WO2005003439A1 - Surfactant system for use in a lipophilic fluid - Google Patents

Surfactant system for use in a lipophilic fluid Download PDF

Info

Publication number
WO2005003439A1
WO2005003439A1 PCT/US2004/020879 US2004020879W WO2005003439A1 WO 2005003439 A1 WO2005003439 A1 WO 2005003439A1 US 2004020879 W US2004020879 W US 2004020879W WO 2005003439 A1 WO2005003439 A1 WO 2005003439A1
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
detergent composition
formula
fatty acid
mixtures
Prior art date
Application number
PCT/US2004/020879
Other languages
French (fr)
Inventor
Donna Jean Haeggberg
John Christian Haught
Kelli Alison Fleisch
William Michael Scheper
Keith Homer Baker
Robb Richard Gardner
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP04756350A priority Critical patent/EP1639187A1/en
Priority to CA002525511A priority patent/CA2525511A1/en
Priority to BRPI0411899-5A priority patent/BRPI0411899A/en
Priority to MXPA05013669A priority patent/MXPA05013669A/en
Priority to AU2004254609A priority patent/AU2004254609A1/en
Publication of WO2005003439A1 publication Critical patent/WO2005003439A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3734Cyclic silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/82Compounds containing silicon
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86Mixtures of anionic, cationic, and non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/162Organic compounds containing Si
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738Alkoxylated silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742Nitrogen containing silicones
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
    • D06L1/04Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds

