WO2005103118A1 - Aqueous dispersions of silicone polyether block copolymers - Google Patents

Aqueous dispersions of silicone polyether block copolymers Download PDF

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Publication number
WO2005103118A1
WO2005103118A1 PCT/US2005/013328 US2005013328W WO2005103118A1 WO 2005103118 A1 WO2005103118 A1 WO 2005103118A1 US 2005013328 W US2005013328 W US 2005013328W WO 2005103118 A1 WO2005103118 A1 WO 2005103118A1
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water
aqueous composition
silicone
spe
ofthe
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PCT/US2005/013328
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French (fr)
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Shaow Lin
Kimmai Nguyen
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Dow Corning Corporation
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Priority to DE602005015102T priority Critical patent/DE602005015102D1/en
Priority to US10/594,399 priority patent/US7887834B2/en
Priority to AT05738468T priority patent/ATE434639T1/en
Priority to JP2007509574A priority patent/JP4908400B2/en
Priority to EP05738468A priority patent/EP1745087B1/en
Priority to KR1020067021809A priority patent/KR101203929B1/en
Publication of WO2005103118A1 publication Critical patent/WO2005103118A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67Vitamins
    • A61K8/671Vitamin A; Derivatives thereof, e.g. ester of vitamin A acid, ester of retinol, retinol, retinal
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • This application relates to aqueous dispersions of (AB) n silicone polyether block copolymers, methods for preparing the dispersion compositions, and personal, household, and healthcare formulations containing the compositions.
  • the aqueous dispersions can be either vesicle or emulsion compositions depending on the (AB) n silicone polyether block copolymers structure and method of preparing the dispersion.
  • Silicone surfactants have been designed for various applications by combining a hydrophobic organopolysiloxane with various hydrophilic moieties.
  • silicone surfactants known as silicone polyethers (SPEs) are based on copolymer structures of polyorganosiloxanes having pendant polyoxyalkylene groups.
  • the copolymer structures of silicone polyethers are the "rake” type, where a predominately linear polyorganosiloxane provides the "backbone” ofthe copolymer architecture with pendant polyoxyalkylene groups forming the "rake”.
  • "ABA" structures are also common, where a pendant polyoxyalkylene group is at each molecular terminal of a linear polyorganosiloxane.
  • (AB) n silicone polyethers are also known, wherein blocks of a siloxane units and polyether units repeat to form the copolymer.
  • (AB) n SPEs are not as predominant in the art as the rake or ABA silicone polyethers.
  • rake and ABA silicone polyethers there are numerous teachings describing various rake and ABA silicone polyethers structures for applications in many personal, household, and health care compositions as emulsifiers, wetting agents, and general-purpose aqueous surfactants. More recently, the aggregation behavior of rake and ABA silicone polyethers has been reported.
  • certain (AB) strips silicone polyethers form unique dispersions in aqueous media.
  • certain defined (AB) n SPE structures will form vesicle compositions in aqueous media.
  • certain (AB) n SPE structures form stable dispersions that can be used to create emulsions. These stable dispersions and vesicles can be used to formulate compositions for the delivery of pharmaceutical and personal care actives.
  • the present invention relates to aqueous compositions having dispersed particles wherein the dispersed particles comprise an (AB) n block silicone polyether copolymer having the average formula; -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C m H 2m O) y ] z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R 1 is a divalent hydrocarbon containing 2 to 30 carbons.
  • the dispersed particles comprise an (AB) n block silicone polyether copolymer having the average formula; -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C m H 2m O) y ] z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R 1 is a divalent hydrocarbon containing 2 to 30 carbons.
  • the present invention further relates to a process for making an aqueous composition
  • a process for making an aqueous composition comprising; I) combining, A) an (AB) n block silicone polyether copolymer having the average formula; -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C m H 2m O) y ] z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R 1 is a divalent hydrocarbon containing 2 to 30 carbons, B) an optional water miscible volatile solvent, with water to form an aqueous dispersion, II) mixing the aqueous dispersion to form dispersed particles ofthe (AB) n silicone polyether copolymer having an average particle size of less than 10 micrometers, III) optionally, removing the water miscible volatile solvent from the aqueous dispersion.
  • the present invention also provides a process for preparing a water continuous emulsion having an average particle size of less than 10 micrometers comprising; I) mixing A) an (AB) n block silicone polyether copolymer having the average formula; -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C m H 2m O) y ] z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R 1 is a divalent hydrocarbon containing 2 to 30 carbons, B) a water miscible volatile solvent to form a hydrophobic phase, II) adding water to the hydrophobic phase to form the water continuous emulsion. [0011] Furthermore, the present invention relates to personal, household, and healthcare formulations containing the inventive aqueous compositions. DETAILED DESCRIPTION OF THE INVENTION
  • the present invention provides aqueous compositions having dispersed particles wherein the dispersed particles comprise an (AB) n block silicone polyether copolymer having the average formula; Formula I -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C m H 2ra O) y ] z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R 1 is a divalent hydrocarbon containing 2 to 30 carbons.
  • the dispersed particles comprise an (AB) n block silicone polyether copolymer having the average formula; Formula I -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C m H 2ra O) y ] z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R 1 is a divalent hydrocarbon containing 2 to 30 carbons
  • the siloxane block in Formula I is a predominately linear siloxane polymer having the formula (R SiO) x , wherein R is independently selected from a monovalent organic group, x is an integer greater than 4.
  • the value of x i.e. the degree of polymerization, DP, ofthe polysiioxane chain ranges from 20 to 100, alternatively from 30 to 75. These structures form vesicles in aqueous media, as discussed infra.
  • the value of x ranges from 5 to 19, alternatively from 5 to 15. These structures form stable emulsions in aqueous media having a particle size of less than 10 micrometers, also discussed infra.
  • the organic groups represented by R in the siloxane polymer are free of aliphatic unsaturation. These organic groups may be independently selected from monovalent hydrocarbon and monovalent halogenated hydrocarbon groups free of aliphatic unsaturation. These monovalent groups may have from 1 to 20 carbon atoms, alternatively 1 to 10 carbon atoms, and are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl; and halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, and dichlorophenyl.
  • alkyl groups such as
  • the siloxane block is a predominately linear polydimethylsiloxane having the formula (Me 2 SiO) x , where x is as defined above.
  • the polyoxyalkylene block ofthe silicone polyether is represented by the formula (C m H 2m O) y wherein m is from 2 to 4 inclusive, and y is greater than 4, alternatively y can range from 5 to 45, or alternatively from 5 to 25.
