy metal ions from contaminated water and a porous membrane usable therefor
US4920000A (en) 1989-04-28 1990-04-24 E. I. Du Pont De Nemours And Company Blend of cotton, nylon and heat-resistant fibers
US4956447A (en) 1989-05-19 1990-09-11 The Procter & Gamble Company Rinse-added fabric conditioning compositions containing fabric sofening agents and cationic polyester soil release polymers and preferred cationic soil release polymers therefor
US5111971A (en) 1989-05-26 1992-05-12 Robert Winer Self-pressurized container having a convoluted liner and an elastomeric sleeve
US5232126A (en) 1989-05-26 1993-08-03 Robert Winer Liner for dispensing container
US5153046A (en) 1990-05-24 1992-10-06 E. I. Du Pont De Nemours And Company Fluorochemical composition for imparting antisoiling protection and lubricity to textile fibers
US5057236A (en) 1990-06-20 1991-10-15 The Clorox Company Surfactant ion pair fluorescent whitener compositions
JPH0759792B2 (ja) 1990-08-22 1995-06-28 花王株式会社 柔軟仕上剤
US5073371A (en) 1990-11-30 1991-12-17 Richardson-Vicks, Inc. Leave-on facial emulsion compositions
US5073372A (en) 1990-11-30 1991-12-17 Richardson-Vicks, Inc. Leave-on facial emulsion compositions
GB9301728D0 (en) 1993-01-28 1993-03-17 Unilever Plc Fabric softening composition
US5267671A (en) 1992-03-16 1993-12-07 The Procter & Gamble Company Apparatus for dispensing rinse water additive in an automatic washing machine
AU4227393A (en) 1992-05-12 1993-12-13 Procter & Gamble Company, The Concentrated fabric softener compositions containing biodegradable fabric softeners
JP2989717B2 (ja) * 1992-10-06 1999-12-13 花王株式会社 衣料用柔軟仕上剤
DE59408909D1 (de) 1993-10-13 1999-12-16 Ciba Sc Holding Ag Neue Fluoreszenzfarbstoffe
DE69510453T2 (de) 1994-04-25 2000-01-13 Procter & Gamble Stabiles wässriges waschmittel mit verbesserten weichmachereigenschaften
GB9409465D0 (en) 1994-05-12 1994-06-29 Ciba Geigy Ag Protective use
MA23554A1 (fr) 1994-05-18 1995-12-31 Procter & Gamble Compositions assouplissantes pour le linge a base d'ammonium quaternaire biodegradables et concentrees contenant des composes ammonium quaternaire avec des chaines alkyle d'acide gras courtes
AU3008695A (en) 1994-07-26 1996-02-22 Procter & Gamble Company, The Rinse added fabric softener compositions containing antioxidants for sun-fade protection for fabrics
US5532023A (en) 1994-11-10 1996-07-02 The Procter & Gamble Company Wrinkle reducing composition
US5474690A (en) 1994-11-14 1995-12-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains
US5739327A (en) 1995-06-07 1998-04-14 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5814242A (en) 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
US5888419A (en) 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
WO1997044375A1 (fr) 1996-05-17 1997-11-27 Minnesota Mining And Manufacturing Company Composes fluores de polyurethane permettant d'obtenir une bonne performance apres lavage ou nettoyage a sec
US6251210B1 (en) 1996-08-07 2001-06-26 Hi-Tex, Inc. Treated textile fabric
US5827508A (en) 1996-09-27 1998-10-27 The Procter & Gamble Company Stable photoprotective compositions
JP4024366B2 (ja) * 1996-11-29 2007-12-19 株式会社林原生物化学研究所 ポリペプチド
BR9701287A (pt) 1997-03-14 1998-11-10 Unilever Nv Composição de tratamento de tecidos na lavagem e processo para tratar tecidos para proporcionar aos mesmos propriedades de repelência à sujeira
US5768918A (en) 1997-04-07 1998-06-23 The Procter & Gamble Company Rinse water additive dispenser
DE19732109A1 (de) 1997-07-25 1999-01-28 Clariant Gmbh Mischungen von optischen Aufhellern
GB9718081D0 (en) 1997-08-28 1997-10-29 Ciba Geigy Ag Fluorescent whitening agent
US6180740B1 (en) 1998-02-27 2001-01-30 E. I. Du Pont De Nemours And Company Stabilization of fluorochemical copolymer emulsions
CA2324377A1 (fr) 1998-03-24 1999-09-30 David A. Offord Tissus et autres matieres modifiees, procedes d'obtention
US5945493A (en) 1998-06-19 1999-08-31 E. I. Du Pont De Nemours And Company Fluorine-containing maleic acid terpolymer soil and stain resists
US5935556A (en) 1998-07-30 1999-08-10 The Procter & Gamble Company Sunscreen compositions
US6251303B1 (en) 1998-09-18 2001-06-26 Massachusetts Institute Of Technology Water-soluble fluorescent nanocrystals
US5972316A (en) 1998-10-16 1999-10-26 The Procter & Gamble Company UV protection compositions
US5968485A (en) 1998-10-16 1999-10-19 The Procter & Gamble Company UV protection compositions
US6162869A (en) 1999-06-22 2000-12-19 Eastman Chemical Company Waterborne acrylic polymers containing polymeric fluorescent compounds
GB2378960A (en) * 2001-08-22 2003-02-26 Unilever Plc Fabric care composition
DE10164262A1 (de) 2001-12-27 2003-07-17 Bayer Ag Zusammensetzung für das chemisch-mechanische Polieren von Metall- und Metall/Dielektrikastrukturen
US20030192130A1 (en) * 2002-04-09 2003-10-16 Kaaret Thomas Walter Fabric treatment for stain release
US20050204477A1 (en) * 2004-03-22 2005-09-22 Casella Victor M Fabric treatment for stain release
US7893014B2 (en) * 2006-12-21 2011-02-22 Gregory Van Buskirk Fabric treatment for stain release
US20050229327A1 (en) * 2004-04-20 2005-10-20 Casella Victor M Fabric treatment for stain release
WO2008152602A1 (fr) * 2007-06-15 2008-12-18 Ecolab Inc. Composition liquide de conditionnement de tissus et son utilisation
JP5281257B2 (ja) * 2007-08-29 2013-09-04 花王株式会社 洗濯方法
US8097047B2 (en) * 2008-04-02 2012-01-17 The Procter & Gamble Company Fabric color rejuvenation composition
US8492325B2 (en) * 2010-03-01 2013-07-23 The Procter & Gamble Company Dual-usage liquid laundry detergents comprising a silicone anti-foam
EP2758503A2 (fr) * 2011-09-20 2014-07-30 The Procter and Gamble Company Compositions détergentes comprenant des rapports de mélange spécifiques d'agents tensio-actifs à base d'isoprénoïde