Definitions

  • the present invention relates to a surfactant system and a consumable detergent composition comprising the same.
  • Background of the Invention A non-aqueous solvent based washing system utilizing lipophilic fluid, such as cyclic siloxanes (especially cyclopentasiloxanes, sometimes termed "D5"), particularly for use with washing machines for in-home use, has recently been developed.
  • lipophilic fluid such as cyclic siloxanes (especially cyclopentasiloxanes, sometimes termed "D5")
  • Such a system is particularly desired for cleaning textile articles without causing damage associated with wet-washing, like shrinkage and dye transfer.
  • To maximize fabric cleaning in such a system it is necessary to use additives for cleaning, softening, finishing, and other similar benefits.
  • the present invention relates to a surfactant system for use in a lipophilic liquid comprising at least two surfactants selected from the group comprising of from about 0.1 wt% to about 30 wt% of a silicone surfactant; from about 0.1 wt% to about 99 wt% of a nonionic surfactant; from about 0 wt% to about 50 wt% of a gemini surfactant; and from about 0 wt% to about 50 wt% of a anionic surfactant.
  • the present invention also relates to a consumable detergent composition for use in a lipophilic fluid comprising: a) from about 1 wt% to about 100 wt% of a surfactant system comprising at least two surfactants consisting of from about 0.1 wt% to about 75 wt% of a silicone surfactant; from about 0.1 wt% to about 99 wt% of a nonionic surfactant; from about 0 wt% to about 40 wt% of a gemini surfactant; from about 0 wt% to about 75 wt% of a anionic surfactant; and b) from about 0 wt% to about 75 wt% of a fatty acid, fatty acid salt and mixtures thereof; c) from about 0 wt% to about 75 wt% of a fatty quat comprising a nitrogen substituted by at least one hydrophobic tail comprising from 2 to 20 carbon atoms; and d) from about 0 wt%
  • fabric article used herein is intended to mean any article that is customarily cleaned in a conventional laundry process or in a dry cleaning process. As such, the term encompasses articles of clothing, linen, drapery, and clothing accessories. The term also encompasses other items made in whole or in part of fabric, such as tote bags, furniture covers, tarpaulins and the like.
  • lipophilic fluid used herein is intended to mean any nonaqueous fluid capable of removing sebum, as described in more detail herein below.
  • soil means any undesirable substance on a fabric article that is desired to be removed.
  • water-based soils it is meant that the soil comprised water at the time it first came in contact with the fabric article, that the soil has high water solubility or affinity, or the soil retains a significant portion of water on the fabric article.
  • water-based soils include, but are not limited to beverages, many food soils, water soluble dyes, bodily fluids such as sweat, urine or blood, outdoor soils such as grass stains and mud.
  • consumer detergent composition means any composition, that when combined with a lipophilic fluid, result in a cleaning solution useful according to the present invention that comes into direct contact with fabric articles to be cleaned. It should be understood that the term encompasses uses other than cleaning, such as conditioning and sizing.
  • processing aid refers to any material that renders the consumable detergent composition more suitable for formulation, stability, and/or dilution with a lipophilic fluid to form a consumable detergent composition useful for the present invention.
  • mixing means combining two or more materials (i.e., fluids, more specifically a lipophilic fluid and a consumable detergent composition) in such a way that a homogeneous mixture is formed, homogeneous is intended to include emulsions.
  • suitable mixing processes are known in the art. Nonlimiting examples of suitable mixing processes include vortex mixing processes and static mixing processes.
  • Down the drain means both the conventional in-home disposal of materials into the municipal water waste removal systems such as by sewer systems or via site specific systems such as septic systems, as well as for commercial applications the removal to on- site water treatment systems or some other centralized containment means for collecting contaminated water from the facility.
  • Incorporated and included herein, as if expressly written herein, are all ranges of numbers when written in a "from X to Y" or “from about X to about Y" format. It should be understood that every limit given throughout this specification will include every lower, or higher limit, as the case may be, as if such lower or higher limit was expressly written herein. Every range given throughout this specification will include every narrower range that falls within such broader range, as if such narrower ranges were all expressly written herein.
  • the surfactant system of the present invention can be a mixture of surfactants that are capable of suspending water in a lipophilic fluid and/or enhancing soil removal benefits of a lipophilic fluid.
  • the surfactants may be soluble in the lipophilic fluid.
  • the surfactant system of the present invention comprises at least one silicone surfactant and at least one nonionic surfactant, and preferably comprises more than one surfactant selected from the group consisting of silicone surfactants, nonionic surfactants, gemini surfactants, anionic surfactants and mixtures thereof.
  • Another embodiment of the present invention comprises a surfactant system comprising at least one silicone surfactant, at least one nonionic surfactant and and preferably comprises more than one surfactant selected from the group consisting of silicone surfactants, nonionic surfactants, gemini surfactants, anionic surfactants, and further comprising a fatty acid, a fatty acid salt, and mixtures thereof, and mixtures thereof.
  • a mixture of surfactants may be selected from the same class (e.g., two or more nonionic surfactants) or may be selected from two or more classes of surfactants (e.g., one anionic, one nonionic, and one silicone surfactant).
  • Silicone Surfactants The surfactant systems of the present invention comprise at least one silicone surfactant.
  • silicone surfactant should provide improved cleaning benefits compared to the lipophilic fluid utilized in the non-aqueous based washing system.
  • One class of silicone surfactants can include siloxane-based surfactants (siloxane-based materials).
  • the siloxane-based surfactants typically have a weight average molecular weight from 500 to 20,000 daltons. Such materials, derived from poly(dimethylsiloxane), are well known in the art. In the present invention, not all such siloxane-based surfactants are suitable, because they do not provide improved cleaning of soils compared to the level of cleaning provided by the lipophilic fluid itself.
  • Suitable siloxane-based surfactants comprise a poly ether siloxane having the formula (I): M a D b D' c D" d M' 2 . a (I) wherein a of formula (I) is 0-2; b of formula (I) is 0-1000; c of formula (I) is 0-50; d of formula (I) is 0-50, provided that a+c+d of formula (I) is at least 1; M of formula (I) is R' 3 .
  • R 1 of formula (I) is independently H, or a monovalent hydrocarbon group, X of formula (I) is hydroxyl group, and e of formula (I) is 0 or 1;
  • M' of formula (I) is selected from C M alkyl, C M hydroalkyl, R 2 3 SiO ⁇ 2 or mixtures thereof, wherein R 2 of formula (I) is independently H, a monovalent hydrocarbon group, or (CH 2 ) f (C 6 Q 4 ) g O-(C 2 H 4 0) h -(C 3 H 6 0)i(C k H 2k ) j -R 3 (formula (II)), provided that at least one R 2 of formula (I) is (CH 2 ) f (C 6 Q 4 ) g O-(C 2 H 4 0) h -(C 3 H 6 0) i (C k H 2k ) j -R 3 , wherein R 3 of
  • D of formula (I) is R 4 2 Si0 2 2 wherein R 4 of formula (I) is independently H or a monovalent hydrocarbon group;
  • D' of formula (I) is R 5 2 Si0 2/ wherein R 5 of formula (I) is independently R 2 of formula (I) provided that at least one R 5 of formula (I) is (CH 2 ) f (C 6 Q ) g O-(C 2 H 4 0) h -(C 3 H 6 0) i (C k H 2k ) j -R 3 (formula (III)), wherein R 3 of formula (III) is independently H, a monovalent hydrocarbon group or an alkoxy group, f of formula (III) is 1-10, g of formula (III) is 0 or 1, h of formula (III) is 1- 50, i of formula (III) is 0-50, j of formula (III) is 0-50, k of formula (III) is 4-8; C 6 Q of formula (III) is unsubstit
  • D" of formula (I) is R 6 Si0 2/2 wherein R 6 of formula (I) is independently H, a monovalent hydrocarbon group or (CH 2 ) ⁇ (C 6 Q 4 ) m (A) n -[(L) 0 -(A') p -] q -(L') r Z(G) s (formula (IV)) wherein 1 of formula (IV) is 1-10; m of formula (IV) is 0 or 1; n of formula (IV) is 0-5; o of formula (IV) is 0- 3; p of formula (IV) is 0 or 1; q of formula (IV) is 0-10; r of formula (IV) is 0-3; s of formula (IV) is 0-3; C 6 Q 4 of formula (IV) is unsubstituted or substituted with Q of formula (IV) is independently H, C MO alkyl, Ci-io alkenyl, and mixtures thereof; A and A' of formula (IV
  • L and L' of formula (IV) are each independently a C ⁇ profession 30 straight chained or branched alkyl or alkenyl or an aryl which is unsubstituted or substituted;
  • Z of formula (IV) is a hydrogen, carboxylic acid, a hydroxy, a phosphate, a phosphate ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a C ⁇ _ 30 alkyl or alkenyl, a carbohydrate unsubstituted
  • Nonlimiting commercially available examples of suitable siloxane-based surfactants are TSF 4446 (ex. General Electric Silicones), XS69-B5476 (ex. General Electric Silicones); Jenamine HSX (ex. DelCon) and Y12147 (ex. OSi Specialties).
  • Nonionic Surfactants The surfactant systems of the present invention comprise at least one nonionic surfactant.
  • Non-limiting examples of nonionic surfactants include the nonionic surfactants below wherein the indicated carbon ranges are that of the hydrophobic portion (tail) of the surfactant.
  • Nonlimiting examples of preferred ethoxylated surfactant are straight-chain, primary alcohol ethoxylates, with R 8 of formula (V) being C 8 -C ⁇ 8 alkyl and/or alkenyl group, more preferably C ⁇ o-C ⁇ 4 , and s of formula (V) being from about 2 to about 8, preferably from about 2 to about 6; straight-chain, secondary alcohol ethoxylates, with R 8 of formula (V) being C 8 -C ⁇ 8 alkyl and/or alkenyl, e.g., 3-hexadecyl, 2-octadecyl, 4-eicosanyl, and 5-eicosanyl, and s being from about 2 to about 10.
  • a preferred ethoxylated material is shown by formula (VI):
  • x of formula (VI) is from about 0 to about 10, preferably from about 0 to about 7, most preferably from about 0 to about 6.
  • Another preferred ethoxylated material has 15 carbons similar to the formula (VI), wherein ethoxylation is from about 0 to about 10, preferably from about 0 to about 7, most preferably from about 0 to about 6.
  • Also preferred ethoxlated materials comprise blends of carbon chainlengths from 10 to 16, wherein ethoxylation is from about 0 to about 10, preferably from about 0 to about7, and most preferably from about 0 to about 6..
  • Gemini Surfactants The surfactant systems of the present invention may optionally comprise a gemini surfactant.
  • Gemini surfactants are compounds having at least two hydrophobic groups and at least one or optionally two hydrophilic groups per molecule have been introduced. These have become known as "gemini surfactants" in the literature, e.g., Chemtech, March 1993, pp 30-33, and J. American Chemical Soc, 115, 10083-10090 (1993) and the references cited therein. A number of the gemini surfactants are reported in the literature, see for example, Okahara et al., J. Japan Oil Chem. Soc.
  • Gemini surfactants suitable for use in the present invention:
  • Ri, and R 2 of formulas (VII) - (VIII) and R of formulas (IX), (X) and (XI), are same or different and are independently selected from H, C ⁇ . 3 o alkyl, C 2 . 2 o alkenyl; and x of formula (X) is from 0.1 to 60.
  • Anionic Surfactants may optionally comprise an anionic surfactant.
  • anionic surfactants useful herein are listed below wherein the indicated carbon ranges are that of the hydrophobic portion (tail) of the surfactant. a) C ⁇ -Cis alkyl benzene sulfonates (LAS); b) C ⁇ o-C 20 primary, branched-chain and random alkyl sulfates (AS); c) Cio-Cis secondary (2,3) alkyl sulfates having formulas (XII) and (XIII):
  • preferred cations include sodium, potassium, ammonium, and mixtures thereof.
  • x in formula (XII) is an integer of at least about 7, preferably at least about 9; y in formula (XIII) is an integer of at least 8, preferably at least about 9; d) C ⁇ o-C ⁇ 8 alkyl alkoxy sulfates (AE X S) wherein preferably x is from 1-30; e) C ⁇ o-C ⁇ 8 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241,
  • the surfactant system of the present invention comprises from about 0.1 wt% to about to about 50 wt%, preferably from about 0.1 wt% to about 25 wt%, preferably from about 1 wt% to about 15 wt%, preferably from about 5 wt% to about 15 wt% by weight of the surfactant system of at least one silicone surfactant and from about 0.1 wt% to about 99 wt%, preferably from about 0.1 wt% to about 85 wt%, preferably from about 10 wt% to about 60 wt%, and preferably from about 35 wt% to about 85 wt% by weight of the surfactant system of at least one nonionic surfactant; from about 0 wt% to about 50 wt%, preferably from about 0 wt% to about 45 wt%, preferably from about 0 wt% to about 10 wt% by weight of the surfactant system of at least one gemini
  • surfactant system of the present invention comprises from about 0.1 wt% to about to about 50 wt%, preferably from about 0.1 wt% to about 25 wt%, preferably from about 1 wt% to about 15 wt%, preferably from about 5 wt% to about 15 wt% by weight of the surfactant system of at least one silicone surfactant; from about 0.1 wt% to about 99 wt%, preferably from about 0.1 wt% to about 85 wt%, preferably from about 0.1 wt% to about 75 wt%, preferably from about 10 wt% to about 60 wt%, preferably from about 25 wt% to about 85 wt%, and preferably from about 35 wt% to about 99 wt% by weight of the surfactant system of at least one nonionic surfactant; from about 0 wt% to about 50 wt%, preferably from about 0 wt% to about 45 wt%,
  • the consumable detergent composition comprises a surfactant system comprises from about 0.1 wt% to about 30 wt%, preferably from about 0.1 wt% to about 20 wt%, preferably from about 0.1 wt% to about 15 wt%, preferably from about 1 wt% to about 15 wt%, preferably from about 5 wt% to about 15 wt%, by weight of the consumable detergent composition of at least one silicone surfactant; from about 0.1 wt% to about 99 wt%, preferably from about 10 wt% to about 99 wt%; preferably from about 10 wt% to about 60 wt%, preferably from about 35 wt% to about 75 wt%, preferably from about 40 wt% to about 70 wt% by weight of the consumable detergent composition of at least one nonionic surfactant
  • the consumable detergent composition comprises a surfactant system comprises from about 0.1 wt% to about 30 wt%, preferably from about 0.1 wt% to about 20 wt%, preferably from about 0.1 wt% to about 15 wt%, preferably from about 1 wt% to about 15 wt%, preferably from about 5 wt% to about 15 wt%, by weight of the consumable detergent composition of at least one silicone surfactant; from about 0.1 wt% to about 99 wt%, preferably from about 0.1% to about 75 wt%, preferably from about 10 wt% to about 99 wt%; preferably from 10 wt% to about 75 wt%, preferably from about 10 wt% to about 60 wt%, preferably from about 35 wt% to about 75 wt%, preferably from about 40 wt% to about 70 wt% by weight of the consumable detergent composition of at least one nonionic surfactant; from about 0.1 w
  • the consumable detergent composition of the present invention may further comprises from about 0 wt% to about 75 wt% by weight of the consumable detergent composition of at least one fatty acid, fatty acid salt, and mixtures thereof.
  • an anionic surfactant is present.
  • the consumable detergent composition of the present invention comprises a surfactant system, optionally a fatty acid, fatty acid salt, and mixtures thereof, optionally a fatty quat, and optionally at least one cleaning adjunct.
  • the surfactant system may be altered dependent upon what type of soil is targeted.
  • Greasy soils traditionally posing problems in water-based systems, are not as challenging in lipophilic fluid based systems, such as the present invention.
  • hydrophilic soils traditionally posing no problems in water-based systems, now raises challenges in lipophilic fluid based systems.
  • hydrophilic soils on cotton fabric articles are especially difficult to address in a non-aqueous solvent based washing system utilizing lipophilic fluid.
  • Lipophilic Fluid as used herein means any liquid or mixture of liquids that are immiscible with water at up to 20% by weight of water.
  • a suitable lipophilic fluid can be fully liquid at ambient temperature and pressure, can be an easily melted solid, e.g., one that becomes liquid at temperatures in the range from about 0°C to about 60°C, or can comprise a mixture of liquid and vapor phases at ambient temperatures and pressures, e.g., at 25°C and 101.3 kPa (1 arm) pressure. It is preferred that the lipophilic fluid herein be nonflammable or, have relatively high flash points and/or low VOC characteristics, these terms having conventional meanings as used in the dry cleaning industry, to equal or, preferably, exceed the characteristics of known conventional dry cleaning fluids.
  • Non-limiting examples of suitable lipophilic fluid materials include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerine derivatives such as glycerine ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, low-volatility nonfluorinated organic solvents, diol solvents, other environmentally-friendly solvents and mixtures thereof.
  • siloxane as used herein means silicone fluids that are non-polar and insoluble in water or lower alcohols.
  • Linear siloxanes (see for example US Patents 5,443,747, and 5,977,040) and cyclic siloxanes are useful herein, including the cyclic siloxanes selected from the group consisting of octamethyl-cyclotetrasiloxane (tetramer), dodecamethyl-cyclohexasiloxane (hexamer), and preferably decamethyl-cyclopentasiloxane (pentamer, commonly referred to as "D5").
  • octamethyl-cyclotetrasiloxane tetramer
  • dodecamethyl-cyclohexasiloxane hexamer
  • D5 decamethyl-cyclopentasiloxane
  • a preferred siloxane comprises more than about 50% cyclic siloxane pentamer, more preferably more than about 75% cyclic siloxane pentamer, most preferably at least about 90% of the cyclic siloxane pentamer.
  • siloxanes that are a mixture of cyclic siloxanes having at least about 90% (preferably at least about 95%) pentamer and less than about 10% (preferably less than about 5%) tetramer and/or hexamer.
  • the lipophilic fluid can include any fraction of dry-cleaning solvents, especially newer types including fluorinated solvents, or perfluorinated amines.
  • perfluorinated amines such as perfluorotributylamines
  • lipophilic fluids include, but are not limited to, diol solvent systems e.g., higher diols such as or C 8 or higher diols, organosilicone solvents including both cyclic and acyclic types, and the like, and mixtures thereof.
  • diol solvent systems e.g., higher diols such as or C 8 or higher diols
  • organosilicone solvents including both cyclic and acyclic types, and the like, and mixtures thereof.
  • Non-limiting examples of low volatility non-fluorinated organic solvents include for example OLEAN ® and other polyol esters, or certain relatively nonvolatile biodegradable mid- chain branched petroleum fractions.
  • glycol ethers include propylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-propyl ether, tripropylene glycol t-butyl ether, tripropylene glycol n-butyl ether.