  • the polyoxyalkylene block typically can comprise oxyethylene units (C 2 H 4 ⁇ ) y , oxypropylene units (C 3 H 6 O) y , oxybutylene units (C H 8 O) y , or mixtures thereof.
  • the polyoxyalkylene block comprises oxyethylene units (CJ O)y.
  • At least one end of each polyoxyalkylene block in Formula I is linked to a siloxane block by a divalent organic group, designated R 1 . This linkage is determined by the reaction employed to prepare the (AB) n block silicone polyether copolymer.
  • the divalent organic groups of R 1 may be independently selected from divalent hydrocarbons containing 2 to 30 carbons and divalent organofunctional hydrocarbons containing 2 to 30 carbons.
  • divalent hydrocarbon groups include; ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and the like.
  • divalent organofunctional hydrocarbons groups include acrylate and methacrylate.
  • R 1 is propylene, (-CH CH 2 CH 2 -).
  • the endblocking unit is also determined by the reaction employed to prepare the (AB) n block silicone polyether copolymer, which is generally the residual reactive groups ofthe reactants used.
  • the (AB) n block silicone polyether copolymers can be prepared by the metal catalyzed hydrosilylation reaction of a diallyl polyether (i.e. an allyl group is present on each molecular terminal end) with a SiH terminated polyorganosiloxane.
  • the resulting (AB) n block silicone polyether copolymer would have polyoxyalkylene blocks linked to the silicone blocks via a propyleneoxy group (-CH 2 CH 2 CH 2 O-), and using a slight molar excess ofthe allyl polyether would result in an allyl endblock unit (-CH 2 CHCH 2 ).
  • Alternative endblock units can result from the addition of other molecules in the reaction employed to prepare the (AB)n block silicone polyether copolymer that are capable of reacting with the siloxane or polyether block intermediates.
  • the addition of organic compounds having mono-terminated aliphatic unsaturation will result in the endcapping ofthe (AB) confront block silicone polyether copolymer with that organic compound.
  • the molecular weights ofthe (AB) confront block silicone polyether copolymers will be determined by the number of repeating siloxane and polyoxyalkylene blocks, as indicated by the subscript z in Formula I. Typically, the value of z is such to provide weight average molecular weights (Mw) to range from 1,500 to 150,000, alternatively, from 10,000 to 100,000.
  • the ratio ofthe silicone block to the polyoxyalkylene block in the (AB) n SPEs can also be used to identify which structures form vesicles or stable aqueous emulsions. This molecular parameter is expressed by the value of x/(x+y) in Formula I. The value of x/(x+y) can vary from 0.2 to 0.9, or alternatively from 0.4 to 0.9.
  • the (AB) n SPEs of the present invention can be prepared by any method known in the art for preparing such block copolymers. Alternatively, the (AB) n SPEs ofthe present invention are prepared according the methods described infra.
  • the present invention further provides a process to prepare an (AB) n block silicone polyether copolymer comprising reacting; a) a SiH terminated organopolysiloxane, b) a polyoxyalkylene having an unsaturated hydrocarbon group at each molecular terminal, c) a hydrosilylation catalyst, d) optionally a solvent, e) optionally an organic endblocker compound having a mono-terminally unsaturated hydrocarbon group, wherein the mole ratio ofthe unsaturated organic groups to SiH in the reaction is at least 1:1.
  • the SiH terminated organopolysiloxanes useful in the process ofthe present invention can be represented by the formula M'DM', where "M”' means a siloxane unit of formula R 2 HSiO 2 , "D” means a siloxane unit of formula R 2 SiO 2 / 2 , where R is independently a monovalent organic group as defined above.
  • the SiH terminated organopolysiloxane is a dimethylhydrogensiloxy-terminated polydimethylsiloxane having the average formula Me 2 HSiO(Me 2 SiO) x SiHMe 2 , where x is as defined above.
  • the polyoxyalkylene useful in the process ofthe present invention may be a polyoxyethylene comprising the average formula -(C 2 H 4 O) y - , where y is defined as above, and is terminated at each molecular chain end (i.e. alpha and omega positions) with a unsaturated organic group.
  • the unsaturated organic group can be an unsaturated hydrocarbon group such as alkenyl or alkynyl group.
  • H 2 C CH-
  • H 2 C CHCH 2 -
  • H 2 C C(CH 3 )CH 2 -
  • H 2 C CHCH 2 CH 2 -
  • H 2 C CHCH 2 CH 2 CH 2 -
  • H 2 C CHCH 2 CH 2 CH 2 CH 2 -.
  • alkynyl groups are shown by the following structures; HC ⁇ C-, HC ⁇ CCH 2 -, HC ⁇ CC(CH 3 ) - , HC ⁇ CC(CH 3 ) 2 - , HC ⁇ CC(CH 3 ) 2 CH 2 - .
  • Polyoxyethylenes having an unsaturated hydrocarbon group at each molecular terminal are known in the art, and many are commercially available.
  • the unsaturated organic group can be an organofunctional hydrocarbon such as an acrylate, methacrylate and the like.
  • a hydrosilylation catalyst which are known in the art.
  • Such hydrosilylation catalysts are illustrated by any metal-containing catalyst which facilitates the reaction of silicon-bonded hydrogen atoms of the SiH terminated organopolysiloxane with the unsaturated hydrocarbon group on the polyoxyethylene.
  • the metals are illustrated by ruthenium, rhodium, palladium, osmium, iridium, or platinum.
  • Hydrosilylation catalysts are illustrated by the following; chloroplatinic acid, alcohol modified chloroplatinic acids, olefin complexes of chloroplatinic acid, complexes of chloroplatinic acid and divinyltetramethyldisiloxane, fine platinum particles adsorbed on carbon carriers, platinum supported on metal oxide carriers such as Pt(Al2 ⁇ 3), platinum black, platinum acetylacetonate, platinum(divinyltetramethyldisiloxane), platinous halides exemplified by PtCl2, PtC-4, Pt(CN)2, complexes of platinous halides with unsaturated compounds exemplified by ethylene, propylene, and organovinylsiloxanes, styrene hexamethyldiplatinum. and RhCl3(Bu2S)3.
  • the amount of hydrosilylation catalyst that is used is not narrowly limited as long as there is a sufficient amount to accelerate a reaction between the polyoxyethylene having an unsaturated hydrocarbon group at each molecular terminal and the SiH terminated organopolysiloxane at room temperature or at temperatures above room temperature.