Also Published As

Publication number Publication date
WO2016115408A1 (fr) 2016-07-21
JP2021073386A (ja) 2021-05-13
JP2018505320A (ja) 2018-02-22
KR20170105074A (ko) 2017-09-18
AU2016206650A1 (en) 2017-08-10
EP3247833A4 (fr) 2018-09-19

Similar Documents

Publication Publication Date Title
US7893014B2 (en) Fabric treatment for stain release
US20070256252A1 (en) Fabric Treatment for Stain Release
US20050166333A1 (en) Fabric treatment for stain release
US20050229327A1 (en) Fabric treatment for stain release
US10577743B2 (en) Laundry additive for providing antimicrobial effects to fabrics and interior surfaces of washing machine
JP2021073386A (ja) しみ抜きのための改善された布地の処理方法
AU2008263396B2 (en) Liquid fabric conditioner composition and method of use
EP3158040A1 (fr) Procédé d'utilisation de composition comprenant un composé d'ammonium quaternaire, un polysaccharide cationique et un polysaccharide non ionique
CA3042725C (fr) Compositions de traitement de textile ayant des polymeres et des agents actifs assouplissants pour textile et procedes procurant un benefice
US20180079993A1 (en) Composition comprising a quaternary ammonium compound, a cationic polysaccharide and a nonionic polymer
US11834631B2 (en) Fabric treatment compositions having low calculated cationic charge density polymers and fabric softening actives and methods for providing a benefit
MXPA02004209A (es) Composicion resistente a las arrugas.
US20190010424A1 (en) Compositions comprising quat and polysaccharides
US20210115357A1 (en) Fabric Treatment Method for Stain Release
CA2390106C (fr) Ameliorations apportees au defroissement de textiles
MXPA02004210A (es) Composicion contra las arrugas.
US10822577B2 (en) Fabric treatment method for stain release
US10900168B2 (en) Fabric treatment for stain repellency

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170814

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20180821

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 11/00 20060101ALI20180814BHEP

Ipc: C11D 3/37 20060101ALI20180814BHEP

Ipc: C11D 3/16 20060101ALI20180814BHEP

Ipc: D06F 35/00 20060101AFI20180814BHEP

Ipc: C11D 1/38 20060101ALI20180814BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20200421

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230301