  • Non-limiting examples of other silicone solvents, in addition to the siloxanes, are well known in the literature, see, for example, Kirk Othmer's Encyclopedia of Chemical Technology, and are available from a number of commercial sources, including GE Silicones, Toshiba Silicone, Bayer, and Dow Corning.
  • one suitable silicone solvent is SF-1528 available from GE Silicones.
  • suitable glycerine derivative solvents for use in the methods and/or apparatuses of the present invention include glyercine derivatives having the formula (XIV):
  • R 1 , R 2 and R 3 of formula (XIV) are each independently selected from: H; branched or linear, substituted or unsubstituted C ⁇ -C 3 o alkyl, C 2 -C 30 alkenyl, C ⁇ -C 3 o alkoxycarbonyl, C 3 -C 30 alkyleneoxyalkyl, C C 30 acyloxy, C 7 -C 30 alkylenearyl; C -C 30 cycloalkyl; C ⁇ -C o aryl; and mixtures thereof.
  • R 1 , R 2 and R 3 of formula (XIV) together can form a C 3 -C 8 aromatic or non-aromatic, heterocyclic or non-heterocyclic ring.
  • suitable glycerine derivative solvents include 2,3-bis(l,l- dimethylethoxy)- 1 -propanol; 2,3-dimethoxy- 1 -propanol; 3-methoxy-2-cyclopentoxy- 1 -propanol; 3-methoxy-l-cyclopentoxy-2-propanol; carbonic acid (2-hydroxy-l-methoxymethyl)ethyl ester methyl ester; glycerol carbonate and mixtures thereof.
  • Non-limiting examples of other environmentally-friendly solvents include lipophilic fluids that have an ozone formation potential of from 0 to about 0.31, lipophilic fluids that have a vapor pressure of from 0 to about 13.3 Pa (0 to about 0.1 mm Hg), and/or lipophilic fluids that have a vapor pressure of greater than 13.3 Pa (0.1 mm Hg), but have an ozone formation potential of from 0 to about 0.31.
  • Non-limiting examples of such lipophilic fluids that have not previously been described above include carbonate solvents (i.e., methyl carbonates, ethyl carbonates, ethylene carbonates, propylene carbonates, glycerine carbonates) and/or succinate solvents (i.e., dimethyl succinates).
  • Ozone Reactivity is a measure of a VOC's ability to form ozone in the atmosphere. It is measured as grams of ozone formed per gram of volatile organics. A methodology to determine ozone reactivity is discussed further in W. P. L. Carter, "Development of Ozone Reactivity Scales of Volatile Organic Compounds", Journal of the Air & Waste Management Association, Vol. 44, Pages 881-899, 1994. "Vapor Pressure" as used can be measured by techniques defined in Method 310 of the California Air Resources Board.
  • the lipophilic fluid comprises more than 50% by weight of the lipophilic fluid of cyclopentasiloxanes, ("D5") and/or linear analogs having approximately similar volatility, and optionally complemented by other silicone solvents.
  • Consumable detergents composition according to the present invention may comprise a fatty acid, fatty acid salt, and mixtures thereof.
  • Surfactant systems of the present invention may comprise a fatty acid, fatty acid salt, and mixtures thereof, optionally comprising a fatty acid, fatty acid salt, and mixtures thereof when no anionic surfactant is present.
  • Suitable fatty acids and fatty acid salts are suitably selected from mono- and di-carboxylic acids comprising the following hydrophobes: saturated or unsaturated, linear or branched hydrocarbons having 6-30 carbons, preferred are branched and/or saturated mono- and di- carboxylic acids; ethoxylated alcohols, polyalkylene oxides (polypropyleneoxide, polybutyleneoxide, polyhexyleneoxide), including pure homopolymers or any copolymers and oligomers; linear or branched siloxanes, hydroxyl- functionalized silicones, alkoxylated silicones (e.g., ethoxylated/propylated silicones), alkylphosphonates, alkylphosphinates, phosphate monoesters of hydrophobic alcohols, phosphate diesters of hydrophobic alcohols; and mixtures thereof.
  • mono- and di-carboxylic acids comprising the following hydrophobes: saturated or unsaturated, linear or branche
  • Suitable fatty acid salts have counterions selected from hydrogen, ammonium, C ⁇ -C 2 o alkylammonium, sodium, potassium, and the like.
  • Phosphate monoester and diesters of hydrophobic alcohols include C ⁇ -C 2 o linear or branched alkyl phosphate monoester or phosphate diesters.
  • the acid form of the phosphate ester (i.e., protonated ester) and corresponding salts are intended to be included.
  • Preferred phosphate monoesters and diesters include those represented by formula (XV): O
  • R of formula (XV) is selected from a C 6 . 20 alkyl, silicone and mixtures thereof.
  • M is a suitable counterion selected from hydrogen, sodium, ammonium, C ⁇ -C 20 alkylammonium and mixtures thereof.
  • Preferred phosphate monoesters comprise formula (XVI) and phosphate diesters comprise formula (XVII). It would be apparent to one of skill in the art that the alkylphosponates may be selected from a fatty acid and fatty acid salt forms.
  • the monester is exemplified in a fatty acid form (formula (XVI)) and the diester is exemplified in a suitable fatty acid salt form (formula (XVII)):
  • Alkylphosphonates may comprise formula (XVIII) (XVIII) Wherein Ri of formula (XVIII) is selected from a linear or branched C 6 -C 20 alkyl, silicone, and mixtures thereof. R 2 of formula (XVIII) is selected from a linear or branched C 6 -C 20 alkyl, silicone, and mixtures thereof. M of formula (XVIII) is a suitable counterion selected from hydrogen, sodium, ammonium, C C 2 o alkylammonium and mixtures thereof. It would be apparent to one of skill in the art that the alkylphosponates may be selected from a fatty acid and fatty acid salt forms. Not to be limited to the shown formulae, shown in formula (XIX) is an alkylphosphonates fatty acid while an alkylphosphonates fatty acid salt is shown in formula (XX).
  • Alkylphosphinates may comprise formula (XXI):
  • Ri of formula (XXI) is selected from a linear or branched C 6 -C 20 alkyl, silicone, and mixtures thereof.
  • M of formula (XXI) is a suitable counterion selected from hydrogen, sodium, ammonium, C ⁇ -C 2 o alkylammonium and mixtures thereof.
  • the alkylphosphinates may be selected from a fatty acid and fatty acid salt forms. Not to be limited to the shown formulae, shown in formula (XXII) is a alkylphosphinate fatty acid
  • Fatty acid, fatty acid salt, and mixtures thereof may comprise from about 0 wt% to about 75 wt%, preferably from about 5 wt% to about 40 wt% by weight of the consumable detergent composition of a fatty acid, fatty acid salt, and mixtures thereof.
  • the fatty acid, fatty acid salt, and mixtures thereof have from 2 to 20 carbon atoms, preferably from 10 to 18 carbon atoms.
  • the fatty acid, fatty acid salt, and mixtures thereof may comprise from about 0 wt% to about 75 wt% by weight of the surfactant system, preferably from 0.1 wt% to about 75 wt% by weight of the surfactant system if no anionic surfactant is present.
  • the consumable detergent composition according to the present invention may comprise a fatty quat.
  • Fatty quats may comprise from about 0 wt% to about 75 wt%, preferably from about 2 wt% to about 20 wt% by weight of the consumable detergent composition.
  • the fatty quat comprises substituted nitrogen wherein the nitrogen is substituted with at least one moiety comprising from about 2 to about 20 carbon atoms, preferably from about 14 to about 20 carbon atoms.
  • Nonlimited examples of the fatty quat may include conventional fabric softening actives.
  • Such fatty quats may include, but are not limited to dialkyldimethylammonium salts having the formula (XIV).
  • R' 'N ⁇ CH ⁇ X (XIV) wherein each R' and R" of formula (XIV) are independently selected fromithe group consisting of 12-30 carbon atoms or derived from tallow, coconut oil or soy, X of formula (XIV) is selected from anionic counter ions, including but not limited to Cl “ or Br " .
  • dialkyledimethylammonium salts include: didodecyldimethylammonium bromide (DDAB), dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyidimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, didocosyldimethyl ammonium chloride, dicoconutdimethyl ammonium chloride, ditallowdimethyl ammonium bromide (DTAB).
  • DDAB didodecyldimethylammonium bromide
  • ARQUAD® ARQUAD®
  • TOMAH9® TOMAH9®
  • VARIQUAT® VARIQUAT®
  • the fatty quat comprise the water-soluble quaternary ammonium compounds useful in the present invention having the formula (XV) RiRaRsR t N'X " (XV) wherein R of formula (XV) is C 8 -Ci 6 alkyl, each of R 2 , R 3 and R of formula (XV) are independently C ⁇ -C 4 alkyl, CpC hydroxy alkyl, benzyl, and -(C 2 H 0) x H where x of formula (XV) has a value from 2 to 5, and X of formula (XV) is a anion selected from Cl " , Br " , methyl sulfate, formate, sulfate, nitrate, and mixtures thereof.
  • a preferred fatty quat embodiment has the formula (XVI): (R) 4 . m -N + [(CH 2 ) n -Y-R 2 ] m X- (XVI) wherein Y of formula (XVI) is selected from -0-(0)C- or -C(0)-0-; m of formula (XVI) is 2 or 3; n of formula (XVI) is from 1 to 4; R of formula (XVI) is selected from Q- ⁇ , preferably C ⁇ _ 3 alkyl group, benzyl, and mixtures thereof; R 2 is selected from C ⁇ - 2 ⁇ , substituted or unsubstituted hydrocarbonyl having at least partial unsaturated and its counterion X " of formula (XVI); X " of formula (XVI) is selected from Cl " , Br " , methyl sulfate, formate, sulfate, n
  • Polar Solvent Compositions according to the present invention may further comprise a polar solvent.
  • polar solvents include: water, alcohols, glycols, polyglycols, ethers, carbonates, dibasic esters, ketones, other oxygenated solvents, and mixtures thereof.
  • alcohols include: C ⁇ -C 3 o alcohols, such as propanol, ethanol, isopropyl alcohol, and the like, benzyl alcohol, and diols such as 1,2-hexanediol.
  • DOWANOL® series by Dow Chemical are examples of glycols and polyglycols useful in the present invention, such as DOWANOL® TPM, TPnP, DPnB, DPnP, TPnB, PPh, DPM, DPMA, DB, and others. Further examples include propylene glycol, butylene glycol, polybutylene glycol and more hydrophobic glycols.
  • Examples of carbonate solvents are ethylene, propylene and butylene carbonantes such as those available under the JEFFSOL® tradename.
  • Polar solvents for the present invention can be further identified through dispersive ( ⁇ o), polar ( ⁇ p) and hydrogen bonding (5 H ) Hansen solubility parameters.
  • Preferred polar solvents or polar solvent mixtures have fractional polar (f P ) and fractional hydrogen bonding (f H ) values of f P >0.02 and f H >0.10, where and more preferably f P >0.05 and f ⁇ >0.20, and most preferably fp>0.07 and f H >0.30.
  • the levels of polar solvent can be from 0 wt% to about 70 wt%, preferably about 1 wt% to about 50 wt% even more preferably about 1 wt% to about 30 wt% by weight of the consumable detergent composition.
  • the polar solvent comprises from about 0.1 wt% to about 1 wt%, preferably 0.5 wt% to about 1 wt%, by weight of the consumable detergent composition of water.
  • preferred levels of polar solvent are from about 0.01 wt% to about 2 wt%, preferably about 0.05 wt% to about 0.8 wt%, even more preferably about 0.1 wt% to about 0.5 wt% by weight of the consumable detergent composition.
  • the detergents compositions preferably comprise from about 2 wt% to about 25 wt%, more preferably from about 5 wt% to about 20 wt%, even more preferably from about 8 wt% to about 15 wt% by weight of the consumable detergent composition.
  • Cleaning Adjuncts The consumable detergent compositions of the present invention optionally further comprise at least one additional cleaning adjunct.
  • the cleaning adjuncts can vary widely and can be used at widely ranging levels.
  • detersive enzymes such as proteases, amylases, cellulases, lipases and the like as well as bleach catalysts including the macrocyclic types having manganese or similar transition metals all useful in laundry and cleaning products can be used herein at very low, or less commonly, higher levels.
  • Cleaning adjuncts that are catalytic, for example enzymes can be used in "forward" or “reverse” modes, a discovery independently useful from the fabric treating methods of the present invention.
  • a lipolase or other hydrolase may be used, optionally in the presence of alcohols as cleaning adjuncts, to convert fatty acids to esters, thereby increasing their solubility in the lipophilic fluid.
  • any cleaning adjunct must be suitable for use in combination with a lipophilic fluid in accordance with the present invention.
  • cleaning adjuncts include, but are not limited to, builders, surfactants other than those described above with respect to the surfactant system, enzymes, bleach activators, bleach catalysts, bleach boosters, bleaches, alkalinity sources, antibacterial agents, colorants, perfumes, pro-perfumes, finishing aids, finishing polymers, lime soap dispersants, odor control agents, odor neutralizers, polymeric dye transfer inhibiting agents, crystal growth inhibitors, photobleaches, heavy metal ion sequestrants, anti-tarnishing agents, anti-microbial agents, anti- oxidants, anti-redeposition agents, soil release polymers, electrolytes, pH modifiers, thickeners, abrasives, divalent or trivalent ions, metal ion salts, enzyme stabilizers, corrosion inhibitors, diamines or polyamines and/or their alkoxylates, suds stabilizing polymers, solvents, process aids, fabric softening agents, optical brighteners, hydrotropes, suds or foam suppressors,
  • the consumable detergent compositions useful for the present invention may comprise processing aids.
  • Processing aids facilitate the formation of the consumable detergent compositions by maintaining the fluidity and/or homogeneity of the consumable detergent composition, and/or aiding in the dilution process.
  • Processing aids suitable for the present invention are solvents, preferably solvents other than those described above, hydrotropes, and/or surfactants, preferably surfactants other than those described above with respect to the surfactant system.
  • Particularly preferred processing aids are protic solvents such as aliphatic alcohols, diols, triols, etc. and nonionic surfactants such as ethoxylated fatty alcohols.
  • Processing aids when present in the consumable detergent compositions, preferably comprise from about 0.02 wt% to about 10 wt%, more preferably from about 0.05 wt% to about 10 wt%, even more preferably from about 0.1 wt% to about 10 wt% by weight of the consumable detergent composition. Processing aids, when present in the consumable detergent compositions, preferably comprise from about 1 wt% to about 75 wt%, more preferably from about 5 wt% to about 50 wt% by weight of the consumable detergent composition.
  • Suitable odor control agents which may optionally be used as finishing agents, include agents include, cyclodextrins, odor neutralizers, odor blockers and mixtures thereof.
  • Suitable odor neutralizers include aldehydes, flavanoids, metallic salts, water-soluble polymers, zeolites, activated carbon and mixtures thereof.
  • Perfumes and perfumery ingredients useful in the consumable detergent compositions for the present invention comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfumes may comprise extremely complex mixtures of such ingredients. Pro-perfumes are also useful in the present invention.
  • Such materials are those precursors or mixtures thereof capable of chemically reacting, e.g., by hydrolysis, to release a perfume.
  • Bleaches especially oxygen bleaches, are another type of laundry additive suitable for use in the consumable detergent compositions for the present invention. This is especially the case for the activated and catalyzed forms with such bleach activators as nonanoyloxybenzenesulfonate and/or any of its linear or branched higher or lower homologs, and/or tetraacetylethylenediamine and/or any of its derivatives or derivatives of phthaloylimidoperoxycaproic acid (PAP; available from Ausimont SpA under trademane EUROCO®) or other imido- or amido-substituted bleach activators including the lactam types, or more generally any mixture of hydrophilic and/or hydrophobic bleach activators (especially acyl derivatives including those of the C ⁇ -Ci ⁇ substituted oxybenzenesulfonates).
  • organic or inorganic peracids both including PAP and other than PAP.
  • Suitable organic or inorganic peracids for use herein include, but are not limited to: percarboxylic acids and salts; percarbonic acids and salts; perimidic acids and salts; peroxymonosulfuric acids and salts; persulphates such as monopersulfate; peroxyacids such as diperoxydodecandioic acid (DPDA); magnesium peroxyphthalic acid; perlauric acid; perbenzoic and alkylperbenzoic acids; and mixtures thereof.
  • DPDA diperoxydodecandioic acid
  • magnesium peroxyphthalic acid perlauric acid
  • perbenzoic and alkylperbenzoic acids and mixtures thereof.
  • Detersive enzymes such as proteases, amylases, cellulases, lipases and the like as well as bleach catalysts including the macrocyclic types having manganese or similar transition metals all useful in laundry and cleaning products can be used herein at very low, or less commonly, higher levels.
  • a lipolase or other hydrolase may be used, optionally in the presence of alcohols as laundry additives, to convert fatty acids to esters, thereby increasing their solubility in the lipohilic fluid.
  • Nonlimiting examples of finishing polymers that are commercially available are: polyvinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, such as Copolymer 958®, weight average molecular weight of about 100,000 daltons and Copolymer 937®, weight average molecular weight of about 1,000,000 daltons, available from GAF Chemicals Corporation; adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer, such as CARTARETIN F-4® and F-23®, available from Sandoz Chemicals Corporation; methacryloyl ethyl betaine/methacrylates copolymer, such as DIAFORMER Z-SM®, available from Mitsubishi Chemicals Corporation; polyvinyl alcohol copolymer resin, such as VINEX 2019®, available from Air Products and Chemicals or MOWEOl®, available from Clariant; adipic acid/epoxypropyl diethylenetriamine copolymer, such as DELSETTE 101®
  • the cleaning additive may also be an antistatic agent.
  • Any suitable well-known antistatic agents used in conventional laundering and dry cleaning are suitable for use in the consumable detergent compositions and methods of the present invention.
  • Especially suitable as antistatic agents are the subset of fabric softeners which are known to provide antistatic benefits.
  • antistatic agent is not to be limited to just this subset of fabric softeners and includes all antistatic agents.
  • Preferred insect and moth repellent laundry additives useful in the compositions of the present invention are perfume ingredients, such as citronellol, citronellal, citral, linalool, cedar extract, geranium oil, sandalwood oil, 2-(diethylphenoxy)ethanol, 1-dodecene, etc.
  • Other examples of insect and/or moth repellents useful in the compositions of the present invention are disclosed in U.S. Pat. Nos. 4,449,987; 4,693,890; 4,696,676; 4,933,371; 5,030,660; 5,196,200; and in "Semio Activity of Flavor and Fragrance Molecules on Various Insect Species", B.D.
  • the surfactant system and the consumable detergent composition may be utilized to clean fabric articles in a non-aqueous solvent based washing system utilizing lipophilic fluid.
  • the method includes the step of contacting a cleaning solution, comprising the surfactant system or the consumable detergent composition of the present invention and a lipophilic fluid, with a fabric article and then extracting the cleaning solution from the fabric article.
  • the method may further comprise a pre-step of mixing the surfactant system or the consumable detergent composition with a lipophilic fluid to form a cleaning solution.
  • the method may further comprise the steps of agitating the fabric article in the cleaning solution; scrubbing the fabric article; drying the fabric article and any combination thereof.
  • the drying step may include heat drying, air drying, or any other known form of drying a fabric article.

