CA2525511A1 - Surfactant system for use in a lipophilic fluid - Google Patents
Surfactant system for use in a lipophilic fluid Download PDFInfo
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- CA2525511A1 CA2525511A1 CA002525511A CA2525511A CA2525511A1 CA 2525511 A1 CA2525511 A1 CA 2525511A1 CA 002525511 A CA002525511 A CA 002525511A CA 2525511 A CA2525511 A CA 2525511A CA 2525511 A1 CA2525511 A1 CA 2525511A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3734—Cyclic silicones
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/82—Compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/162—Organic compounds containing Si
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3738—Alkoxylated silicones
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3742—Nitrogen containing silicones
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
- D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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 Liuophilic 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 gust 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.
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 gust 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 S sy tem 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 polyether siloxane having the formula (I):
MaDbDrCDrrdMr2_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_eXeSi01,2 wherein R' of formula (I) is independently H, or a monovalent hydrocarbon group, X of formula (I) is hydroxyl group, and a of formula (I) is 0 or 1;
M' of formula (I) is selected from C1_4 alkyl, C,_4 hydroalkyl, R23Si0;,2 or mixtures thereof, wherein RZ of formula (I) is independently H, a monovalent hydrocarbon group, or CHZ C6Qø)gO- CzH40 ;,-(C3H60 ; CkHZk)~-R formula II , provided that at least one R of ( ) ( ) ) 3 ( formula (I) is (CHZ)~{C6Q~)gO-(CZH4O);,-(C3H6O);(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; C6Qd of formula (II) is unsubstituted or substituted with Q of formula (II) is independently H, CI_lo alkyl, C1_io alkenyl, and mixtures thereof.
D of formula (I) is R4zSi02,2 wherein R4 of formula (I) is independently H or a monovalent hydrocarbon group;
D' of formula (I) is RSZSiO2i2 wherein RS of formula (I) is independently RZ
of formula (I) provided that at least one RS of formula (I) is (CHZ)~{C6Q4)g0-(C2H4O)h-(C3H6O);(CkH2k)~-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; C6Q4 of formula (III) is unsubstituted or substituted with Q of formula (III) is independently H, CI_IO alkyl, Cl_lo alkenyl, and mixtures thereof.
D" of formula (I) is R62Si02,z wherein R6 of formula (I) is independently H, a monovalent hydrocarbon group or (CHZ);(C6Q4)m(A)n [(L)o (A')p ]q (L°)rZ(G)5 (formula (IV)) wherein 1 of formula (IV) is 1-10; m of formula (IV) is 0 or l; 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, C1_,o alkyl, C,_,o 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 C,_4 fluoroalkyl, a CI_4 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 C1_3o 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 phosphato, 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 C1_3o alkyl or alkenyl, a carbohydrate unsubstituted or substituted with a Cl_lo alkyl or alkenyl or an ammonium;
G of formula (IV) is an anion or cation such as H+, Na++, Li+, K+, NH4+, Ca+2, Mg+a, Cl-, Br , I-, mesylate ortosylate.
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-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units;
b) C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as PLURONIC° from BASF;
c) C14-Czz mid-chain branched alcohols, BA, as discussed in US 6,150,322;
d) C,a-Czz mid-chain branched alkyl alkoxylates, BAEX, wherein x 1-30, as discussed in US
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 S sy tem 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 polyether siloxane having the formula (I):
MaDbDrCDrrdMr2_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_eXeSi01,2 wherein R' of formula (I) is independently H, or a monovalent hydrocarbon group, X of formula (I) is hydroxyl group, and a of formula (I) is 0 or 1;
M' of formula (I) is selected from C1_4 alkyl, C,_4 hydroalkyl, R23Si0;,2 or mixtures thereof, wherein RZ of formula (I) is independently H, a monovalent hydrocarbon group, or CHZ C6Qø)gO- CzH40 ;,-(C3H60 ; CkHZk)~-R formula II , provided that at least one R of ( ) ( ) ) 3 ( formula (I) is (CHZ)~{C6Q~)gO-(CZH4O);,-(C3H6O);(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; C6Qd of formula (II) is unsubstituted or substituted with Q of formula (II) is independently H, CI_lo alkyl, C1_io alkenyl, and mixtures thereof.