  • the exact necessary amount of this catalyst will depend on the particular catalyst utilized and is not easily predictable. However, for platinum-containing catalysts the amount can be as low as one weight part of platinum for every one million weight parts of components the polyoxyethylene having an unsaturated hydrocarbon group at each molecular terminal and the SiH terminated organopolysiloxane.
  • the catalyst can be added at an amount 10 to 120 weight parts per one million parts of components the polyoxyethylene having an unsaturated organic group at each molecular terminal and the SiH terminated organopolysiloxane, but is typically added in an amount from 10 to 60 weight parts per one million parts ofthe polyoxyethylene having an unsaturated organic group at each molecular terminal and the SiH terminated organopolysiloxane.
  • the hydrosilylation reaction can be conducted neat or in the presence of d), a solvent.
  • the solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol, a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether, a halogenated hydrocarbon such as dichloromethane, 1,1,1- trichloroethane or methylene chloride, chloro
  • the amount of solvent can be up to 50 weight percent, but is typically from 20 to 50 weight percent, said weight percent being based on the total weight of components in the hydrosilylation reaction.
  • the solvent used during the hydrosilylation reaction can be subsequently removed from the resulting silicone polyether by various known methods.
  • Additional components can be added to the hydrosilylation reaction which are known to enhance such reactions. These components include salts such as sodium acetate which have a buffering effect in combination with platinum catalysts.
  • the (AB) n SPEs of Formula I have a value of x (i.e. the degree of polymerization, DP, ofthe polysiioxane chain in the siloxane units) that ranges from 20 to 100, alternatively from 30 to 75. These structures form vesicles in aqueous media.
  • vesicle compositions can be prepared by mixing the (AB) n SPEs with water using any technique known common in the state ofthe art for creating vesicle compositions. The type and extent ofthe mixing technique will depend on the specific structure ofthe (AB) n SPE chosen.
  • Optional component B) is a water-miscible volatile solvent.
  • water- miscible means the solvent forms a dispersion with water at room temperature for at least 1 several hours.
  • Volatile means the solvent has a higher vapor pressure than water at various temperatures.
  • Suitable water-miscible volatile solvents as component B) include organic solvents such as alcohols, ethers, glycols, esters, acids, halogenated hydrocarbons, diols.
  • organic solvents should be miscible with water at the proportion and lower in order to effectively disperse silicones and maintain stable and uniform dispersion overtime.
  • water-miscible alcohols include methanol, ethanol, propanol, isopropanol, butanol, and higher hydrocarbon alcohols; ethers include gylcol ethers, methyl-ethyl ether, methyl isobutyl ether (MIBK), etc; glycols include propylene glycols, esters include esters of triglycerol, the esterification products of acid and alcohol; halogenated hydrocarbons include chloroform.
  • water-miscible organic solvents are solvents with relatively low boiling points ( ⁇ 100°C) or high evaporation rate, so they may be removed under vacuum with ease.
  • the most preferred water-miscible organic solvents for this invention are volatile alcohols including methanol, ethanol, isopropanol, and propanol. These alcohols can be removed from aqueous mixtures containing silicone dispersions via vacuum stripping at ambient temperature.
  • the aqueous compositions may further optionally comprise a silicone or organic oil, component C).
  • the silicone can be any organopolysiloxane having the general formula RjSiO( .i) /2 in which i has an average value of one to three and R is a monovalent organic group.
  • the organopolysiloxane can be cyclic, linear, branched, and mixtures thereof.
  • Component C) may be a volatile methyl siloxane (VMS) which includes low molecular weight linear and cyclic volatile methyl siloxanes. Volatile methyl siloxanes conforming to the CTFA definition of cyclomethicones are considered to be within the definition of low molecular weight siloxane.
  • VMS volatile methyl siloxane
  • component C) is an organic oil
  • Suitable organic oils include, but are not limited to, natural oils such as coconut oil; hydrocarbons such as mineral oil and hydrogenated polyisobutene; fatty alcohols such as octyldodecanol; esters such as C12 -C15 alkyl benzoate; diesters such as propylene dipelarganate; and triesters, such as glyceryl trioctanoate.
  • the organic oil components can also be mixture of low viscosity and high viscosity oils.
  • Suitable low viscosity oils have a viscosity of 5 to 100 mPa-s at 25°C, and are generally esters having the structure RCO-OR' wherein RCO represents the carboxylic acid radical and wherein OR' is an alcohol residue.
  • low viscosity oils examples include isotridecyl isononanoate, PEG-4 diheptanoate, isostearyl neopentanoate, tridecyl neopentanoate, cetyl octanoate, cetyl palmitate, cetyl ricinoleate, cetyl stearate, cetyl myristate, coco-dicaprylate/caprate, decyl isostearate, isodecyl oleate, isodecyl neopentanoate, isohexyl neopentanoate, octyl palmitate, dioctyl malate, tridecyl octanoate, myristyl myristate, octododecanol, or mixtures of octyldodecanol, acetylated lanolin alcohol, cetyl acetate, isod
  • the high viscosity surface oils generally have a viscosity of 200-1 ,000,000 mPa-s at 25°C, preferably a viscosity of 100,000-250,000 mPa-s.
  • Surface oils include castor oil, lanolin and lanolin derivatives, triisocetyl citrate, sorbitan sesquioleate, CIO- 18 triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil, cottonseed oil, glyceryl triacetyl hydroxystearate, glyceryl triacetyl ricinoleate, glyceryl trioctanoate, hydrogenated castor oil, linseed oil, mink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, sunflower seed oil, tallow, tricaprin, trihydroxystearin, triisostearin, trilaurin, trilinolein, trimyristin, triolein,
  • mineral oils such as liquid paraffin or liquid petroleum
  • animal oils such as perhydrosqualene or arara oil
  • vegetable oils such as sweet almond, calophyllum, palm, castor, avocado, jojaba, olive or cereal germ oil.
  • esters of lanolic acid, of oleic acid, of lauric acid, of stearic acid or of myristic acid for example; alcohols, such as oleyl alcohol, linoleyl or linolenyl alcohol, isostearyl alcohol or octyldodecanol; or acetylglycerides, octanoates, decanoates or ricinoleates of alcohols or of polyalcohols.