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)
  • Detergent Compositions (AREA)

Abstract

The present invention relates to a surfactant system and a consumable detergent composition comprising the same. The surfactant system is used in a lipophilic liquid and comprises from 0.1 to 30 wt. % of a silicone surfactant, from 0.1 to 99 wt. % of a nonionic surfactant, from 0 to 50 wt. % of a gemini surfactant and from 0 to 50 wt. % of an anionic surfactant.

Description

Surfactant System for Use in a Lipophilic Fluid
Field of Invention The present invention relates to a surfactant system and a consumable detergent composition comprising the same. Background of the Invention A non-aqueous solvent based washing system utilizing lipophilic fluid, such as cyclic siloxanes (especially cyclopentasiloxanes, sometimes termed "D5"), particularly for use with washing machines for in-home use, has recently been developed. Such a system is particularly desired for cleaning textile articles without causing damage associated with wet-washing, like shrinkage and dye transfer. To maximize fabric cleaning in such a system it is necessary to use additives for cleaning, softening, finishing, and other similar benefits. Traditional water soluble surfactants, such as anionic surfactants, do not function in the same manner in a non-aqueous solvent based washing system utilizing lipophilic fluid compared to a water-based washing system. The surfactant system in a non-aqueous solvent based washing system may be altered dependent upon what type of soil is targeted. Greasy soils, traditionally posing problems in water-based systems, are not as challenging in lipophilic fluid based systems, such as the present invention. However, hydrophilic soils, traditionally posing no problems in water-based systems, raise challenges in lipophilic fluid based systems. Optimization of a surfactant system in a non- aqueous solvent based washing system utilizing lipophilic fluid is an unmet need. Therefore, an unmet need exists for an optimized surfactant system for use in a non-aqueous solvent based washing system utilizing lipophilic fluid and a detergent composition for use in the same. Summary of the Invention The present invention relates to a surfactant system for use in a lipophilic liquid comprising at least two surfactants selected from the group comprising of from about 0.1 wt% to about 30 wt% of a silicone surfactant; from about 0.1 wt% to about 99 wt% of a nonionic surfactant; from about 0 wt% to about 50 wt% of a gemini surfactant; and from about 0 wt% to about 50 wt% of a anionic surfactant. The present invention also relates to a consumable detergent composition for use in a lipophilic fluid comprising: a) from about 1 wt% to about 100 wt% of a surfactant system comprising at least two surfactants consisting of from about 0.1 wt% to about 75 wt% of a silicone surfactant; from about 0.1 wt% to about 99 wt% of a nonionic surfactant; from about 0 wt% to about 40 wt% of a gemini surfactant; from about 0 wt% to about 75 wt% of a anionic surfactant; and b) from about 0 wt% to about 75 wt% of a fatty acid, fatty acid salt and mixtures thereof; c) from about 0 wt% to about 75 wt% of a fatty quat comprising a nitrogen substituted by at least one hydrophobic tail comprising from 2 to 20 carbon atoms; and d) from about 0 wt% to about 75 wt% of the consumable detergent composition of a polar solvent, a mixture of polar solvents and adjuncts. Detailed Description of the Invention The term "fabric article" used herein is intended to mean any article that is customarily cleaned in a conventional laundry process or in a dry cleaning process. As such, the term encompasses articles of clothing, linen, drapery, and clothing accessories. The term also encompasses other items made in whole or in part of fabric, such as tote bags, furniture covers, tarpaulins and the like. The term "lipophilic fluid" used herein is intended to mean any nonaqueous fluid capable of removing sebum, as described in more detail herein below. The term "soil" means any undesirable substance on a fabric article that is desired to be removed. By the terms "water-based" or "hydrophilic" soils, it is meant that the soil comprised water at the time it first came in contact with the fabric article, that the soil has high water solubility or affinity, or the soil retains a significant portion of water on the fabric article. Examples of water-based soils include, but are not limited to beverages, many food soils, water soluble dyes, bodily fluids such as sweat, urine or blood, outdoor soils such as grass stains and mud. The term "consumable detergent composition" means any composition, that when combined with a lipophilic fluid, result in a cleaning solution useful according to the present invention that comes into direct contact with fabric articles to be cleaned. It should be understood that the term encompasses uses other than cleaning, such as conditioning and sizing. The term "processing aid" refers to any material that renders the consumable detergent composition more suitable for formulation, stability, and/or dilution with a lipophilic fluid to form a consumable detergent composition useful for the present invention. The term "mixing" as used herein means combining two or more materials (i.e., fluids, more specifically a lipophilic fluid and a consumable detergent composition) in such a way that a homogeneous mixture is formed, homogeneous is intended to include emulsions. Suitable mixing processes are known in the art. Nonlimiting examples of suitable mixing processes include vortex mixing processes and static mixing processes. "Down the drain", as used herein, means both the conventional in-home disposal of materials into the municipal water waste removal systems such as by sewer systems or via site specific systems such as septic systems, as well as for commercial applications the removal to on- site water treatment systems or some other centralized containment means for collecting contaminated water from the facility. Incorporated and included herein, as if expressly written herein, are all ranges of numbers when written in a "from X to Y" or "from about X to about Y" format. It should be understood that every limit given throughout this specification will include every lower, or higher limit, as the case may be, as if such lower or higher limit was expressly written herein. Every range given throughout this specification will include every narrower range that falls within such broader range, as if such narrower ranges were all expressly written herein.
Surfactant System The surfactant system of the present invention can be a mixture of surfactants that are capable of suspending water in a lipophilic fluid and/or enhancing soil removal benefits of a lipophilic fluid. The surfactants may be soluble in the lipophilic fluid. The surfactant system of the present invention comprises at least one silicone surfactant and at least one nonionic surfactant, and preferably comprises more than one surfactant selected from the group consisting of silicone surfactants, nonionic surfactants, gemini surfactants, anionic surfactants and mixtures thereof. Another embodiment of the present invention comprises a surfactant system comprising at least one silicone surfactant, at least one nonionic surfactant and and preferably comprises more than one surfactant selected from the group consisting of silicone surfactants, nonionic surfactants, gemini surfactants, anionic surfactants, and further comprising a fatty acid, a fatty acid salt, and mixtures thereof, and mixtures thereof. A mixture of surfactants may be selected from the same class (e.g., two or more nonionic surfactants) or may be selected from two or more classes of surfactants (e.g., one anionic, one nonionic, and one silicone surfactant). Silicone Surfactants The surfactant systems of the present invention comprise at least one silicone surfactant. Additionally, the silicone surfactant should provide improved cleaning benefits compared to the lipophilic fluid utilized in the non-aqueous based washing system. One class of silicone surfactants can include siloxane-based surfactants (siloxane-based materials). The siloxane-based surfactants typically have a weight average molecular weight from 500 to 20,000 daltons. Such materials, derived from poly(dimethylsiloxane), are well known in the art. In the present invention, not all such siloxane-based surfactants are suitable, because they do not provide improved cleaning of soils compared to the level of cleaning provided by the lipophilic fluid itself. Suitable siloxane-based surfactants comprise a poly ether siloxane having the formula (I): MaDbD'cD"dM'2.a (I) wherein a of formula (I) is 0-2; b of formula (I) is 0-1000; c of formula (I) is 0-50; d of formula (I) is 0-50, provided that a+c+d of formula (I) is at least 1; M of formula (I) is R'3.eXeSiOι/2 wherein R1 of formula (I) is independently H, or a monovalent hydrocarbon group, X of formula (I) is hydroxyl group, and e of formula (I) is 0 or 1; M' of formula (I) is selected from CM alkyl, CM hydroalkyl, R2 3SiOι 2 or mixtures thereof, wherein R2 of formula (I) is independently H, a monovalent hydrocarbon group, or (CH2)f(C6Q4)gO-(C2H40)h-(C3H60)i(CkH2k)j-R3 (formula (II)), provided that at least one R2 of formula (I) is (CH2)f(C6Q4)gO-(C2H40)h-(C3H60)i(CkH2k)j-R3, wherein R3 of formula (II) is independently H, a monovalent hydrocarbon group or an alkoxy group, f of formula (II) is 1-10, g of formula (II) is 0 or 1, h of formula (II) is 1-50, i of formula (II) is 0-50, j of formula (II) is 0-50, k of formula (II) is 4-8; CβQ4 of formula (II) is unsubstituted or substituted with Q of formula (II) is independently H, Q-io alkyl, Ci-io alkenyl, and mixtures thereof. D of formula (I) is R4 2Si02 2 wherein R4 of formula (I) is independently H or a monovalent hydrocarbon group; D' of formula (I) is R5 2Si02/ wherein R5 of formula (I) is independently R2 of formula (I) provided that at least one R5 of formula (I) is (CH2)f(C6Q )gO-(C2H40)h-(C3H60)i(CkH2k)j-R3 (formula (III)), wherein R3 of formula (III) is independently H, a monovalent hydrocarbon group or an alkoxy group, f of formula (III) is 1-10, g of formula (III) is 0 or 1, h of formula (III) is 1- 50, i of formula (III) is 0-50, j of formula (III) is 0-50, k of formula (III) is 4-8; C6Q of formula (III) is unsubstituted or substituted with Q of formula (III) is independently H, CMO alkyl, C 0 alkenyl, and mixtures thereof. D" of formula (I) is R6 Si02/2 wherein R6 of formula (I) is independently H, a monovalent hydrocarbon group or (CH2)ι(C6Q4)m(A)n-[(L)0-(A')p-]q-(L')rZ(G)s (formula (IV)) wherein 1 of formula (IV) is 1-10; m of formula (IV) is 0 or 1; n of formula (IV) is 0-5; o of formula (IV) is 0- 3; p of formula (IV) is 0 or 1; q of formula (IV) is 0-10; r of formula (IV) is 0-3; s of formula (IV) is 0-3; C6Q4 of formula (IV) is unsubstituted or substituted with Q of formula (IV) is independently H, CMO alkyl, Ci-io alkenyl, and mixtures thereof; A and A' of formula (IV) are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a .4 fluoroalkyl, a CM fluoroalkenyl, a branched or straight chained polyalkylene oxide, a phosphate, a sulfonyl, a sulfate, an ammonium, and mixtures thereof; L and L' of formula (IV) are each independently a Cι„30 straight chained or branched alkyl or alkenyl or an aryl which is unsubstituted or substituted; Z of formula (IV) is a hydrogen, carboxylic acid, a hydroxy, a phosphate, a phosphate ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a Cι_30 alkyl or alkenyl, a carbohydrate unsubstituted or substituted with a CMO alkyl or alkenyl or an ammonium; G of formula (IV) is an anion or cation such as H"1", Na+, Li+, K+, NH4 +, Ca+2, Mg+2, Cl", Br , I\ mesylate or tosylate. Examples of the types of siloxane-based surfactants described herein above may be found in EP-1.043.443A1, EP-1,041,189 and WO-01 34,706 (all to GE Silicones) and US-5,676,705, US-5,683,977, US-5,683,473, and EP-1,092,803A1 (all assigned to Lever Brothers). Nonlimiting commercially available examples of suitable siloxane-based surfactants are TSF 4446 (ex. General Electric Silicones), XS69-B5476 (ex. General Electric Silicones); Jenamine HSX (ex. DelCon) and Y12147 (ex. OSi Specialties). Nonionic Surfactants The surfactant systems of the present invention comprise at least one nonionic surfactant. Non-limiting examples of nonionic surfactants include the nonionic surfactants below wherein the indicated carbon ranges are that of the hydrophobic portion (tail) of the surfactant. a) C6-Cι2 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; b) C12-Ci8 alcohol and Cβ-Cι2 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as PLURONIC® from BASF; c) Cι4-C22 mid-chain branched alcohols, BA, as discussed in US 6,150,322; d) Cι4-C22 mid-chain branched alkyl alkoxylates, BAE wherein x 1-30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; e) Alkylpolysaccharides as discussed in U.S. 4,565,647 by Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US 4,483,780 and US 4,483,779; f) Polyhydroxy fatty acid amides as discussed in US 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; g) ether capped poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO 01/42408; h) Polyethylene oxide condensates of nonyl phenol and myristyl alcohol, such as in US 4,685,930; i) fatty alcohol ethoxylates, nonlimiting examples of ethoxylated materials, such as ethoxylated surfactants include compounds having the general formula (V): R8-Z-(CH2CH20)SB (V) wherein R8 of formula (V) is an alkyl group or an alkyl aryl group, selected from the group consisting of primary, secondary and branched chain alkyl hydrocarbyl groups, primary, secondary and branched chain alkenyl hydrocarbyl groups, and/or primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups having a hydrophobic portion (tail) from about 6 to about 20 carbon atoms, preferably from about 8 to about 18, more preferably from about 10 to about 15 carbon atoms; s of formula (V) is an integer from about 1 to about 45, preferably from about 1 to about 20, more preferably from about 1 to about 15; B of formula (V) is a hydrogen, a carboxylate group, or a sulfate group; and linking group Z of formula (V) is -0-, -C(0)0-, -C(0)N(R)-, -CN(0)R- and mixtures thereof, in which R of formula (V), when present, is R8 of formula (V) or hydrogen. Nonlimiting examples of preferred ethoxylated surfactant are straight-chain, primary alcohol ethoxylates, with R8 of formula (V) being C8-Cι8 alkyl and/or alkenyl group, more preferably Cιo-Cι4, and s of formula (V) being from about 2 to about 8, preferably from about 2 to about 6; straight-chain, secondary alcohol ethoxylates, with R8 of formula (V) being C8-Cι8 alkyl and/or alkenyl, e.g., 3-hexadecyl, 2-octadecyl, 4-eicosanyl, and 5-eicosanyl, and s being from about 2 to about 10. A preferred ethoxylated material is shown by formula (VI):
Figure imgf000007_0001
(VI) wherein x of formula (VI) is from about 0 to about 10, preferably from about 0 to about 7, most preferably from about 0 to about 6. Another preferred ethoxylated material has 15 carbons similar to the formula (VI), wherein ethoxylation is from about 0 to about 10, preferably from about 0 to about 7, most preferably from about 0 to about 6. Also preferred ethoxlated materials comprise blends of carbon chainlengths from 10 to 16, wherein ethoxylation is from about 0 to about 10, preferably from about 0 to about7, and most preferably from about 0 to about 6.. Gemini Surfactants The surfactant systems of the present invention may optionally comprise a gemini surfactant. Gemini surfactants are compounds having at least two hydrophobic groups and at least one or optionally two hydrophilic groups per molecule have been introduced. These have become known as "gemini surfactants" in the literature, e.g., Chemtech, March 1993, pp 30-33, and J. American Chemical Soc, 115, 10083-10090 (1993) and the references cited therein. A number of the gemini surfactants are reported in the literature, see for example, Okahara et al., J. Japan Oil Chem. Soc. 746 (Yukagaku) (1989); Zhu et al., 67 JAOCS 7,459 (July 1990); Zhu et al., 68 JAOCS 7,539 (1991); Menger et al., J. Am. Chemical Soc. 113, 1451 (1991); Masuyama et al., 41 J. Japan Chem. Soc. 4,301 (1992); Zhu et al., 69 JAOCS 1,30 (January 1992); Zhu et al., 69 JAOCS 7,626 July 1992); Menger et al., 115 J. Am. Chem. Soc. 2, 10083 (1993); Rosen, Chemtech 30 (March 1993); and Gao et al., 71 JAOCS 7,771 (July 1994). A number of gemini surfactants have also been disclosed in the patent literature including US 5,160,450, US 3,244,724, US 2,524,218, 2,530,147, 2,374,354, and US 6,358,914. The following are nonlimiting examples of Gemini surfactants suitable for use in the present invention:
Figure imgf000008_0001
wherein Ri, and R2 of formulas (VII) - (VIII) and R of formulas (IX), (X) and (XI), are same or different and are independently selected from H, Cι.3o alkyl, C2.2o alkenyl; and x of formula (X) is from 0.1 to 60.
Anionic Surfactants The surfactant systems of the present invention may optionally comprise an anionic surfactant. Nonlimiting examples of anionic surfactants useful herein are listed below wherein the indicated carbon ranges are that of the hydrophobic portion (tail) of the surfactant. a) Cπ-Cis alkyl benzene sulfonates (LAS); b) Cιo-C20 primary, branched-chain and random alkyl sulfates (AS); c) Cio-Cis secondary (2,3) alkyl sulfates having formulas (XII) and (XIII):
OSO3 " Ivf OSO3" M I CH3(CH2)X(CH)CH3 or CH3(CH2)y(CH)CH2CH3 (XII) (XIII) M in formulas (XII) and (XIII) is hydrogen or a cation which provides charge neutrality. Non-limiting examples of preferred cations include sodium, potassium, ammonium, and mixtures thereof. Wherein x in formula (XII) is an integer of at least about 7, preferably at least about 9; y in formula (XIII) is an integer of at least 8, preferably at least about 9; d) Cιo-Cι8 alkyl alkoxy sulfates (AEXS) wherein preferably x is from 1-30; e) Cιo-Cι8 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548.; i) Cι2-C20 methyl ester sulfonate (MES); j) Cio - Cis alpha-olefϊn sulfonate (AOS); and k) C6 - C20 Sulfosuccinates available under the trade names of AEROSOL OT® and AEROSOL TR-70® (ex. Cytec). In one embodiment, the surfactant system of the present invention comprises from about 0.1 wt% to about to about 50 wt%, preferably from about 0.1 wt% to about 25 wt%, preferably from about 1 wt% to about 15 wt%, preferably from about 5 wt% to about 15 wt% by weight of the surfactant system of at least one silicone surfactant and from about 0.1 wt% to about 99 wt%, preferably from about 0.1 wt% to about 85 wt%, preferably from about 10 wt% to about 60 wt%, and preferably from about 35 wt% to about 85 wt% by weight of the surfactant system of at least one nonionic surfactant; from about 0 wt% to about 50 wt%, preferably from about 0 wt% to about 45 wt%, preferably from about 0 wt% to about 10 wt% by weight of the surfactant system of at least one gemini surfactant; from about 0 wt% to about 50 wt%, from about 0 wt% to about 45 wt%, preferably from about 10 wt% to about 50 wt%, preferably from about 15 wt% to about 45 wt% by weight of the surfactant system of at least one anionic surfactant. Another embodiment of the surfactant system of the present invention comprises from about 0.1 wt% to about to about 50 wt%, preferably from about 0.1 wt% to about 25 wt%, preferably from about 1 wt% to about 15 wt%, preferably from about 5 wt% to about 15 wt% by weight of the surfactant system of at least one silicone surfactant; from about 0.1 wt% to about 99 wt%, preferably from about 0.1 wt% to about 85 wt%, preferably from about 0.1 wt% to about 75 wt%, preferably from about 10 wt% to about 60 wt%, preferably from about 25 wt% to about 85 wt%, and preferably from about 35 wt% to about 99 wt% by weight of the surfactant system of at least one nonionic surfactant; from about 0 wt% to about 50 wt%, preferably from about 0 wt% to about 45 wt%, preferably from about 0 wt% to about 10 wt% by weight of the surfactant system of at least one gemini surfactant; from about 0 wt% to about 50 wt%, from about 0 wt% to about 45 wt%, preferably from about 10 wt% to about 50 wt%, preferably from about 15 wt% to about 45 wt% by weight of the surfactant system of at least one anionic surfactant; and the surfactant system further comprising from about 0 wt% to about 75 wt% by weight of the surfactant system of at least one fatty acid, fatty acid salt, and mixtures thereof. Optionally if a fatty acid, fatty acid salt, and mixtures thereof that is not present then an anionic surfactant must be present. In another embodiment, the consumable detergent composition comprises a surfactant system comprises from about 0.1 wt% to about 30 wt%, preferably from about 0.1 wt% to about 20 wt%, preferably from about 0.1 wt% to about 15 wt%, preferably from about 1 wt% to about 15 wt%, preferably from about 5 wt% to about 15 wt%, by weight of the consumable detergent composition of at least one silicone surfactant; from about 0.1 wt% to about 99 wt%, preferably from about 10 wt% to about 99 wt%; preferably from about 10 wt% to about 60 wt%, preferably from about 35 wt% to about 75 wt%, preferably from about 40 wt% to about 70 wt% by weight of the consumable detergent composition of at least one nonionic surfactant; from about 0 wt% to about 50 wt%, from about 0 wt% to about 30 wt%, preferably from about 0 wt% to about 20 wt%, preferably from about 0 wt% to about 10 wt%, by weight of the consumable detergent composition of at least one gemini surfactant; from about 0 wt% to about 75 wt%, preferably from about 0 wt% to about 50 wt%, preferably from about 0 wt% to about 25 wt%, preferably from about 10 wt% to about 75 wt%, by weight of the consumable detergent composition of at least one anionic surfactant. In another embodiment, the consumable detergent composition comprises a surfactant system comprises from about 0.1 wt% to about 30 wt%, preferably from about 0.1 wt% to about 20 wt%, preferably from about 0.1 wt% to about 15 wt%, preferably from about 1 wt% to about 15 wt%, preferably from about 5 wt% to about 15 wt%, by weight of the consumable detergent composition of at least one silicone surfactant; from about 0.1 wt% to about 99 wt%, preferably from about 0.1% to about 75 wt%, preferably from about 10 wt% to about 99 wt%; preferably from 10 wt% to about 75 wt%, preferably from about 10 wt% to about 60 wt%, preferably from about 35 wt% to about 75 wt%, preferably from about 40 wt% to about 70 wt% by weight of the consumable detergent composition of at least one nonionic surfactant; from about 0 wt% to about 50 wt%, from about 0 wt% to about 30 wt%, preferably from about 0 wt% to about 20 wt%, preferably from about 0 wt% to about 10 wt%, preferably from about 15 wt% to about 30 wt%, by weight of the consumable detergent composition of at least one gemini surfactant; from about 0 wt% to about 75 wt%, preferably from about 0 wt% to about 50 wt%, preferably from about 0 wt% to about 25 wt%, preferably from about 10 wt% to about 75 wt%, by weight of the consumable detergent composition of at least one anionic surfactant. Optionally, if the anionic surfactant is not present a fatty acid, fatty acid salt, and mixtures thereof is present. The consumable detergent composition of the present invention may further comprises from about 0 wt% to about 75 wt% by weight of the consumable detergent composition of at least one fatty acid, fatty acid salt, and mixtures thereof. Optionally, if a fatty acid, fatty acid salt, and mixtures thereof that is not present then an anionic surfactant is present. Consumable Detergent Composition The consumable detergent composition of the present invention comprises a surfactant system, optionally a fatty acid, fatty acid salt, and mixtures thereof, optionally a fatty quat, and optionally at least one cleaning adjunct. The surfactant system may be altered dependent upon what type of soil is targeted. Greasy soils, traditionally posing problems in water-based systems, are not as challenging in lipophilic fluid based systems, such as the present invention. However, hydrophilic soils, traditionally posing no problems in water-based systems, now raises challenges in lipophilic fluid based systems. Specifically, hydrophilic soils on cotton fabric articles are especially difficult to address in a non-aqueous solvent based washing system utilizing lipophilic fluid. Lipophilic Fluid "Lipophilic fluid" as used herein means any liquid or mixture of liquids that are immiscible with water at up to 20% by weight of water. In general, a suitable lipophilic fluid can be fully liquid at ambient temperature and pressure, can be an easily melted solid, e.g., one that becomes liquid at temperatures in the range from about 0°C to about 60°C, or can comprise a mixture of liquid and vapor phases at ambient temperatures and pressures, e.g., at 25°C and 101.3 kPa (1 arm) pressure. It is preferred that the lipophilic fluid herein be nonflammable or, have relatively high flash points and/or low VOC characteristics, these terms having conventional meanings as used in the dry cleaning industry, to equal or, preferably, exceed the characteristics of known conventional dry cleaning fluids. Non-limiting examples of suitable lipophilic fluid materials include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerine derivatives such as glycerine ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, low-volatility nonfluorinated organic solvents, diol solvents, other environmentally-friendly solvents and mixtures thereof. "Siloxane" as used herein means silicone fluids that are non-polar and insoluble in water or lower alcohols. Linear siloxanes (see for example US Patents 5,443,747, and 5,977,040) and cyclic siloxanes are useful herein, including the cyclic siloxanes selected from the group consisting of octamethyl-cyclotetrasiloxane (tetramer), dodecamethyl-cyclohexasiloxane (hexamer), and preferably decamethyl-cyclopentasiloxane (pentamer, commonly referred to as "D5"). A preferred siloxane comprises more than about 50% cyclic siloxane pentamer, more preferably more than about 75% cyclic siloxane pentamer, most preferably at least about 90% of the cyclic siloxane pentamer. Also preferred for use herein are siloxanes that are a mixture of cyclic siloxanes having at least about 90% (preferably at least about 95%) pentamer and less than about 10% (preferably less than about 5%) tetramer and/or hexamer. The lipophilic fluid can include any fraction of dry-cleaning solvents, especially newer types including fluorinated solvents, or perfluorinated amines. Some perfluorinated amines such as perfluorotributylamines, while unsuitable for use as lipophilic fluid, may be present as one of many possible adjuncts present in the lipophilic fluid-containing composition. Other suitable lipophilic fluids include, but are not limited to, diol solvent systems e.g., higher diols such as or C8 or higher diols, organosilicone solvents including both cyclic and acyclic types, and the like, and mixtures thereof. Non-limiting examples of low volatility non-fluorinated organic solvents include for example OLEAN® and other polyol esters, or certain relatively nonvolatile biodegradable mid- chain branched petroleum fractions. Non-limiting examples of glycol ethers include propylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-propyl ether, tripropylene glycol t-butyl ether, tripropylene glycol n-butyl ether. Non-limiting examples of other silicone solvents, in addition to the siloxanes, are well known in the literature, see, for example, Kirk Othmer's Encyclopedia of Chemical Technology, and are available from a number of commercial sources, including GE Silicones, Toshiba Silicone, Bayer, and Dow Corning. For example, one suitable silicone solvent is SF-1528 available from GE Silicones. Non-limiting examples of suitable glycerine derivative solvents for use in the methods and/or apparatuses of the present invention include glyercine derivatives having the formula (XIV):
Figure imgf000012_0001
(XIV) wherein R1, R2 and R3 of formula (XIV) are each independently selected from: H; branched or linear, substituted or unsubstituted Cι-C3o alkyl, C2-C30 alkenyl, Cι-C3o alkoxycarbonyl, C3-C30 alkyleneoxyalkyl, C C30 acyloxy, C7-C30 alkylenearyl; C -C30 cycloalkyl; Cδ-C o aryl; and mixtures thereof. Two or more of R1, R2 and R3 of formula (XIV) together can form a C3-C8 aromatic or non-aromatic, heterocyclic or non-heterocyclic ring. Non-limiting examples of suitable glycerine derivative solvents include 2,3-bis(l,l- dimethylethoxy)- 1 -propanol; 2,3-dimethoxy- 1 -propanol; 3-methoxy-2-cyclopentoxy- 1 -propanol; 3-methoxy-l-cyclopentoxy-2-propanol; carbonic acid (2-hydroxy-l-methoxymethyl)ethyl ester methyl ester; glycerol carbonate and mixtures thereof. Non-limiting examples of other environmentally-friendly solvents include lipophilic fluids that have an ozone formation potential of from 0 to about 0.31, lipophilic fluids that have a vapor pressure of from 0 to about 13.3 Pa (0 to about 0.1 mm Hg), and/or lipophilic fluids that have a vapor pressure of greater than 13.3 Pa (0.1 mm Hg), but have an ozone formation potential of from 0 to about 0.31. Non-limiting examples of such lipophilic fluids that have not previously been described above include carbonate solvents (i.e., methyl carbonates, ethyl carbonates, ethylene carbonates, propylene carbonates, glycerine carbonates) and/or succinate solvents (i.e., dimethyl succinates). "Ozone Reactivity" as used herein is a measure of a VOC's ability to form ozone in the atmosphere. It is measured as grams of ozone formed per gram of volatile organics. A methodology to determine ozone reactivity is discussed further in W. P. L. Carter, "Development of Ozone Reactivity Scales of Volatile Organic Compounds", Journal of the Air & Waste Management Association, Vol. 44, Pages 881-899, 1994. "Vapor Pressure" as used can be measured by techniques defined in Method 310 of the California Air Resources Board. Preferably, the lipophilic fluid comprises more than 50% by weight of the lipophilic fluid of cyclopentasiloxanes, ("D5") and/or linear analogs having approximately similar volatility, and optionally complemented by other silicone solvents. Fatty Acid, Fatty Acid Salt. And Mixtures Thereof Consumable detergents composition according to the present invention may comprise a fatty acid, fatty acid salt, and mixtures thereof. Surfactant systems of the present invention may comprise a fatty acid, fatty acid salt, and mixtures thereof, optionally comprising a fatty acid, fatty acid salt, and mixtures thereof when no anionic surfactant is present. Suitable fatty acids and fatty acid salts are suitably selected from mono- and di-carboxylic acids comprising the following hydrophobes: saturated or unsaturated, linear or branched hydrocarbons having 6-30 carbons, preferred are branched and/or saturated mono- and di- carboxylic acids; ethoxylated alcohols, polyalkylene oxides (polypropyleneoxide, polybutyleneoxide, polyhexyleneoxide), including pure homopolymers or any copolymers and oligomers; linear or branched siloxanes, hydroxyl- functionalized silicones, alkoxylated silicones (e.g., ethoxylated/propylated silicones), alkylphosphonates, alkylphosphinates, phosphate monoesters of hydrophobic alcohols, phosphate diesters of hydrophobic alcohols; and mixtures thereof. Suitable fatty acid salts have counterions selected from hydrogen, ammonium, Cι-C2o alkylammonium, sodium, potassium, and the like. Phosphate monoester and diesters of hydrophobic alcohols include Cβ-C2o linear or branched alkyl phosphate monoester or phosphate diesters. The acid form of the phosphate ester (i.e., protonated ester) and corresponding salts are intended to be included. Preferred phosphate monoesters and diesters include those represented by formula (XV): O
RO OR OM (XV) wherein R of formula (XV) is selected from a C6.20 alkyl, silicone and mixtures thereof. M is a suitable counterion selected from hydrogen, sodium, ammonium, Cι-C20 alkylammonium and mixtures thereof. Preferred phosphate monoesters comprise formula (XVI) and phosphate diesters comprise formula (XVII). It would be apparent to one of skill in the art that the alkylphosponates may be selected from a fatty acid and fatty acid salt forms. Not to be limited to the shown formulas, the monester is exemplified in a fatty acid form (formula (XVI)) and the diester is exemplified in a suitable fatty acid salt form (formula (XVII)):
Figure imgf000014_0001
Figure imgf000014_0002
(XVII) Alkylphosphonates may comprise formula (XVIII)
Figure imgf000015_0001
(XVIII) Wherein Ri of formula (XVIII) is selected from a linear or branched C6-C20 alkyl, silicone, and mixtures thereof. R2 of formula (XVIII) is selected from a linear or branched C6-C20 alkyl, silicone, and mixtures thereof. M of formula (XVIII) is a suitable counterion selected from hydrogen, sodium, ammonium, C C2o alkylammonium and mixtures thereof. It would be apparent to one of skill in the art that the alkylphosponates may be selected from a fatty acid and fatty acid salt forms. Not to be limited to the shown formulae, shown in formula (XIX) is an alkylphosphonates fatty acid while an alkylphosphonates fatty acid salt is shown in formula (XX).
Figure imgf000015_0002