D of formula (I) is R4zSi02,2 wherein R4 of formula (I) is independently H or a monovalent hydrocarbon group;
D' of formula (I) is RSZSiO2i2 wherein RS of formula (I) is independently RZ
of formula (I) provided that at least one RS of formula (I) is (CHZ)~{C6Q4)g0-(C2H4O)h-(C3H6O);(CkH2k)~-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; C6Q4 of formula (III) is unsubstituted or substituted with Q of formula (III) is independently H, CI_IO alkyl, Cl_lo alkenyl, and mixtures thereof.
D" of formula (I) is R62Si02,z wherein R6 of formula (I) is independently H, a monovalent hydrocarbon group or (CHZ);(C6Q4)m(A)n [(L)o (A')p ]q (L°)rZ(G)5 (formula (IV)) wherein 1 of formula (IV) is 1-10; m of formula (IV) is 0 or l; 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, C1_,o alkyl, C,_,o 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 C,_4 fluoroalkyl, a CI_4 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 C1_3o 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 phosphato, 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 C1_3o alkyl or alkenyl, a carbohydrate unsubstituted or substituted with a Cl_lo alkyl or alkenyl or an ammonium;
G of formula (IV) is an anion or cation such as H+, Na++, Li+, K+, NH4+, Ca+2, Mg+a, Cl-, Br , I-, mesylate ortosylate.
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-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units;
b) C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as PLURONIC° from BASF;
c) C14-Czz mid-chain branched alcohols, BA, as discussed in US 6,150,322;
d) C,a-Czz mid-chain branched alkyl alkoxylates, BAEX, 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;
Polyhydroxy fatty acid amides as discussed in US 5,332,528, WO 92/06162, WO
93/19146, WO 93119038, 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 R$ 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 -O-, -C(O)O-, -C(O)N(R)-, -CN(O)R- and mixtures thereof, in which R of formula (V), when present, is R$ of formula (V) or hydrogen.
Nonlimiting examples of preferred ethoxylated surfactant are straight-chain, primary alcohol ethoxylates, with R8 of formula (V) being C$-C1$ alkyl and/or alkenyl group, more preferably Cio-Cia, 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-Cl8 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):
O,(CH~CH20)XH
(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 7771 (July 1994).
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;
Polyhydroxy fatty acid amides as discussed in US 5,332,528, WO 92/06162, WO
93/19146, WO 93119038, 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 R$ 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 -O-, -C(O)O-, -C(O)N(R)-, -CN(O)R- and mixtures thereof, in which R of formula (V), when present, is R$ of formula (V) or hydrogen.
Nonlimiting examples of preferred ethoxylated surfactant are straight-chain, primary alcohol ethoxylates, with R8 of formula (V) being C$-C1$ alkyl and/or alkenyl group, more preferably Cio-Cia, 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-Cl8 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):
O,(CH~CH20)XH
(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 7771 (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:
R
Ri R2 OII OII
R~ ~ R~NH R~N~(RO)x (CH2)2 (CH2)2 I I
Rl OH R~ ~ R~NH R~N~(RO)x R2 R2 IOI IpI OR
(VII) (VIII) (IX) (X) (XI) wherein Rl, and RZ of formulas (VII) - (VIII) and R of formulas (IX), (X) and (XI), are same or different and are independently selected from H, C1_3o alkyl, CZ_ZO 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) C1,-C1g alkyl benzene sulfonates (LAS);
b) Clo-Czo primary, branched-chain and random alkyl sulfates (AS);
c) Clo-C18 secondary (2,3) alkyl sulfates having formulas (XII) and (XIII):
OS03- M~ OS03- M~
CH3(CH2)x~C~OHs or CH3(Cg2)y(C~Og2CH3 (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) C,o-CI$ alkyl alkoxy sulfates (AExS) wherein preferably x is from 1-30;
e) C1o-C1$ 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;
6,358,914.