  • vesicles in the compositions ofthe present invention can be confirmed by techniques common in the state ofthe art. Typically, vesicles having a lamellar phase structure which exhibit birefringence when examined with a cross polarizing microscope. Alternatively, the formation of vesicles can be demonstrated by Cyro-
  • the amount ofthe (AB) n block silicone polyether copolymer (Component A), optional water-miscible volatile solvent (Component B), and water can vary in the compositions ofthe present invention, but typically range as follows; A) 2 to 50 wt%, alternatively 2 to 25 wt %, or alternatively 2 to 15 wt%, B) 0 to 50 wt%, alternatively 2 to 30 wt %, or alternatively 2 to 20 wt%, C) 0 to 50 wt %, alternatively 1 to 20 wt %, or alternatively 2 to 10 wt%, and sufficient amounts of water to provide the sum ofthe wt% of A), B), and water to equal 100%.
  • the vesicle compositions can be prepared according to the methods of the present invention, as discussed infra.
  • the present invention also provides a process for making an aqueous composition
  • a process for making an aqueous composition comprising; I) combining, A) an (AB) n block silicone polyether copolymer having the average formula; -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C m H 2m O) y ] z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R 1 is a divalent hydrocarbon containing 2 to 30 carbons, B) an optional water miscible volatile solvent, with water to form an aqueous dispersion, II) mixing the aqueous dispersion to form dispersed particles ofthe (AB) classroom silicone polyether copolymer having an average particle size of less than 10 micrometers, III) optionally, removing the water miscible volatile solvent from the aqueous dispersion.
  • Step I) involves combining an (AB) n S
  • step I) a water-miscible volatile solvent.
  • Components A) and B) in step I) are the same as described above.
  • the amount of components A), B), and water combined in step I) can vary in the process, but typically range as follows; A) 2 to 50 wt%, alternatively 2 to 25 wt %, or alternatively 2 to 15 wt%, B) 0 to 50 wt%, alternatively 2 to 30 wt %, or alternatively 2 to 20 wt%, and sufficient amounts of water to provide the sum ofthe wt% of A), B), and water to equal
  • Step II in the above process is mixing the aqueous dispersion formed in Step I to form dispersed particles ofthe (AB) confront silicone polyether copolymer having an average particle size of less than 10 micrometers.
  • Mixing techniques can be simple stirring, homogenizing, sonalating, and other mixing techniques known in the art.
  • the mixing can be conducted in a batch, semi-continuous, or continuous process.
  • Step III in the above process is optional, and involves removing the water miscible volatile solvent, component B).
  • the water miscible volatile solvent is removed by known techniques in the art, such as subjecting the vesicle composition to reduced pressures, while optionally heating the composition.
  • Devices illustrative of such techniques include rotary evaporators and thin film strippers.
  • the (AB) n SPEs of Formula I have a value of x (i.e. the degree of polymerization, DP, ofthe polysiioxane chain in the siloxane units) that ranges from 5 to 19, alternatively from 5 to 10. These structures form stable emulsions in aqueous media having a particle size of less than 10 micrometers.
  • the stable emulsions can be prepared by mixing the (AB) n SPEs ofthe second embodiment with water, according to known techniques for preparing water continuous emulsions. Alternatively, the emulsion compositions can be prepared according to the methods ofthe present invention, as discussed infra.
  • the present invention thus provides a process for preparing a water continuous emulsion having an average particle size of less than 10 micrometers comprising; I) mixing A) an (AB) n block silicone polyether copolymer having the average formula; -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C m H 2m O) y ] z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R 1 is a divalent hydrocarbon containing 2 to 30 carbons, B) an optional water miscible volatile solvent to form a hydrophobic phase, II) adding water to the hydrophobic phase to form the water continuous emulsion.
  • step II) The (AB) n SPEs, component A) and optional water-miscible volatile solvent, component B) in step II) ofthe above process are the same as described above.
  • water is then added to the mixture in step II ofthe present process to prepare a water continuous emulsion.
  • the mixing and water addition steps can be conducted in a batch, semi-continuous, or continuous process.
  • the hydrophobic phase of step I) can also comprise a silicone or organic oil, as component C), and is the same as described above
  • the hydrophobic phase of step I) can also comprise optionally a personal, household, or healthcare active.
  • a personal, household, or health care ingredient can also be selected from a personal or health care "active", that is, any compound known to have either cosmetic and/or pharmaceutical activity.
  • a representative listing of such personal or health care actives are disclosed in US Patent 6,168,782, which is hereby incorporated by reference. The common assignee's U.S.
  • Patent 5,948,855 (September 7, 1999), also contains an extensive list of some appropriate oil soluble active ingredients such as vitamins and drugs which can be used in the oil phase ofthe oil in water emulsions, among which are vitamins, including but not limited to, Vitamin A ⁇ , RETINOL, C2-C ⁇ g esters of RETINOL, Vitamin E, TOCOPHEROL, esters of Vitamin E, and mixtures thereof.
  • RETINOL includes trans-RETINOL, 13-cis-RETINOL, 11-cis-RETINOL, 9-cis-RETINOL, and 3,4-didehydro-RETINOL.
  • vitamins which are appropriate include RETIN YL ACETATE, RETINYL PALMITATE, RETINYL PROPIONATE, ⁇ -TOCOPHEROL, TOCOPHERSOLAN, TOCOPHERYL ACETATE, TOCOPHERYL LINOLEATE, TOCOPHERYL NICOTINATE, and TOCOPHERYL SUCCINATE.
  • the amount of components A), B), C), and D) can vary in the process to prepare the emulsions ofthe present invention, but typically range as follows; A) 2 to 60 wt%, alternatively 2 to 50 wt %, or alternatively 2 to 40 wt%, B) 0 to 50 wt%, alternatively 2 to 30 wt %, or alternatively 2 to 20 wt%, C) 0 to 30 wt%, alternatively 0 to 25 wt %, or alternatively 0 to 20 wt%, D) 0 to 30 wt%, alternatively 0 to 25 wt %, or alternatively 0 to 20 wt%, where sufficient amount of water is added to provide the sum ofthe wt% of A), B), C), D), and water to equal 100%.
  • the present invention also relates to vesicle compositions further comprising a personal, household, or health care ingredient.
  • the vesicle compositions can be used to entrap, and subsequently deliver after application, a personal, household care, or health care ingredient.
  • a listing of possible personal, household, or health care ingredients is taught in WO 03/101412, which is incorporated herein by reference.
  • the personal or health care ingredient can also be selected from a personal or health care "active", that is, any compound known to have either cosmetic and/or pharmaceutical activity.
  • a representative listing of such personal or health care actives are disclosed in US Patent 6,168,782, which is hereby incorporated by reference.
  • compositions prepared according to the invention can be used in various over-the- counter (OTC) personal care compositions, health care compositions, and household care compositions, but especially in the personal care arena.