(XIX)
Figure imgf000015_0003
(XX)
Alkylphosphinates may comprise formula (XXI):
Figure imgf000015_0004
(XXI)
Wherein Ri of formula (XXI) is selected from a linear or branched C6-C20 alkyl, silicone, and mixtures thereof. M of formula (XXI) is a suitable counterion selected from hydrogen, sodium, ammonium, Cι-C2o alkylammonium and mixtures thereof. It would be apparent to one of skill in the art that the alkylphosphinates may be selected from a fatty acid and fatty acid salt forms. Not to be limited to the shown formulae, shown in formula (XXII) is a alkylphosphinate fatty acid
Figure imgf000016_0001
(XXII)
Fatty acid, fatty acid salt, and mixtures thereof may comprise from about 0 wt% to about 75 wt%, preferably from about 5 wt% to about 40 wt% by weight of the consumable detergent composition of a fatty acid, fatty acid salt, and mixtures thereof. The fatty acid, fatty acid salt, and mixtures thereof have from 2 to 20 carbon atoms, preferably from 10 to 18 carbon atoms. The fatty acid, fatty acid salt, and mixtures thereof may comprise from about 0 wt% to about 75 wt% by weight of the surfactant system, preferably from 0.1 wt% to about 75 wt% by weight of the surfactant system if no anionic surfactant is present. Fatty Ouat The consumable detergent composition according to the present invention may comprise a fatty quat. Fatty quats may comprise from about 0 wt% to about 75 wt%, preferably from about 2 wt% to about 20 wt% by weight of the consumable detergent composition. The fatty quat comprises substituted nitrogen wherein the nitrogen is substituted with at least one moiety comprising from about 2 to about 20 carbon atoms, preferably from about 14 to about 20 carbon atoms. Nonlimited examples of the fatty quat may include conventional fabric softening actives. Such fatty quats may include, but are not limited to dialkyldimethylammonium salts having the formula (XIV). R' 'N^CH^X (XIV) wherein each R' and R" of formula (XIV) are independently selected fromithe group consisting of 12-30 carbon atoms or derived from tallow, coconut oil or soy, X of formula (XIV) is selected from anionic counter ions, including but not limited to Cl" or Br". Nonlimiting examples of the dialkyledimethylammonium salts include: didodecyldimethylammonium bromide (DDAB), dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyidimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, didocosyldimethyl ammonium chloride, dicoconutdimethyl ammonium chloride, ditallowdimethyl ammonium bromide (DTAB). Commercially available examples include, but are not limited to: ADOGEN®, ARQUAD®, TOMAH9®, VARIQUAT®. In one embodiment, the fatty quat comprise the water-soluble quaternary ammonium compounds useful in the present invention having the formula (XV) RiRaRsRtN'X" (XV) wherein R of formula (XV) is C8-Ci6 alkyl, each of R2, R3 and R of formula (XV) are independently Cι-C4 alkyl, CpC hydroxy alkyl, benzyl, and -(C2H 0)xH where x of formula (XV) has a value from 2 to 5, and X of formula (XV) is a anion selected from Cl", Br", methyl sulfate, formate, sulfate, nitrate, and mixtures thereof. Not more than one of R2, R3 or R( of formula (XV) should be selected as benzyl. A preferred fatty quat embodiment has the formula (XVI): (R)4.m-N+[(CH2)n-Y-R2]m X- (XVI) wherein Y of formula (XVI) is selected from -0-(0)C- or -C(0)-0-; m of formula (XVI) is 2 or 3; n of formula (XVI) is from 1 to 4; R of formula (XVI) is selected from Q-β, preferably Cι_3 alkyl group, benzyl, and mixtures thereof; R2 is selected from Cπ-2ι, substituted or unsubstituted hydrocarbonyl having at least partial unsaturated and its counterion X" of formula (XVI); X" of formula (XVI) is selected from Cl", Br", methyl sulfate, formate, sulfate, nitrate, and mixtures thereof. See US 5,545,380. Polar Solvent Compositions according to the present invention may further comprise a polar solvent. Non-limiting examples of polar solvents include: water, alcohols, glycols, polyglycols, ethers, carbonates, dibasic esters, ketones, other oxygenated solvents, and mixtures thereof. Further examples of alcohols include: Cι-C3o alcohols, such as propanol, ethanol, isopropyl alcohol, and the like, benzyl alcohol, and diols such as 1,2-hexanediol. The DOWANOL® series by Dow Chemical are examples of glycols and polyglycols useful in the present invention, such as DOWANOL® TPM, TPnP, DPnB, DPnP, TPnB, PPh, DPM, DPMA, DB, and others. Further examples include propylene glycol, butylene glycol, polybutylene glycol and more hydrophobic glycols. Examples of carbonate solvents are ethylene, propylene and butylene carbonantes such as those available under the JEFFSOL® tradename. Polar solvents for the present invention can be further identified through dispersive (δo), polar (δp) and hydrogen bonding (5H) Hansen solubility parameters. Preferred polar solvents or polar solvent mixtures have fractional polar (fP) and fractional hydrogen bonding (fH) values of fP>0.02 and fH>0.10, where and
Figure imgf000017_0001
more preferably fP>0.05 and fκ>0.20, and most preferably fp>0.07 and fH>0.30. In the consumable detergent composition of the present invention, the levels of polar solvent can be from 0 wt% to about 70 wt%, preferably about 1 wt% to about 50 wt% even more preferably about 1 wt% to about 30 wt% by weight of the consumable detergent composition. In a preferred embodiment, the polar solvent comprises from about 0.1 wt% to about 1 wt%, preferably 0.5 wt% to about 1 wt%, by weight of the consumable detergent composition of water. When the composition of the present invention comprises an amino-functional silicone as the only emulsifying agent, preferred levels of polar solvent are from about 0.01 wt% to about 2 wt%, preferably about 0.05 wt% to about 0.8 wt%, even more preferably about 0.1 wt% to about 0.5 wt% by weight of the consumable detergent composition. When the consumable detergent composition of the present invention comprises higher levels of polar solvent, the detergents compositions preferably comprise from about 2 wt% to about 25 wt%, more preferably from about 5 wt% to about 20 wt%, even more preferably from about 8 wt% to about 15 wt% by weight of the consumable detergent composition. Cleaning Adjuncts The consumable detergent compositions of the present invention optionally further comprise at least one additional cleaning adjunct. The cleaning adjuncts can vary widely and can be used at widely ranging levels. For example, detersive enzymes such as proteases, amylases, cellulases, lipases and the like as well as bleach catalysts including the macrocyclic types having manganese or similar transition metals all useful in laundry and cleaning products can be used herein at very low, or less commonly, higher levels. Cleaning adjuncts that are catalytic, for example enzymes, can be used in "forward" or "reverse" modes, a discovery independently useful from the fabric treating methods of the present invention. For example, a lipolase or other hydrolase may be used, optionally in the presence of alcohols as cleaning adjuncts, to convert fatty acids to esters, thereby increasing their solubility in the lipophilic fluid. This is a "reverse" operation, in contrast with the normal use of this hydrolase in water to convert a less water- soluble fatty ester to a more water-soluble material. In any event, any cleaning adjunct must be suitable for use in combination with a lipophilic fluid in accordance with the present invention. Some suitable cleaning adjuncts include, but are not limited to, builders, surfactants other than those described above with respect to the surfactant system, enzymes, bleach activators, bleach catalysts, bleach boosters, bleaches, alkalinity sources, antibacterial agents, colorants, perfumes, pro-perfumes, finishing aids, finishing polymers, lime soap dispersants, odor control agents, odor neutralizers, polymeric dye transfer inhibiting agents, crystal growth inhibitors, photobleaches, heavy metal ion sequestrants, anti-tarnishing agents, anti-microbial agents, anti- oxidants, anti-redeposition agents, soil release polymers, electrolytes, pH modifiers, thickeners, abrasives, divalent or trivalent ions, metal ion salts, enzyme stabilizers, corrosion inhibitors, diamines or polyamines and/or their alkoxylates, suds stabilizing polymers, solvents, process aids, fabric softening agents, optical brighteners, hydrotropes, suds or foam suppressors, suds or foam boosters and mixtures thereof. Optionally, the consumable detergent compositions useful for the present invention may comprise processing aids. Processing aids facilitate the formation of the consumable detergent compositions by maintaining the fluidity and/or homogeneity of the consumable detergent composition, and/or aiding in the dilution process. Processing aids suitable for the present invention are solvents, preferably solvents other than those described above, hydrotropes, and/or surfactants, preferably surfactants other than those described above with respect to the surfactant system. Particularly preferred processing aids are protic solvents such as aliphatic alcohols, diols, triols, etc. and nonionic surfactants such as ethoxylated fatty alcohols. Processing aids, when present in the consumable detergent compositions, preferably comprise from about 0.02 wt% to about 10 wt%, more preferably from about 0.05 wt% to about 10 wt%, even more preferably from about 0.1 wt% to about 10 wt% by weight of the consumable detergent composition. Processing aids, when present in the consumable detergent compositions, preferably comprise from about 1 wt% to about 75 wt%, more preferably from about 5 wt% to about 50 wt% by weight of the consumable detergent composition. Suitable odor control agents, which may optionally be used as finishing agents, include agents include, cyclodextrins, odor neutralizers, odor blockers and mixtures thereof. Suitable odor neutralizers include aldehydes, flavanoids, metallic salts, water-soluble polymers, zeolites, activated carbon and mixtures thereof. Perfumes and perfumery ingredients useful in the consumable detergent compositions for the present invention comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfumes may comprise extremely complex mixtures of such ingredients. Pro-perfumes are also useful in the present invention. Such materials are those precursors or mixtures thereof capable of chemically reacting, e.g., by hydrolysis, to release a perfume. Bleaches, especially oxygen bleaches, are another type of laundry additive suitable for use in the consumable detergent compositions for the present invention. This is especially the case for the activated and catalyzed forms with such bleach activators as nonanoyloxybenzenesulfonate and/or any of its linear or branched higher or lower homologs, and/or tetraacetylethylenediamine and/or any of its derivatives or derivatives of phthaloylimidoperoxycaproic acid (PAP; available from Ausimont SpA under trademane EUROCO®) or other imido- or amido-substituted bleach activators including the lactam types, or more generally any mixture of hydrophilic and/or hydrophobic bleach activators (especially acyl derivatives including those of the Cβ-Ciβ substituted oxybenzenesulfonates). Also suitable are organic or inorganic peracids both including PAP and other than PAP. Suitable organic or inorganic peracids for use herein include, but are not limited to: percarboxylic acids and salts; percarbonic acids and salts; perimidic acids and salts; peroxymonosulfuric acids and salts; persulphates such as monopersulfate; peroxyacids such as diperoxydodecandioic acid (DPDA); magnesium peroxyphthalic acid; perlauric acid; perbenzoic and alkylperbenzoic acids; and mixtures thereof. Detersive enzymes such as proteases, amylases, cellulases, lipases and the like as well as bleach catalysts including the macrocyclic types having manganese or similar transition metals all useful in laundry and cleaning products can be used herein at very low, or less commonly, higher levels. For example, a lipolase or other hydrolase may be used, optionally in the presence of alcohols as laundry additives, to convert fatty acids to esters, thereby increasing their solubility in the lipohilic fluid. Nonlimiting examples of finishing polymers that are commercially available are: polyvinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, such as Copolymer 958®, weight average molecular weight of about 100,000 daltons and Copolymer 937®, weight average molecular weight of about 1,000,000 daltons, available from GAF Chemicals Corporation; adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer, such as CARTARETIN F-4® and F-23®, available from Sandoz Chemicals Corporation; methacryloyl ethyl betaine/methacrylates copolymer, such as DIAFORMER Z-SM®, available from Mitsubishi Chemicals Corporation; polyvinyl alcohol copolymer resin, such as VINEX 2019®, available from Air Products and Chemicals or MOWEOl®, available from Clariant; adipic acid/epoxypropyl diethylenetriamine copolymer, such as DELSETTE 101®, available from Hercules Incorporated; polyamine resins, such as CYPRO 515®, available from Cytec Industries; poly quaternary amine resins, such as KYMENE 557H®, available from Hercules Incorporated; and polyvinylpyrrolidone/acrylic acid, such as SOKALAN EG 310®, available from BASF. The cleaning additive may also be an antistatic agent. Any suitable well-known antistatic agents used in conventional laundering and dry cleaning are suitable for use in the consumable detergent compositions and methods of the present invention. Especially suitable as antistatic agents are the subset of fabric softeners which are known to provide antistatic benefits. For example those fabric softeners that have a fatty acyl group which has an iodine value of above 20, such as N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methylsulfate. However, it is to be understood that the term antistatic agent is not to be limited to just this subset of fabric softeners and includes all antistatic agents. Preferred insect and moth repellent laundry additives useful in the compositions of the present invention are perfume ingredients, such as citronellol, citronellal, citral, linalool, cedar extract, geranium oil, sandalwood oil, 2-(diethylphenoxy)ethanol, 1-dodecene, etc. Other examples of insect and/or moth repellents useful in the compositions of the present invention are disclosed in U.S. Pat. Nos. 4,449,987; 4,693,890; 4,696,676; 4,933,371; 5,030,660; 5,196,200; and in "Semio Activity of Flavor and Fragrance Molecules on Various Insect Species", B.D. Mookherjee et al., published in Bioactive Volatile Compounds from Plants. ACS Symposium Series 525, R. Teranishi, R.G. Buttery, and H. Sugisawa, 1993, pp. 35-48. Method of Cleaning The surfactant system and the consumable detergent composition may be utilized to clean fabric articles in a non-aqueous solvent based washing system utilizing lipophilic fluid. The method includes the step of contacting a cleaning solution, comprising the surfactant system or the consumable detergent composition of the present invention and a lipophilic fluid, with a fabric article and then extracting the cleaning solution from the fabric article. The method may further comprise a pre-step of mixing the surfactant system or the consumable detergent composition with a lipophilic fluid to form a cleaning solution. The method may further comprise the steps of agitating the fabric article in the cleaning solution; scrubbing the fabric article; drying the fabric article and any combination thereof. The drying step may include heat drying, air drying, or any other known form of drying a fabric article.
Examples
Figure imgf000021_0001
Figure imgf000022_0001
'TERGITOL 15-S-3® - available from Dow (Union Carbide Corporation)
2AEROSOL TR® 70% - available from CYTEX.
3ENVIROGEM ADOl® - available from Air Products
4See US 5,545,340
5XS-69B5476 - available from General Electric
6TSF4446 - available from General Electric
Figure imgf000022_0002
Figure imgf000023_0001
2AEROSOL TR® 70% - available from CYTEX. 3ENVIROGEM ADOl® - available from Air Products 4See US 5,545,340
5XS-69B5476 - available from General Electric 6TSF4446 - available from General Electric
Figure imgf000023_0002
ERGITOL 15-S-3® - available from Dow (Union Carbide Corporation) 2AEROSOL TR® 70% - available from CYTEX. 3ENVIROGEM ADOl® - available from Air Products 4See US 5,545,340 5XS-69B5476 - available from General Electric 6TSF4446 - available from General Electric
Figure imgf000024_0001
2See US 5,545,340
3TSF4446 - available from General Electric
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention. All documents cited are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.