The following are nonlimiting examples of Gemini surfactants suitable for use in the present invention:
R
Ri R2 OII OII
R~ ~ R~NH R~N~(RO)x (CH2)2 (CH2)2 I I
Rl OH R~ ~ R~NH R~N~(RO)x R2 R2 IOI IpI OR
(VII) (VIII) (IX) (X) (XI) wherein Rl, and RZ of formulas (VII) - (VIII) and R of formulas (IX), (X) and (XI), are same or different and are independently selected from H, C1_3o alkyl, CZ_ZO 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) C1,-C1g alkyl benzene sulfonates (LAS);
b) Clo-Czo primary, branched-chain and random alkyl sulfates (AS);
c) Clo-C18 secondary (2,3) alkyl sulfates having formulas (XII) and (XIII):
OS03- M~ OS03- M~
CH3(CH2)x~C~OHs or CH3(Cg2)y(C~Og2CH3 (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) C,o-CI$ alkyl alkoxy sulfates (AExS) wherein preferably x is from 1-30;
e) C1o-C1$ 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) Ctz-Czo methyl ester sulfonate (MES);
j) Clo-CI$ alpha-olefin sulfonate (AOS); and k) C6 - Czo 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.
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) Ctz-Czo methyl ester sulfonate (MES);
j) Clo-CI$ alpha-olefin sulfonate (AOS); and k) C6 - Czo 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.
LlpOphilic 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 atm) 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 "DS"). 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 C6 or C$ 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):
RiO~~ OR3 O~ R2 (XIV) wherein R', RZ and R3 of formula (XIV) are each independently selected from:
H; branched or linear, substituted or unsubstituted Ct-C3o alkyl, CZ-C3o alkenyl, C1-C3o alkoxycarbonyl, C3-C3o alkyleneoxyalkyl, C,-C3o acyloxy, C~-C3o alkylenearyl; C4-C3o cycloalkyl; C6-C3o aryl; and mixtures thereof. Two or more of Rl, Rz 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(1,1-dimethylethoxy)-1-propanol; 2,3-dimethoxy-1-propanol; 3-methoxy-2-cyclopentoxy-1-propanol;
3-methoxy-1-cyclopentoxy-2-propanol; carbonic acid (2-hydroxy-1-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 nun 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, ("DS") 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, CI-Czo alkylammonium, sodium, potassium, and the like.
Phosphate monoester and diesters of hydrophobic alcohols include Cg-CZp 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
P
RO ".~ ~ ~' CR
~D~~I
t ~~;'~
wherein R of fornmla (XV) is selected from a C6_ZO alkyl, silicone and mixtures thereof. M is a suitable counterion selected from hydrogen, sodium, ammonium, C1-CZO
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)):
C
P
C, ~~ ~ '~ O H
OH
~~~.Z), O
~ 00 H
N~
CFi3 (XVII) Alkylphosphonates may comprise formula (XVIII) O
R~ ~~OR2 OM
(XVIII) Wherein Rl of formula (XVIII) is selected from a linear or branched C6-C2o alkyl, silicone, and mixtures thereof. Rz of formula (XVIII) is selected from a linear or branched C6-CZO alkyl, silicone, and mixtures thereof. M of formula (XVIII) is a suitable counterion selected from hydrogen, sodium, ammonium, C1-CZO 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).
~P
\OH
OH
(XIX) II
P\
I O \/ \
C1 s l CH3 XX
Alkylphosphinates may comprise formula (XXI):
O
R1/ ~~R
OM
(XXI) Wherein R, of formula (XXI) is selected from a linear or branched C6-CZO
alkyl, silicone, and mixtures thereof. M of formula (XXI) is a suitable counterion selected from hydrogen, sodium, ammonium, Ci-CZO 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 a -p ~ w OH
(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.