  • OTC over-the- counter
  • they can be used in antiperspirants, deodorants, skin creams, skin care lotions, moisturizers, facial treatments such as acne or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colognes, sachets, sunscreens, pre-shave and after-shave lotions, liquid soaps, shaving soaps, shaving lathers, hair shampoos, hair conditioners, hair sprays, mousses, permanents, depilatories, hair cuticle coats, make-ups, color cosmetics, foundations, blushes, lipsticks, lip balms, eyeliners, mascaras, oil removers, color cosmetic removers, nail polishes, and powders.
  • Polyglycol AA600, AAl 200, and AA2000 were used as obtained from Clariant (Mt. Holly,
  • TEM Cyro-Transmission Electron Microscopy
  • the grid was then plunged into a liquid ethane contained in a small vessel located in a larger liquid nitrogen vessel under -175 °C atmosphere in the cryo-plunge system to vitrify the water film on the grid and to avoid water crystallization.
  • the quenched sample grid was transferred in to the cryo-grid box in the cryo- plunge system.
  • the grid box containing the sample was transferred into a Gatan cryo-transfer system filled with liquid nitrogen and loaded in a cryo-TEM stage, which has been positioned in the cryo-transfer system and cooled down to below -160 °C.
  • the sample was loaded in TEM (JEOL 2000FX) and the images were observed at below -160 °C.
  • Vesicle Compositions from (AB) compliment SPE 2 [0055] The following procedure was used to prepare the vesicle compositions summarized in Table 3 as Examples 12 and 13.
  • Isopropanol was added to (AB) compliment SPE 2, (a (AB)n block copolymer of M'D 50 M' siloxane and polyglycol AAl 200 polyether, having a weight-average molecular weight Mw of 50,108 g/mole), to provide a homogeneous mixture.
  • water was added slowly to form a homogeneous dispersion having an average particle size of 0.208 ⁇ m.
  • the IPA in the dispersion was then removed using a Rotovapor under vacuum at ambient temperature, to yield an alcohol-free, homogeneous dispersion having an average particle size of 0.223 ⁇ m, designated as Example 13.
  • Vesicle compositions of (AB) n SPE 1 an (AB)n block copolymer of M'D 30 M' siloxane and polyglycol AAl 200 polyether, having a weight-average molecular weight Mw of 19486 g/mole were prepared following the procedure of Examples 12-13. These vesicle compositions are summarized in Table 4 as Examples 17 - 19. All three compositions had an average particle size distribution of less than 40 nm (0.040 ⁇ m). These examples demonstrate that the removal of alcohol did not affect the quality of dispersion and the homogenization step is optional.
  • Nesicle compositions were prepared from (AB) compliment SPE 3 A andB, (AB)n silicone polyether block copolymers of M'D 5 M' siloxane and polyglycol AA1200 polyether having a weight-average molecular weight Mw of 40, 158 and 44,885 g/mole, respectively. These dispersions were made following the procedure described in Examples 12 - 13 and are summarized in Table 5.
  • Alcohol-free vesicle compositions were prepared from (AB) compliment SPE 3 B an (AB)n silicone polyether block copolymer of M'D 75 M' siloxane and polyglycol AA1200 polyether, having a weight-average molecular weight Mw of 44,885 g/mole following the procedure of Examples 12 -13, and removing the alcohol under reduced pressure.
  • the compositions are summarized in Table 6.
  • Nitamin A palmitate was first mixed with isopropanol at 50/50 ratio.
  • the vitamin / IPA mixture was then mixed with (AB)n SPE 1, a (AB)n block copolymer of M'D 3 oM' siloxane and polyglycol AA1200 polyether, having a weight-average molecular weight Mw of 19486 g/mole to homogenous.
  • Ethanol was then admixed to form a homogeneous mixture. While under continuous mixing, de-ionized water was slowly and gradually incorporated into the SPE / vitamin / alcohol mixture, till homogenous.
  • Example 26 The mixture was homogenized, using an APN-2000 Gaulin homogenizer, producing a homogeneous dispersion with sub-micron particle size, identified as Example 26 in Table 8.
  • Example 26 composition was then further homogenized.
  • the alcohol was removed under reduced pressure at ambient temperature to produce a composition having an average particle size of 0.54 um, listed as Example 27 in Table 8. The removal of alcohol processing aid did not affect the dispersion quality and the particle size.
  • the following vitamin A palmitate loaded (AB)n SPE vesicles in water dispersion was prepared according to the method shown in the previous examples of this invention.
  • the (AB)n SPE is a copolymer of 50 dp siloxane and Polyglycol AA1200 polyether.
  • the final composition ofthe vesicle dispersion is shown in Table 9.
  • the vitamin-loaded SPE vesicles can easily be formulated into skin care formulations. Oil-based vitamins can be easily incorporated into water-based formulations. The following examples provide such illustrations.
  • Part A were mixed and heated to 85 °C to homogeneous. Cool the part A mixture to 40 °C, then incorporate the part B ingredients. Cooled the mixture to ambient temperature.
  • the (AB) n type SPE vesicles can be easily formulated into aqueous based gel formulations. SPE vesicles provide a convenient means to incorporate oil-soluble vitamins into water-rich gel formulations.
  • Vitamin A palmitate-loaded SPE 19.88 vesicles To prepare the gel, the following procedure was followed: The ingredients in Part A were mixed to homogeneous. Nitamin A palmitate-loaded SPE vesicles dispersion was then incorporated and mixed to homogeneous. The final product is a beige, smooth gel. [0067] To further demonstrate the integrity of vesicles in formulations, cryo-TEM images of the "as formulated" products were taken. An image ofthe gel from the above example is shown figure 6. As illustrated, the vesicles and aggregates of vesicles were well preserved.
  • FIG. 7 A cryo-TEM image ofthe "as prepared” body lotion illustrated in Example A, prepared from (AB)n SPE vesicle is shown in figure 7.
  • Dispersions of (AB)n SPE 31 A copolymer were prepared in alcohol-water mixture.
  • the solid (AB)n SPE copolymer was dispersed, via a mechanical shear device, into isopropanol / water mixtures at a ratio of 5/85, and 20/70, respectively, as summarized in Table 10. Additionally, a dispersion of sub-micron size in water was also obtained by vacuum stripping IPA off the mixture.
  • Vitamin A palmitate loaded (AB)n SPE particle dispersions Vitamin A palmitate loaded (AB)n SPE particle dispersions.