Claims

What is claimed is:
1. A surfactant system for use in a lipophilic liquid comprising: a) from about 0.1 wt% to about 30 wt% of a silicone surfactant b) from about 0.1 wt% to about 99 wt% of a nonionic surfactant; c) from 0 wt% to about 50 wt% of a gemini surfactant; d) from 0 wt% to about 50 wt% of a anionic surfactant; and
2. The surfactant system of Claim 1 wherein the surfactant system further comprises: e) from about 0.1 wt% to about 75 wt% of a fatty acid, fatty acid salt and mixtures thereof.
3. The surfactant system of Claim 1 wherein the nonionic surfactant is selected from the group consisting of: i) secondary alcohol surfactant having a hydrophobic tail comprising from about 10 to about 20 carbons; ii) secondary alkoxylated alcohol surfactant having a hydrophobic tail comprising from about 10 to about 20 carbons and an average of from 0.1 to about 10 alkoxy moieties, wherein the alkoxy moieties are selected from ethoxy, propoxy, butoxy, and any combination thereof; iii) primary alcohol surfactant having a hydrophobic tail comprising from about 10 to about 20 carbons; iv) primary alkoxylated alcohol surfactant having a hydrophobic tail comprising from about 10 to about 20 carbons and an average of from 0.1 to about 10 alkoxy moieties, wherein the alkoxy moieties are selected from ethoxy, propoxy, butoxy, and any combination thereof; and v) any combination thereof.
4. The surfactant system of Claim 2 wherein the fatty acid, fatty acid salt and mixtures thereof is selected from the group consisting of mono- and di-carboxylic acids comprising the following hydrophobes: saturated or unsaturated, linear or branched hydrocarbons having 6-30 carbons, preferred are branched and/or saturated mono- and di- carboxylic acids; ethoxylated alcohols, polyalkylene oxides; linear or branched siloxanes, hydroxyl-functionalized silicones, alkoxylated silicones alkylphosphonates, alkylphosphinates, phosphate monoesters of hydrophobic alcohols, phosphate diesters of hydrophobic alcohols; and mixtures thereof.
5. The surfactant system of Claim 1 wherein the surfactant system comprises from about 0.1 wt% to about 50 wt%, by weight of the surfactant system of a gemini surfactant selected from the group consisting of:
Figure imgf000026_0001
Figure imgf000026_0002
; and any mixtures thereof, wherein R, Ri, and R2 of the gemini surfactant are same or different and are independently selected from H, Cι.30 alkyl, C2.20 alkenyl; and x is from 0.1 to 60.
6. A cleaning solution comprising the surfactant system according to claim 1 and a lipophilic fluid.
7. A cleaning solution according to Claim 7 wherein the lipophilic fluid is decamethacyclopentasiloxane.
8. A consumable detergent composition for use in a lipophilic fluid comprising: a) from about 1 wt% to about 100 wt% of the consumable detergent composition of a surfactant system comprising at least two surfactants consisting of; i) from about 0.1 wt% to about 75 wt% of the consumable detergent composition of a silicone surfactant; ii) from about 0.1 wt% to about 99 wt% of the consumable detergent composition of a nonionic surfactant; and iii) from 0 wt% to about 40 wt% of the consumable detergent composition of a gemini surfactant; iv) from 0 wt% to about 75 wt% of the consumable detergent composition of a anionic surfactant; b) from 0 wt% to about 75 wt% of the consumable detergent composition of a fatty acid, fatty acid salt and mixtures thereof having a hydrophobic tail comprising from 2 to 20 carbon atoms; c) from 0 wt% to about 75 wt% of the consumable detergent composition of a fatty quat comprising a nitrogen substituted by at least one hydrophobic tail comprising from 2 to 20 carbon atoms; and d) from 0 wt% to about 75 wt%, by weight of the consumable detergent composition of a polar solvent, a mixture of polar solvents and adjuncts.
9. A consumable detergent composition according to Claim 10 further comprising from about 5 wt% to about 40 wt% of the consumable detergent composition of the fatty acid, fatty acid salt and mixtures thereof and from about 2 wt% to about 30 wt% of the consumable detergent composition of a fatty quat.
10. A method of using the cleaning solution of Claim 7 comprising the steps of: a) contacting a cleaning solution with a fabric article; and b) extracting the cleaning solution from the fabric article.
PCT/US2004/020879 2003-06-27 2004-06-28 Surfactant system for use in a lipophilic fluid WO2005003439A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP04756350A EP1639187A1 (en) 2003-06-27 2004-06-28 Surfactant system for use in a lipophilic fluid
CA002525511A CA2525511A1 (en) 2003-06-27 2004-06-28 Surfactant system for use in a lipophilic fluid
BRPI0411899-5A BRPI0411899A (en) 2003-06-27 2004-06-28 surfactant system for use in a lipophilic fluid
MXPA05013669A MXPA05013669A (en) 2003-06-27 2004-06-28 Surfactant system for use in a lipophilic fluid.
AU2004254609A AU2004254609A1 (en) 2003-06-27 2004-06-28 Surfactant system for use in a lipophilic fluid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US48334503P 2003-06-27 2003-06-27
US60/483,345 2003-06-27

Publications (1)

Publication Number Publication Date
WO2005003439A1 true WO2005003439A1 (en) 2005-01-13

Family

ID=33563922

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2004/020879 WO2005003439A1 (en) 2003-06-27 2004-06-28 Surfactant system for use in a lipophilic fluid

Country Status (8)

Country Link
US (1) US7202202B2 (en)
EP (1) EP1639187A1 (en)
CN (1) CN1813094A (en)
AU (1) AU2004254609A1 (en)
BR (1) BRPI0411899A (en)
CA (1) CA2525511A1 (en)
MX (1) MXPA05013669A (en)
WO (1) WO2005003439A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102309945A (en) * 2010-07-05 2012-01-11 深圳市美凯特科技有限公司 Multicomponent surface active agent and preparation method thereof
WO2016191103A1 (en) * 2015-05-22 2016-12-01 The Procter & Gamble Company Method of making surfactant compositions and detergent compositions comprising alkoxylatep glycerine as a solvent
CN111346571A (en) * 2020-03-23 2020-06-30 佛山市天宝利硅工程科技有限公司 Sulfate-based anionic gemini surfactant and preparation method thereof

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070056119A1 (en) * 2003-06-27 2007-03-15 Gardner Robb R Method for treating hydrophilic stains in a lipophlic fluid system
US8148315B2 (en) * 2003-06-27 2012-04-03 The Procter & Gamble Company Method for uniform deposition of fabric care actives in a non-aqueous fabric treatment system
US20050000030A1 (en) * 2003-06-27 2005-01-06 Dupont Jeffrey Scott Fabric care compositions for lipophilic fluid systems
US20040266643A1 (en) * 2003-06-27 2004-12-30 The Procter & Gamble Company Fabric article treatment composition for use in a lipophilic fluid system
US7318843B2 (en) * 2003-06-27 2008-01-15 The Procter & Gamble Company Fabric care composition and method for using same
US7202202B2 (en) 2003-06-27 2007-04-10 The Procter & Gamble Company Consumable detergent composition for use in a lipophilic fluid
US20050129478A1 (en) * 2003-08-08 2005-06-16 Toles Orville L. Storage apparatus
US9650558B2 (en) * 2011-02-02 2017-05-16 Baker Hughes Incorporated Oil field treatment fluids
AR104725A1 (en) 2015-05-22 2017-08-09 Procter & Gamble SURFACTANT COMPOSITIONS AND DETERGENTS CONTAINING ETOXYLED GLYCERINE
US9932546B2 (en) 2015-05-22 2018-04-03 The Procter & Gamble Company Surfactant and detergent compositions containing propoxylated glycerine
CN111346570B (en) * 2020-03-23 2022-02-18 佛山市天宝利硅工程科技有限公司 Sulfonic anion gemini surfactant and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1043443A1 (en) * 1999-04-09 2000-10-11 General Electric Company Cleaning processes and compositions
WO2002097024A1 (en) * 2001-05-30 2002-12-05 Nof Corporation Detergent composition for dry cleaning
WO2003006733A1 (en) * 2001-07-10 2003-01-23 The Procter & Gamble Company Compositions and methods for removal of incidental soils from fabric articles