Fa uat 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~R~~~(CH3)zX
(XIV) wherein each R' and R" of formula (XIV) are independently selected from the 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 Bi .
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) RIRZR3R4N~X_ (XV) wherein RI of formula (XV) is C$-C16 alkyl, each of R2, R3 and R4 of formula (XV) are independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(CZH40)XH where x of formula (XV) has a value from 2 to S, 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 R4 of formula (XV) should be selected as benzyl.
A preferred fatty quat embodiment has the formula (XVI):
(R)4-ni NFL(CH2)ri Y-RZ~m X_ (XVI) wherein Y of formula (XVI) is selected from -O-(O)C- or -C(O)-O-; m of fornmla (XVI) is 2 or 3; n of formula (XVI) is from 1 to 4; R of formula (XVI) is selected from C1_6, preferably C1_s alkyl group, benzyl, and mixtures thereof; RZ is selected from Cn-21, 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: CI-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 (8D), polar (SP) and hydrogen bonding (8H) 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 fP=8p~(bD+8P+~H) and fH-SH~(~D+~P+~H)o more preferably fP>0.05 and fH>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.~ 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 ~ wt% to about 15 wt% by weight of the consumable detergent composition.
Cleaninnt~ 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 andlor 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, andlor surfactants, preferably surfactants other than those described above with respect to the surfactant system. Particularly preferred processing aids are erotic 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 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 axe 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, andlor 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 andlor hydrophobic bleach activators (especially acyl derivatives including those of the C6-C16 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 ox MOWEO1~, 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;
polyquaternary 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
Symposiurr~
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 exampleexample example example example #1 #2 #3 #4 #5 Wt% Wt% wt% Wt% wt%
Alkyloxypolyethyleneoxyethanol'25.0 29.6 27.5 0.0 0.0 Sodium bis(tridecyl)sulfosuccinatez0.0 0.0 0.0 25.0 0.0 Alkane diol3 25.0 25.0 25.0 25.0 50.0 Oleic Acid 20.0 20.0 20.0 20.0 20.0 Propylene Glycol 15.4 15.4 15.4 15.4 15.4 Alkyl Succinate Quat 0.0 0.0 0.0 0.0 0.0 Dipalmithyl 4.6 0.0 4.6 4.6 4.6 hydroxyethylammonium methylsulfate (unsaturated) ~
Amino functional polysiloxane52.5 2.5 0.0 2.5 2.5 Dimethyl hydroxypropyl methyl 7.5 7.5 7.5 7.5 7.5 siloxane (ethoxylated)6 Water 0.0 0.0 0.0 0.0 0.0 Total 100.0 100.0 100.0 100.0 100.0 1TERGITOL 15-S-3~ - available from Dow (Union Carbide Corporation) ZAEROSOL TR~ 70% - available from CYTEX.
3ENVIROGEM ADO 1 ~ - available from Air Products 4See US 5,545,340 SXS-69B5476 - available from General Electric 6TSF4446 - available from General Electric exampleexampleexampleexampleexampleexampleexample #6 #7 #8 #9 #10 11 #12 wt% Wt% wt% wt% wt% % t%
Alkyloxypolyethyleneoxy ethanoll 25.0 20.00 18.00 40.00 50.00 59.00 59.00 Sodium bis(tridecyl)sulfosuccinate225.0 0.0 0.0 0.0 0.0 0.0 0.0 Alkane diol3 4.6 20.00 18.00 0.0 0.0 0.0 0.0 Oleic Acid 20.0 20.00 20.00 20.00 20.00 0.0 0.0 Propylene Glycol 15.4 15.60 14.60 15.60 20.00 12.00 12.00 Alkyl Succinate Quat0.0 0.0 5.00 0.0 0.0 0.0 0.0 Dipalmithyl hydroxyethylammonium methylsulfate (unsaturated)0.0 0.0 0.0 0.0 0.0 .00 .00 bis-2-ethylhexylphosphate dicocomethyl ammonium0.0 0.0 0.0 0.0 0.0 15.00 0.0 salt 2-[(2E)-hexadec-2-en-1-yl]
succinate mono (2-ethylhexyl) esterdicocomethyl 0.0 0.0 0.0 0.0 0.0 0.0 15.00 ammonium salt Amino functional 2.5 2.50 2.50 2.50 2.50 0.0 0.0 polysiloxanes Dimethyl hydroxypropyl methyl 7.5 7.5 7.5 7.5 7.5 10.00 10.00 siloxane (ethoxylated)6 Water 0.0 14.40 14.40 14.40 0.0 0.0 0.0 Total 100.0100.0 100.0 100.0 100.0 100.0 100.0 TERGITOL 15-S-3~ - available from Dow (Union Carbide Corporation) ZAEROSOL TR~ 70% - available from CYTEX.