  • Nitamin A palmitate is not soluble in water and can not be dispersed in water directly.
  • the example shows that particle dispersion forming (AB)n SPE block copolymer can be used to incorporate water-insoluble vitamins and form a stable dispersion in water.
  • the dispersion was prepared as followed: A 50/50 by weight pre-mixture of vitamin A palmitate and Dow Corning® DC 1-2287 vinyl silicone fluid was prepared. The premix was incorporated to form a homogeneous mixture with (AB)n SPE 31A copolymer. Deionized water was slowly incorporated into the above mixture while under continuous mixing. As shown in Table 11, a dispersion having an average particle size of 1.68 ⁇ m was obtained in water. The vitamin A palmitate payload in the dispersion particles was 17%.
  • Si/W emulsions of different compositions were prepared via high shear emulsification process.
  • the method of preparation includes the following steps: the silicone fluids were incorporated into (AB) n SPE 32A copolymer to form a homogeneous mixture. A small amount of water was incorporated into the phase A mixture, followed by high shear mixing to disperse the water using a Speed Mixer. Water additions in small quantity continued until the mixture inverted or form a continuous, smooth cream (called inverted into a water-continuous emulsion concentrate). The remaining water was added to further dilute the emulsion to desired concentration and consistency. The final emulsions had an average particle size between 1.3 and 2.1 ⁇ m.
  • (AB)n SPE 31B is the block copolymer reaction product of M'D ⁇ 5 M' siloxane and polyglycol AA2000 polyether (segment length of 44 EO units) and has a melting temperature 45 - 47 °C.
  • Si/W emulsions Examples were made by mechanical emulsification using a high-shear mixer (Speed Mixer), similar to the ones described above. The step-wise procedures can be found in the previous examples.
  • the final Si/W emulsions had an average particle size of 0.394 ⁇ m and 0.725 ⁇ m, respectively, as summarized in Table 13.
  • (AB)n SPE block copolymer in Si/W emulsion form can be used to carry and protect water-insoluble oils and substances. These emulsions can subsequently be incorporated into water-based end products and formulations.
  • Nitamin A palmitate is water-insoluble and cannot be incorporated directly into water-based formulations. These examples showed that stable Si/W emulsions containing various amount of vitamin A palmitate were successfully prepared from (AB)n SPE block copolymer.
  • Si/W emulsions were prepared using SPE 32 A copolymer, an (AB)n block copolymer product of M'D ⁇ 5 M' siloxane and polyglycol AA1200 polyether and has a melting temperature of 27 - 32 °C.
  • DC 245 silicone cyclics and DC 1-2287 vinyl silicone fluids were used to prepare the following Si/W and (Si+O)/W emulsions.
  • the two vitamin A palmitate loaded (AB)n SPE block copolymer emulsions had a particle size of 1.62 ⁇ m and 1.02 ⁇ m, respectively.
  • the vitamin payload was 13.4 % and 20.3%, respectively.
  • Vitamin loaded emulsions formulated into skin care products
  • Vitamin A palmitate loaded (AB)n SPE particle dispersions in water were prepared according to the method shown in the previous examples.
  • Example 46 was prepared from (AB)n SPE copolymer of 15 dp silloxane and Polyglycol AA2000 polyether, and
  • Example 47 dispersion from (AB)n SPE copolymer of 15 dp siloxane and Polyglycol AA1200 polyether. The final compositions of these dispersions are shown in Table 15.
  • the vitamin-loaded SPE particle dispersions were formulated into skin care formulations.
  • the (AB)n type SPE particle dispersions can be formulated into aqueous based gel formulations.
  • SPE vesicles provide a convenient means to incorporate oil-soluble vitamins into water-rich gel formulations.
  • Vitamin A palmitate-loaded SPE 19.88 particle dispersions To prepare the gel, the following procedure was followed: The ingredients in Part A were mixed to homogeneous. Vitamin A palmitate-loaded SPE particle dispersion was then incorporated and mixed to homogeneous. The final product is a beige, smooth gel. [0085] To further demonstrate the integrity ofthe dispersion particles in formulations, cryo- TEM images ofthe "as formulated" products were taken. The resulting image ofthe gel from the above example confirmed the dispersion particles were well preserved.
  • the emulsion labeled as Example 48 was prepared from (AB)n SPE 32A, a copolymer of 15 dp siloxane and Polyglycol AA2000 polyether, and the emulsion labeled as Example 49 from (AB)n SPE 3 IB, a copolymer of 15 dp siloxane and Polyglycol AA2000 polyether.
  • the final compositions of these dispersions are shown in the following table. In this case, no water- miscible solvent was required.
  • DC 1-2287 a methylvinylsilicone cyclics (from Dow Corning Corp.) was used.
  • the compositions of these two emulsions are shown in Table 16 below. [0087]
  • the stability ofthe emulsions prepared from (AB)n SPE copolymers are also shown. The particle sizes of these emulsions after 5 weeks aging @ 40°C were found comparable to their initial values, as illustrated in Table 16.

Abstract

Aqueous dispersions of (AB)n silicone polyether block copolymers, methods for preparing the dispersion compositions, and personal, household, and healthcare formulations containing the compositions are disclosed. The aqueous dispersions can be either vesicle or emulsion compositions depending on the (AB)n silicone polyether block copolymers structure and method of preparing the dispersion.

Description

AQUEOUS DISPERSIONS OF SILICONE POLYETHER BLOCK COPOLYMERS Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to US Patent Application No. 60/563,663 as filed on April 20, 2004, US Patent Application 60/611,258 as filed on September 17, 2004, US Patent Application 60/611 , 151 as filed on September 17, 2004, and US Patent Application No. 60/611,229 as filed on September 17, 2004.
FIELD OF THE INVENTION
[0002] This application relates to aqueous dispersions of (AB)n silicone polyether block copolymers, methods for preparing the dispersion compositions, and personal, household, and healthcare formulations containing the compositions. The aqueous dispersions can be either vesicle or emulsion compositions depending on the (AB)n silicone polyether block copolymers structure and method of preparing the dispersion.