Family Cites Families (100)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE522094A (en) 1952-08-12
BE611618A (en) 1960-12-23
NL135412C (en) 1965-07-15
CH1702468D (en) 1967-12-02
BE756805A (en) 1969-09-29 1971-03-29 Dow Chemical Co METHOD AND COMPOSITIONS FOR PROCESSING FLEXIBLE SUBSTRATES SUCH AS FABRICS OR PAPER
GB1315843A (en) 1970-05-05 1973-05-02 Ici Ltd Emulsions
GB1364452A (en) 1970-11-06 1974-08-21 Ici Ltd Application of finishing agents
FR2205562B1 (en) 1972-11-09 1976-10-29 Rhone Progil
US4124517A (en) 1975-09-22 1978-11-07 Daikin Kogyo Kabushiki Kaisha Dry cleaning composition
JPS531204A (en) 1976-06-25 1978-01-09 Kao Corp Nonaqueous detergent compositions
DE2628480A1 (en) 1976-06-25 1978-01-05 Oreal Cleaning compsn. for fabrics - contg. emulsion of water and organic solvent
JPS5318646A (en) 1976-08-03 1978-02-21 Japan Exlan Co Ltd Soil conditioner
DE2644073C3 (en) 1976-09-30 1979-11-29 Henkel Kgaa, 4000 Duesseldorf Detergent booster for dry cleaning textiles
JPS5354208A (en) 1976-10-27 1978-05-17 Kao Corp Detergent composition for dry cleaning
DE3581421D1 (en) * 1984-03-15 1991-02-28 Procter & Gamble HAIR TREATMENT WITH CONDITIONING PROPERTIES.
US4685930A (en) 1984-11-13 1987-08-11 Dow Corning Corporation Method for cleaning textiles with cyclic siloxanes
CA1239326A (en) 1984-11-13 1988-07-19 Dow Corning Corporation Method for cleaning textiles with cyclic siloxanes
US4639321A (en) 1985-01-22 1987-01-27 The Procter And Gamble Company Liquid detergent compositions containing organo-functional polysiloxanes
US4708807A (en) 1986-04-30 1987-11-24 Dow Corning Corporation Cleaning and waterproofing composition
US4824602A (en) * 1986-10-27 1989-04-25 The Procter & Gamble Company Processes for purification of quaternary cationic surfactant materials and cosmetic compositions containing same
DE3739711A1 (en) 1987-11-24 1989-06-08 Kreussler Chem Fab Use of polydialkylcyclosiloxanes as dry-cleaning solvents
US5273684A (en) * 1988-07-27 1993-12-28 Ciba-Geigy Corporation Composition for wetting hydrophobic capillary materials and the use thereof
EP0360736B1 (en) * 1988-09-01 1994-09-28 Ciba-Geigy Ag Aqueous wetting and detergent composition stable in hard water, its production and use in textile pretreatment
US4911853A (en) 1988-12-21 1990-03-27 The Procter & Gamble Company Dry cleaning fluid with curable amine functional silicone for fabric wrinkle reduction
JPH0768115B2 (en) 1989-05-17 1995-07-26 花王株式会社 Cleaning composition
DE3925846A1 (en) 1989-08-04 1991-02-14 Huels Chemische Werke Ag EMULSIFIERS FOR THE PRODUCTION OF STABLE, AQUEOUS POLYSILOXANE OR POLYSILOXANE PARAFFINOEL EMULSIONS
US5057240A (en) 1989-10-10 1991-10-15 Dow Corning Corporation Liquid detergent fabric softening laundering composition
MY118065A (en) 1989-10-26 2004-08-30 Toshiba Silicone Cleaning compositions
JPH04245970A (en) 1991-01-28 1992-09-02 Mitsubishi Heavy Ind Ltd Dry-cleaning method
GB9102757D0 (en) * 1991-02-08 1991-03-27 Albright & Wilson Biocidal and agrochemical suspensions
JPH05171566A (en) 1991-12-26 1993-07-09 Nikka Chem Co Ltd Finishing agent for dry cleaning
BR9405958A (en) 1993-04-02 1995-12-12 Dow Chemical Co Continuous microemulsion of single phase oil concentrated cleaning emulsion and method for cleaning metal with grease
US5741760A (en) * 1993-08-04 1998-04-21 Colgate-Palmolive Company Aqueous cleaning composition which may be in microemulsion form comprising polyalkylene oxide-polydimethyl siloxane
US5540853A (en) * 1994-10-20 1996-07-30 The Procter & Gamble Company Personal treatment compositions and/or cosmetic compositions containing enduring perfume
US5876510A (en) 1995-03-09 1999-03-02 The Dow Chemical Company Process for cleaning articles
US6036727A (en) 1995-06-05 2000-03-14 Creative Products Resource, Inc. Anhydrous dry-cleaning compositions containing polysulfonic acid, and dry-cleaning kits for delicate fabrics
GB9604849D0 (en) 1996-03-07 1996-05-08 Reckitt & Colman Inc Improvements in or relating to organic compositions
US5705562A (en) 1995-11-20 1998-01-06 Dow Corning Corporation Spontaneously formed clear silicone microemulsions
US5985177A (en) * 1995-12-14 1999-11-16 Shiseido Co., Ltd. O/W/O type multiple emulsion and method of preparing the same
US6086903A (en) * 1996-02-26 2000-07-11 The Proctor & Gamble Company Personal treatment compositions and/or cosmetic compositions containing enduring perfume
FR2751532B1 (en) * 1996-07-23 1998-08-28 Oreal WASHING AND CONDITIONING COMPOSITIONS BASED ON SILICONE AND DIALKYLETHER
US6060546A (en) 1996-09-05 2000-05-09 General Electric Company Non-aqueous silicone emulsions
US6114298A (en) 1996-11-13 2000-09-05 The Procter & Gamble Company Hard surface cleaning and disinfecting compositions comprising essential oils
US5888250A (en) 1997-04-04 1999-03-30 Rynex Holdings Ltd. Biodegradable dry cleaning solvent
US6273919B1 (en) 1997-04-04 2001-08-14 Rynex Holdings Ltd. Biodegradable ether dry cleaning solvent
GB9708182D0 (en) 1997-04-23 1997-06-11 Dow Corning Sa A method of making silicone in water emulsions
US6056789A (en) 1997-08-22 2000-05-02 Greenearth Cleaning Llc. Closed loop dry cleaning method and solvent
US6042618A (en) 1997-08-22 2000-03-28 Greenearth Cleaning Llc Dry cleaning method and solvent
US5865852A (en) 1997-08-22 1999-02-02 Berndt; Dieter R. Dry cleaning method and solvent
US5942007A (en) 1997-08-22 1999-08-24 Greenearth Cleaning, Llp Dry cleaning method and solvent
US6042617A (en) 1997-08-22 2000-03-28 Greenearth Cleaning, Llc Dry cleaning method and modified solvent
US6063135A (en) 1997-08-22 2000-05-16 Greenearth Cleaning Llc Dry cleaning method and solvent/detergent mixture
US6059845A (en) 1997-08-22 2000-05-09 Greenearth Cleaning, Llc Dry cleaning apparatus and method capable of utilizing a siloxane composition as a solvent
US5925469A (en) * 1997-12-18 1999-07-20 Dow Corning Corporation Organopolysiloxane emulsions
DE19908170A1 (en) 1998-03-05 1999-10-21 J P Haas Gmbh & Co Kg Electrolyte-free liquid laundry detergent composition
US6335768B1 (en) 1998-05-04 2002-01-01 Motorola Inc. Method and system for broadcasting digital audio and video to an analog wireless device
JPH11323381A (en) 1998-05-08 1999-11-26 Kao Corp Detergent for dry cleaning
US6200943B1 (en) 1998-05-28 2001-03-13 Micell Technologies, Inc. Combination surfactant systems for use in carbon dioxide-based cleaning formulations
US6136778A (en) 1998-07-22 2000-10-24 Kamiya; Akira Environment safeguarding aqueous detergent composition comprising essential oils
US6083901A (en) 1998-08-28 2000-07-04 General Electric Company Emulsions of fragrance releasing silicon compounds
TW374095B (en) 1998-10-07 1999-11-11 Dow Corning Taiwan Inc A process for cleaning textile
US6013683A (en) 1998-12-17 2000-01-11 Dow Corning Corporation Single phase silicone and water compositions
DE60011691T2 (en) 1999-03-31 2005-07-07 General Electric Co. Composition and process for dry cleaning
JP2000290689A (en) 1999-04-05 2000-10-17 Shin Etsu Chem Co Ltd Detergent for dry cleaning
EP1173537A1 (en) 1999-04-16 2002-01-23 The Dow Chemical Company Method and composition for reduced water damage laundry care
FR2795634A1 (en) * 1999-06-30 2001-01-05 Oreal MASCARA COMPRISING FILM-FORMING POLYMERS
GB9915964D0 (en) 1999-07-07 1999-09-08 Unilever Plc Fabric conditioning composition
WO2001021501A1 (en) * 1999-09-20 2001-03-29 The Procter & Gamble Company Article for the delivery of foam products
US6309425B1 (en) 1999-10-12 2001-10-30 Unilever Home & Personal Care, Usa, Division Of Conopco, Inc. Cleaning composition and method for using the same
US6312476B1 (en) 1999-11-10 2001-11-06 General Electric Company Process for removal of odors from silicones
US6258130B1 (en) 1999-11-30 2001-07-10 Unilever Home & Personal Care, A Division Of Conopco, Inc. Dry-cleaning solvent and method for using the same
US6368359B1 (en) 1999-12-17 2002-04-09 General Electric Company Process for stabilization of dry cleaning solutions
US6521580B2 (en) 2000-02-22 2003-02-18 General Electric Company Siloxane dry cleaning composition and process
US6313079B1 (en) 2000-03-02 2001-11-06 Unilever Home & Personal Care Usa, Division Of Conopco Heterocyclic dry-cleaning surfactant and method for using the same
US20020004953A1 (en) 2000-03-03 2002-01-17 Perry Robert J. Siloxane dry cleaning composition and process
US20030074742A1 (en) 2000-03-03 2003-04-24 General Electric Company Siloxane dry cleaning composition and process
US6548465B2 (en) 2000-03-10 2003-04-15 General Electric Company Siloxane dry cleaning composition and process
US6670317B2 (en) * 2000-06-05 2003-12-30 Procter & Gamble Company Fabric care compositions and systems for delivering clean, fresh scent in a lipophilic fluid treatment process
US6939837B2 (en) 2000-06-05 2005-09-06 Procter & Gamble Company Non-immersive method for treating or cleaning fabrics using a siloxane lipophilic fluid
US6706076B2 (en) 2000-06-05 2004-03-16 Procter & Gamble Company Process for separating lipophilic fluid containing emulsions with electric coalescence
US6673764B2 (en) * 2000-06-05 2004-01-06 The Procter & Gamble Company Visual properties for a wash process using a lipophilic fluid based composition containing a colorant
US6828292B2 (en) 2000-06-05 2004-12-07 Procter & Gamble Company Domestic fabric article refreshment in integrated cleaning and treatment processes
US6691536B2 (en) * 2000-06-05 2004-02-17 The Procter & Gamble Company Washing apparatus
US6706677B2 (en) * 2000-06-05 2004-03-16 Procter & Gamble Company Bleaching in conjunction with a lipophilic fluid cleaning regimen
US6610108B2 (en) 2001-03-21 2003-08-26 General Electric Company Vapor phase siloxane dry cleaning process
CA2441595C (en) * 2001-03-23 2012-07-03 Genencor International, Inc. Proteins producing an altered immunogenic response and methods of making and using the same
CA2447885C (en) * 2001-06-22 2009-05-12 The Procter & Gamble Company Fabric care compositions for lipophilic fluid systems
JP2003041290A (en) 2001-08-01 2003-02-13 Nicca Chemical Co Ltd Detergent composition for dry cleaning
US6972279B2 (en) * 2001-09-10 2005-12-06 Procter & Gamble Company Silicone polymers for lipophilic fluid systems
EP1425458A1 (en) * 2001-09-10 2004-06-09 The Procter & Gamble Company Polymers for lipophilic fluid systems
EP1304158A1 (en) 2001-10-09 2003-04-23 Tiense Suikerraffinaderij N.V. Hydrophobically modified saccharide surfactants
ATE341656T1 (en) 2001-12-06 2006-10-15 Procter & Gamble COMPOSITIONS AND METHODS FOR REMOVAL OF SOIL FROM TEXTILE ITEMS USING SOIL MODIFICATION
US6734153B2 (en) * 2001-12-20 2004-05-11 Procter & Gamble Company Treatment of fabric articles with specific fabric care actives
FR2842456B1 (en) * 2002-07-22 2004-12-24 Bourgogne Grasset METHOD FOR TAMPOGRAPHY AND SUBLIMATION MARKING AND SUBLIMABLE TAMPOGRAPHY INKS
US20040033924A1 (en) * 2002-08-14 2004-02-19 Murphy Dennis Stephen Methods for conferring fabric care benefits during laundering
US7202202B2 (en) 2003-06-27 2007-04-10 The Procter & Gamble Company Consumable detergent composition for use in a lipophilic fluid
US20050000030A1 (en) 2003-06-27 2005-01-06 Dupont Jeffrey Scott Fabric care compositions for lipophilic fluid systems
US20040266643A1 (en) 2003-06-27 2004-12-30 The Procter & Gamble Company Fabric article treatment composition for use in a lipophilic fluid system
US8148315B2 (en) 2003-06-27 2012-04-03 The Procter & Gamble Company Method for uniform deposition of fabric care actives in a non-aqueous fabric treatment system
US7318843B2 (en) 2003-06-27 2008-01-15 The Procter & Gamble Company Fabric care composition and method for using same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1043443A1 (en) * 1999-04-09 2000-10-11 General Electric Company Cleaning processes and compositions
WO2002097024A1 (en) * 2001-05-30 2002-12-05 Nof Corporation Detergent composition for dry cleaning
US20040142838A1 (en) * 2001-05-30 2004-07-22 Takaya Azuma Detergent composition for dry cleaning
WO2003006733A1 (en) * 2001-07-10 2003-01-23 The Procter & Gamble Company Compositions and methods for removal of incidental soils from fabric articles

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102309945A (en) * 2010-07-05 2012-01-11 深圳市美凯特科技有限公司 Multicomponent surface active agent and preparation method thereof
CN102309945B (en) * 2010-07-05 2012-12-19 深圳市美凯特科技有限公司 Multicomponent surface active agent and preparation method thereof
WO2016191103A1 (en) * 2015-05-22 2016-12-01 The Procter & Gamble Company Method of making surfactant compositions and detergent compositions comprising alkoxylatep glycerine as a solvent
CN111346571A (en) * 2020-03-23 2020-06-30 佛山市天宝利硅工程科技有限公司 Sulfate-based anionic gemini surfactant and preparation method thereof

Also Published As

Publication number Publication date
US20050009723A1 (en) 2005-01-13
US7202202B2 (en) 2007-04-10
MXPA05013669A (en) 2006-02-24
CN1813094A (en) 2006-08-02
EP1639187A1 (en) 2006-03-29
CA2525511A1 (en) 2005-01-13
BRPI0411899A (en) 2006-08-29
AU2004254609A1 (en) 2005-01-13

Similar Documents

Publication Publication Date Title
US7101835B2 (en) Compositions for lipophilic fluid systems comprising 1,2-hexanediol
AU2002318367A1 (en) Fabric care compositions for lipophilic fluid systems
US6828295B2 (en) Non-silicone polymers for lipophilic fluid systems
US7202202B2 (en) Consumable detergent composition for use in a lipophilic fluid
CA2455959C (en) Silicone polymers for lipophilic fluid systems
EP1639186A1 (en) Fabric care composition and method of using same
US7323014B2 (en) Down the drain cleaning system
US20040226581A1 (en) Method of removing solid waste from home dry cleaning system
US20040117918A1 (en) Fluorine-containing solvents and compositions and methods employing same
US20050223500A1 (en) Solvent treatment of fabric articles
US20040111806A1 (en) Compositions comprising glycol ether solvents and methods employing same
EP1639180A1 (en) Method of removing solid waste from home dry cleaning system

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2525511

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2004756350

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: PA/a/2005/013669

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2006517772

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2004254609

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 20048179571

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 2004254609

Country of ref document: AU

Date of ref document: 20040628

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 2004254609

Country of ref document: AU

WWP Wipo information: published in national office

Ref document number: 2004756350

Country of ref document: EP

ENP Entry into the national phase

Ref document number: PI0411899

Country of ref document: BR