3ENVIROGEM ADO1~ - available from Air Products 4See US 5,545,340 SXS-69B5476 - available from General Electric 6TSF4446 - available from General Electric exampleexampleexampleexampleexampleexampleexample #11 #12 #13 #14 #15 #16 #17 wt% wt% wt% wt% wt% wt% wt%
Alkyloxypolyethyleneoxy ethanol' 65.0 50.0 62.5 47.5 50.0 52.5 57.5 Anionic Surfactant10.0 0.0 5.0 2.5 0.0 5.0 10.0 Fatty acid andlor fatty acid salt 0.0 10.0 5.0 2.5 5.0 0.0 5.0 Propylene Glycol 15.0 15.0 15.0 20.0 20.0 20.0 10.0 Amino functional polysiloxane5 0.0 0.0 2.5 2.5 2.5 2.5 2.5 Dimethyl hydroxypropyl methyl siloxane (ethoxylated)6 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Water 0.0 15.0 0.0 15.0 12.5 10.0 5.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 ,___ _____ 1'~KCil'1'UL 15-S-3C~ - available from Dow (Union Carbide Corporation) ZAEROSOL TR~ 70% - available from CYTEX.
3ENVIROGEM ADO1 ~ - available from Air Products 4See US 5,545,340 S~S-69B5476 - available from General Electric 6TSF4446 - available from General Electric exampleexampleexampleexample ~18 #19 20 ' 21 t% t% wt%
Alkyloxypolyethyleneoxy 59.0059.00 59.00 59.00 ethanol' Propylene Glycol 12.0012.00 12.00 12.00 Dipalmithyl hydroxyethylammonium methylsulfate 4.00 .00 .0 0.0 (unsaturated)2 2-[(2E)-oct-2-en-1-yl] succinic 0.0 0.0 0.0 9.00 acid monobutyl ester bis-2-ethylhexylphosphate dicocomethyl15.000.0 0.0 0.0 ammonium salt 2-[(2E)-hexadec-2-en-1-yl) succinate mono (2-0.0 15.00 0.0 0.0 ethylhexyl) esterdicocomethyl ammonium salt 2-[(2E)-oct-2-en-1-ylJ succinate monobutyl ester 0.0 0.0 15.00 10.00 dicocomethyl ammonium salt Dimethyl hydroxypropyl methyl siloxane10.0010.00 10.00 10.00 (ethoxylated)3 Water 0.0 0.0 0.0 0.0 Total 100 100 100 100 'TERGITOL 15-S-3~ - available from Dow (Union Carbide Corporation) ZSee 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.
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.