BACKGROUND OF THE INVENTION
[0003] Silicone surfactants have been designed for various applications by combining a hydrophobic organopolysiloxane with various hydrophilic moieties. For example, the silicone surfactants known as silicone polyethers (SPEs) are based on copolymer structures of polyorganosiloxanes having pendant polyoxyalkylene groups. Most commonly, the copolymer structures of silicone polyethers are the "rake" type, where a predominately linear polyorganosiloxane provides the "backbone" ofthe copolymer architecture with pendant polyoxyalkylene groups forming the "rake". "ABA" structures are also common, where a pendant polyoxyalkylene group is at each molecular terminal of a linear polyorganosiloxane. (AB)n silicone polyethers are also known, wherein blocks of a siloxane units and polyether units repeat to form the copolymer. (AB)n SPEs are not as predominant in the art as the rake or ABA silicone polyethers. For example, there are numerous teachings describing various rake and ABA silicone polyethers structures for applications in many personal, household, and health care compositions as emulsifiers, wetting agents, and general-purpose aqueous surfactants. More recently, the aggregation behavior of rake and ABA silicone polyethers has been reported. [0004] Long-standing needs in the field of cosmetic and drug formulation/delivery field are to identify vesicle compositions that form and entrap actives easily, are stable under various chemical and mechanical stresses, and yet are able to deliver the actives in a controlled manner under desired conditions. Vesicles derived from silicone surfactants, and more particularly silicone polyether surfactants, are of interest because of additional inherent benefits that this class of surfactants possesses vs. other types. For example, silicone polyether surfactants often have improved aesthetics in personal care formulations. [0005] US Patents 5,364,633 and 5,411,744 by Hill teaches the self-assembly of silicone vesicles in aqueous dispersions of certain silicone polyethers. PCT application US03/38455 by Lin teaches the entrapment of various oils in silicone vesicles and their use in various personal care formulations.
[0006] The present inventors have discovered that certain (AB)„ silicone polyethers form unique dispersions in aqueous media. In one embodiment, certain defined (AB)n SPE structures will form vesicle compositions in aqueous media. In a second embodiment, certain (AB)n SPE structures form stable dispersions that can be used to create emulsions. These stable dispersions and vesicles can be used to formulate compositions for the delivery of pharmaceutical and personal care actives.
[0007] While (AB)n silicone polyether block copolymers are known, the selection ofthe specific structures or certain molecular variables that enables the copolymers to form stable dispersions in aqueous media is heretofore unknown.
SUMMARY OF THE INVENTION
[0008] The present invention relates to aqueous compositions having dispersed particles wherein the dispersed particles comprise an (AB)n block silicone polyether copolymer having the average formula; -[R1(R2SiO)x(R2SiR1O)(CmH2mO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons. [0009] The present invention further relates to a process for making an aqueous composition comprising; I) combining, A) an (AB)n block silicone polyether copolymer having the average formula; -[R1(R2SiO)x(R2SiR1O)(CmH2mO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons, B) an optional water miscible volatile solvent, with water to form an aqueous dispersion, II) mixing the aqueous dispersion to form dispersed particles ofthe (AB)n silicone polyether copolymer having an average particle size of less than 10 micrometers, III) optionally, removing the water miscible volatile solvent from the aqueous dispersion. [0010] The present invention also provides a process for preparing a water continuous emulsion having an average particle size of less than 10 micrometers comprising; I) mixing A) an (AB)n block silicone polyether copolymer having the average formula; -[R1(R2SiO)x(R2SiR1O)(CmH2mO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons, B) a water miscible volatile solvent to form a hydrophobic phase, II) adding water to the hydrophobic phase to form the water continuous emulsion. [0011] Furthermore, the present invention relates to personal, household, and healthcare formulations containing the inventive aqueous compositions. DETAILED DESCRIPTION OF THE INVENTION
[0012] The present invention provides aqueous compositions having dispersed particles wherein the dispersed particles comprise an (AB)n block silicone polyether copolymer having the average formula; Formula I -[R1(R2SiO)x(R2SiR1O)(CmH2raO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons. [0013] The siloxane block in Formula I is a predominately linear siloxane polymer having the formula (R SiO)x , wherein R is independently selected from a monovalent organic group, x is an integer greater than 4. In a first embodiment the value of x (i.e. the degree of polymerization, DP, ofthe polysiioxane chain ranges from 20 to 100, alternatively from 30 to 75. These structures form vesicles in aqueous media, as discussed infra. In a second embodiment, the value of x ranges from 5 to 19, alternatively from 5 to 15. These structures form stable emulsions in aqueous media having a particle size of less than 10 micrometers, also discussed infra. [0014] The organic groups represented by R in the siloxane polymer are free of aliphatic unsaturation. These organic groups may be independently selected from monovalent hydrocarbon and monovalent halogenated hydrocarbon groups free of aliphatic unsaturation. These monovalent groups may have from 1 to 20 carbon atoms, alternatively 1 to 10 carbon atoms, and are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl; and halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, and dichlorophenyl. At least 50 percent, alternatively at least 80%, ofthe organic groups free of aliphatic unsaturation in the organopolysiloxane may be methyl (denoted as Me). Typically, the siloxane block is a predominately linear polydimethylsiloxane having the formula (Me2SiO)x, where x is as defined above. [0015] The polyoxyalkylene block ofthe silicone polyether is represented by the formula (CmH2mO)y wherein m is from 2 to 4 inclusive, and y is greater than 4, alternatively y can range from 5 to 45, or alternatively from 5 to 25. The polyoxyalkylene block typically can comprise oxyethylene units (C2H4θ)y , oxypropylene units (C3H6O)y, oxybutylene units (C H8O)y, or mixtures thereof. Typically, the polyoxyalkylene block comprises oxyethylene units (CJ O)y. [0016] At least one end of each polyoxyalkylene block in Formula I is linked to a siloxane block by a divalent organic group, designated R1. This linkage is determined by the reaction employed to prepare the (AB)n block silicone polyether copolymer. The divalent organic groups of R1 may be independently selected from divalent hydrocarbons containing 2 to 30 carbons and divalent organofunctional hydrocarbons containing 2 to 30 carbons. Representative, non-limiting examples of such divalent hydrocarbon groups include; ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and the like. Representative, non-limiting examples of such divalent organofunctional hydrocarbons groups include acrylate and methacrylate. Typically, R1 is propylene, (-CH CH2CH2-). [0017] The (AB)n block silicone polyethers are endblocked. The endblocking unit is also determined by the reaction employed to prepare the (AB)n block silicone polyether copolymer, which is generally the residual reactive groups ofthe reactants used. For example, the (AB)n block silicone polyether copolymers can be prepared by the metal catalyzed hydrosilylation reaction of a diallyl polyether (i.e. an allyl group is present on each molecular terminal end) with a SiH terminated polyorganosiloxane. The resulting (AB)n block silicone polyether copolymer would have polyoxyalkylene blocks linked to the silicone blocks via a propyleneoxy group (-CH2CH2CH2O-), and using a slight molar excess ofthe allyl polyether would result in an allyl endblock unit (-CH2CHCH2). Alternative endblock units can result from the addition of other molecules in the reaction employed to prepare the (AB)n block silicone polyether copolymer that are capable of reacting with the siloxane or polyether block intermediates. For example, the addition of organic compounds having mono-terminated aliphatic unsaturation (such as a mono allyl terminated polyether) will result in the endcapping ofthe (AB)„ block silicone polyether copolymer with that organic compound. Typically, the endblocking unit ofthe (AB)n block silicone polyether is an allyl ether (CH2=CHCH2O-) or allyl polyether. [0018] The molecular weights ofthe (AB)„ block silicone polyether copolymers will be determined by the number of repeating siloxane and polyoxyalkylene blocks, as indicated by the subscript z in Formula I. Typically, the value of z is such to provide weight average molecular weights (Mw) to range from 1,500 to 150,000, alternatively, from 10,000 to 100,000.