LlpOphilic 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 atm) 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 "DS"). 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 C6 or C$ 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):
RiO~~ OR3 O~ R2 (XIV) wherein R', RZ and R3 of formula (XIV) are each independently selected from:
H; branched or linear, substituted or unsubstituted Ct-C3o alkyl, CZ-C3o alkenyl, C1-C3o alkoxycarbonyl, C3-C3o alkyleneoxyalkyl, C,-C3o acyloxy, C~-C3o alkylenearyl; C4-C3o cycloalkyl; C6-C3o aryl; and mixtures thereof. Two or more of Rl, Rz 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(1,1-dimethylethoxy)-1-propanol; 2,3-dimethoxy-1-propanol; 3-methoxy-2-cyclopentoxy-1-propanol;
3-methoxy-1-cyclopentoxy-2-propanol; carbonic acid (2-hydroxy-1-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 nun 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, ("DS") 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, CI-Czo alkylammonium, sodium, potassium, and the like.
Phosphate monoester and diesters of hydrophobic alcohols include Cg-CZp 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
P
RO ".~ ~ ~' CR
~D~~I
t ~~;'~
wherein R of fornmla (XV) is selected from a C6_ZO alkyl, silicone and mixtures thereof. M is a suitable counterion selected from hydrogen, sodium, ammonium, C1-CZO
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)):
C
P
C, ~~ ~ '~ O H
OH
~~~.Z), O
~ 00 H
N~
CFi3 (XVII) Alkylphosphonates may comprise formula (XVIII) O
R~ ~~OR2 OM
(XVIII) Wherein Rl of formula (XVIII) is selected from a linear or branched C6-C2o alkyl, silicone, and mixtures thereof. Rz of formula (XVIII) is selected from a linear or branched C6-CZO alkyl, silicone, and mixtures thereof. M of formula (XVIII) is a suitable counterion selected from hydrogen, sodium, ammonium, C1-CZO 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).
~P
\OH
OH
(XIX) II
P\
I O \/ \
C1 s l CH3 XX
Alkylphosphinates may comprise formula (XXI):
O
R1/ ~~R
OM
(XXI) Wherein R, of formula (XXI) is selected from a linear or branched C6-CZO
alkyl, silicone, and mixtures thereof. M of formula (XXI) is a suitable counterion selected from hydrogen, sodium, ammonium, Ci-CZO 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 a -p ~ w OH
(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.
Fa uat 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~R~~~(CH3)zX
(XIV) wherein each R' and R" of formula (XIV) are independently selected from the 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 Bi .
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) RIRZR3R4N~X_ (XV) wherein RI of formula (XV) is C$-C16 alkyl, each of R2, R3 and R4 of formula (XV) are independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(CZH40)XH where x of formula (XV) has a value from 2 to S, 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 R4 of formula (XV) should be selected as benzyl.
A preferred fatty quat embodiment has the formula (XVI):
(R)4-ni NFL(CH2)ri Y-RZ~m X_ (XVI) wherein Y of formula (XVI) is selected from -O-(O)C- or -C(O)-O-; m of fornmla (XVI) is 2 or 3; n of formula (XVI) is from 1 to 4; R of formula (XVI) is selected from C1_6, preferably C1_s alkyl group, benzyl, and mixtures thereof; RZ is selected from Cn-21, 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: CI-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 (8D), polar (SP) and hydrogen bonding (8H) 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 fP=8p~(bD+8P+~H) and fH-SH~(~D+~P+~H)o more preferably fP>0.05 and fH>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.~ 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 ~ wt% to about 15 wt% by weight of the consumable detergent composition.
Cleaninnt~ 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 andlor 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, andlor surfactants, preferably surfactants other than those described above with respect to the surfactant system. Particularly preferred processing aids are erotic 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 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 axe 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, andlor 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 andlor hydrophobic bleach activators (especially acyl derivatives including those of the C6-C16 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 ox MOWEO1~, 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;
polyquaternary 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
Symposiurr~
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 exampleexample example example example #1 #2 #3 #4 #5 Wt% Wt% wt% Wt% wt%
Alkyloxypolyethyleneoxyethanol'25.0 29.6 27.5 0.0 0.0 Sodium bis(tridecyl)sulfosuccinatez0.0 0.0 0.0 25.0 0.0 Alkane diol3 25.0 25.0 25.0 25.0 50.0 Oleic Acid 20.0 20.0 20.0 20.0 20.0 Propylene Glycol 15.4 15.4 15.4 15.4 15.4 Alkyl Succinate Quat 0.0 0.0 0.0 0.0 0.0 Dipalmithyl 4.6 0.0 4.6 4.6 4.6 hydroxyethylammonium methylsulfate (unsaturated) ~
Amino functional polysiloxane52.5 2.5 0.0 2.5 2.5 Dimethyl hydroxypropyl methyl 7.5 7.5 7.5 7.5 7.5 siloxane (ethoxylated)6 Water 0.0 0.0 0.0 0.0 0.0 Total 100.0 100.0 100.0 100.0 100.0 1TERGITOL 15-S-3~ - available from Dow (Union Carbide Corporation) ZAEROSOL TR~ 70% - available from CYTEX.
3ENVIROGEM ADO 1 ~ - available from Air Products 4See US 5,545,340 SXS-69B5476 - available from General Electric 6TSF4446 - available from General Electric exampleexampleexampleexampleexampleexampleexample #6 #7 #8 #9 #10 11 #12 wt% Wt% wt% wt% wt% % t%
Alkyloxypolyethyleneoxy ethanoll 25.0 20.00 18.00 40.00 50.00 59.00 59.00 Sodium bis(tridecyl)sulfosuccinate225.0 0.0 0.0 0.0 0.0 0.0 0.0 Alkane diol3 4.6 20.00 18.00 0.0 0.0 0.0 0.0 Oleic Acid 20.0 20.00 20.00 20.00 20.00 0.0 0.0 Propylene Glycol 15.4 15.60 14.60 15.60 20.00 12.00 12.00 Alkyl Succinate Quat0.0 0.0 5.00 0.0 0.0 0.0 0.0 Dipalmithyl hydroxyethylammonium methylsulfate (unsaturated)0.0 0.0 0.0 0.0 0.0 .00 .00 bis-2-ethylhexylphosphate dicocomethyl ammonium0.0 0.0 0.0 0.0 0.0 15.00 0.0 salt 2-[(2E)-hexadec-2-en-1-yl]
succinate mono (2-ethylhexyl) esterdicocomethyl 0.0 0.0 0.0 0.0 0.0 0.0 15.00 ammonium salt Amino functional 2.5 2.50 2.50 2.50 2.50 0.0 0.0 polysiloxanes Dimethyl hydroxypropyl methyl 7.5 7.5 7.5 7.5 7.5 10.00 10.00 siloxane (ethoxylated)6 Water 0.0 14.40 14.40 14.40 0.0 0.0 0.0 Total 100.0100.0 100.0 100.0 100.0 100.0 100.0 TERGITOL 15-S-3~ - available from Dow (Union Carbide Corporation) ZAEROSOL TR~ 70% - available from CYTEX.
3ENVIROGEM ADO1~ - available from Air Products 4See US 5,545,340 SXS-69B5476 - available from General Electric 6TSF4446 - available from General Electric exampleexampleexampleexampleexampleexampleexample #11 #12 #13 #14 #15 #16 #17 wt% wt% wt% wt% wt% wt% wt%
Alkyloxypolyethyleneoxy ethanol' 65.0 50.0 62.5 47.5 50.0 52.5 57.5 Anionic Surfactant10.0 0.0 5.0 2.5 0.0 5.0 10.0 Fatty acid andlor fatty acid salt 0.0 10.0 5.0 2.5 5.0 0.0 5.0 Propylene Glycol 15.0 15.0 15.0 20.0 20.0 20.0 10.0 Amino functional polysiloxane5 0.0 0.0 2.5 2.5 2.5 2.5 2.5 Dimethyl hydroxypropyl methyl siloxane (ethoxylated)6 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Water 0.0 15.0 0.0 15.0 12.5 10.0 5.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 ,___ _____ 1'~KCil'1'UL 15-S-3C~ - available from Dow (Union Carbide Corporation) ZAEROSOL TR~ 70% - available from CYTEX.
3ENVIROGEM ADO1 ~ - available from Air Products 4See US 5,545,340 S~S-69B5476 - available from General Electric 6TSF4446 - available from General Electric exampleexampleexampleexample ~18 #19 20 ' 21 t% t% wt%
Alkyloxypolyethyleneoxy 59.0059.00 59.00 59.00 ethanol' Propylene Glycol 12.0012.00 12.00 12.00 Dipalmithyl hydroxyethylammonium methylsulfate 4.00 .00 .0 0.0 (unsaturated)2 2-[(2E)-oct-2-en-1-yl] succinic 0.0 0.0 0.0 9.00 acid monobutyl ester bis-2-ethylhexylphosphate dicocomethyl15.000.0 0.0 0.0 ammonium salt 2-[(2E)-hexadec-2-en-1-yl) succinate mono (2-0.0 15.00 0.0 0.0 ethylhexyl) esterdicocomethyl ammonium salt 2-[(2E)-oct-2-en-1-ylJ succinate monobutyl ester 0.0 0.0 15.00 10.00 dicocomethyl ammonium salt Dimethyl hydroxypropyl methyl siloxane10.0010.00 10.00 10.00 (ethoxylated)3 Water 0.0 0.0 0.0 0.0 Total 100 100 100 100 'TERGITOL 15-S-3~ - available from Dow (Union Carbide Corporation) ZSee 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 (10)
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
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.
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.
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.
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:
;and any mixtures thereof.
wherein R, R1, and R2 of the gemini surfactant are same or different and are independently selected from H, C1-30 alkyl, C2-20 alkenyl; and x is from 0.1 to 60.
to about 50 wt%, by weight of the surfactant system of a gemini surfactant selected from the group consisting of:
;and any mixtures thereof.
wherein R, R1, and R2 of the gemini surfactant are same or different and are independently selected from H, C1-30 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.
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.
a) contacting a cleaning solution with a fabric article; and b) extracting the cleaning solution from the fabric article.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US48334503P | 2003-06-27 | 2003-06-27 | |
US60/483,345 | 2003-06-27 | ||
PCT/US2004/020879 WO2005003439A1 (en) | 2003-06-27 | 2004-06-28 | Surfactant system for use in a lipophilic fluid |
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Publication Number | Publication Date |
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CA2525511A1 true CA2525511A1 (en) | 2005-01-13 |
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ID=33563922
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002525511A Abandoned CA2525511A1 (en) | 2003-06-27 | 2004-06-28 | Surfactant system for use in a lipophilic fluid |
Country Status (8)
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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) |
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-
2004
- 2004-06-22 US US10/873,976 patent/US7202202B2/en not_active Expired - Fee Related
- 2004-06-28 CA CA002525511A patent/CA2525511A1/en not_active Abandoned
- 2004-06-28 AU AU2004254609A patent/AU2004254609A1/en not_active Abandoned
- 2004-06-28 CN CNA2004800179571A patent/CN1813094A/en active Pending
- 2004-06-28 MX MXPA05013669A patent/MXPA05013669A/en unknown
- 2004-06-28 BR BRPI0411899-5A patent/BRPI0411899A/en not_active IP Right Cessation
- 2004-06-28 WO PCT/US2004/020879 patent/WO2005003439A1/en active Application Filing
- 2004-06-28 EP EP04756350A patent/EP1639187A1/en not_active Withdrawn
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EP1639187A1 (en) | 2006-03-29 |
CN1813094A (en) | 2006-08-02 |
US7202202B2 (en) | 2007-04-10 |
WO2005003439A1 (en) | 2005-01-13 |
BRPI0411899A (en) | 2006-08-29 |
US20050009723A1 (en) | 2005-01-13 |
AU2004254609A1 (en) | 2005-01-13 |
MXPA05013669A (en) | 2006-02-24 |
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