[0019] The ratio ofthe silicone block to the polyoxyalkylene block in the (AB)n SPEs can also be used to identify which structures form vesicles or stable aqueous emulsions. This molecular parameter is expressed by the value of x/(x+y) in Formula I. The value of x/(x+y) can vary from 0.2 to 0.9, or alternatively from 0.4 to 0.9. [0020] The (AB)n SPEs of the present invention can be prepared by any method known in the art for preparing such block copolymers. Alternatively, the (AB)n SPEs ofthe present invention are prepared according the methods described infra.
[0021] The present invention further provides a process to prepare an (AB)n block silicone polyether copolymer comprising reacting; a) a SiH terminated organopolysiloxane, b) a polyoxyalkylene having an unsaturated hydrocarbon group at each molecular terminal, c) a hydrosilylation catalyst, d) optionally a solvent, e) optionally an organic endblocker compound having a mono-terminally unsaturated hydrocarbon group, wherein the mole ratio ofthe unsaturated organic groups to SiH in the reaction is at least 1:1. [0022] The SiH terminated organopolysiloxanes useful in the process ofthe present invention can be represented by the formula M'DM', where "M"' means a siloxane unit of formula R2HSiO 2, "D" means a siloxane unit of formula R2SiO2/2, where R is independently a monovalent organic group as defined above. Typically, the SiH terminated organopolysiloxane is a dimethylhydrogensiloxy-terminated polydimethylsiloxane having the average formula Me2HSiO(Me2SiO)xSiHMe2, where x is as defined above. SiH terminated organopolysiloxanes and methods for their preparation are well known in the art. [0023] The polyoxyalkylene useful in the process ofthe present invention may be a polyoxyethylene comprising the average formula -(C2H4O)y - , where y is defined as above, and is terminated at each molecular chain end (i.e. alpha and omega positions) with a unsaturated organic group. The unsaturated organic group can be an unsaturated hydrocarbon group such as alkenyl or alkynyl group. Representative, non- limiting examples ofthe alkenyl groups are shown by the following structures; H2C=CH-, H2C=CHCH2-, H2C=C(CH3)CH2- , H2C=CHCH2CH2-, H2C=CHCH2CH2CH2-, and
H2C=CHCH2CH2CH2CH2-. Representative, non- limiting examples of alkynyl groups are shown by the following structures; HC≡C-, HC≡CCH2-, HC≡CC(CH3) - , HC≡CC(CH3)2 - , HC≡CC(CH3)2CH2- . Polyoxyethylenes having an unsaturated hydrocarbon group at each molecular terminal are known in the art, and many are commercially available. Alternatively, the unsaturated organic group can be an organofunctional hydrocarbon such as an acrylate, methacrylate and the like. Typically the polyoxyethylene has the average formula H2C=CHCH O(CH2CH2O)yCH2CH=CH2 wherein y is greater than 4, or alternatively ranges from range from 5 to 30, or alternatively from 5 to 22. [0024] The SiH terminated organopolysiloxane and polyoxyalkylene having an unsaturated organic group at each molecular terminal are reacted in the presence of a hydrosilylation catalyst, which are known in the art. Such hydrosilylation catalysts are illustrated by any metal-containing catalyst which facilitates the reaction of silicon-bonded hydrogen atoms of the SiH terminated organopolysiloxane with the unsaturated hydrocarbon group on the polyoxyethylene. The metals are illustrated by ruthenium, rhodium, palladium, osmium, iridium, or platinum.
[0025] Hydrosilylation catalysts are illustrated by the following; chloroplatinic acid, alcohol modified chloroplatinic acids, olefin complexes of chloroplatinic acid, complexes of chloroplatinic acid and divinyltetramethyldisiloxane, fine platinum particles adsorbed on carbon carriers, platinum supported on metal oxide carriers such as Pt(Al2θ3), platinum black, platinum acetylacetonate, platinum(divinyltetramethyldisiloxane), platinous halides exemplified by PtCl2, PtC-4, Pt(CN)2, complexes of platinous halides with unsaturated compounds exemplified by ethylene, propylene, and organovinylsiloxanes, styrene hexamethyldiplatinum. and RhCl3(Bu2S)3.
[0026] The amount of hydrosilylation catalyst that is used is not narrowly limited as long as there is a sufficient amount to accelerate a reaction between the polyoxyethylene having an unsaturated hydrocarbon group at each molecular terminal and the SiH terminated organopolysiloxane at room temperature or at temperatures above room temperature. The exact necessary amount of this catalyst will depend on the particular catalyst utilized and is not easily predictable. However, for platinum-containing catalysts the amount can be as low as one weight part of platinum for every one million weight parts of components the polyoxyethylene having an unsaturated hydrocarbon group at each molecular terminal and the SiH terminated organopolysiloxane. The catalyst can be added at an amount 10 to 120 weight parts per one million parts of components the polyoxyethylene having an unsaturated organic group at each molecular terminal and the SiH terminated organopolysiloxane, but is typically added in an amount from 10 to 60 weight parts per one million parts ofthe polyoxyethylene having an unsaturated organic group at each molecular terminal and the SiH terminated organopolysiloxane.
[0027] The hydrosilylation reaction can be conducted neat or in the presence of d), a solvent. The solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol, a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether, a halogenated hydrocarbon such as dichloromethane, 1,1,1- trichloroethane or methylene chloride, chloroform, dimethyl sulfoxide, dimethyl formamide, acetonitrile, tetrahydrofuran, white spirits, mineral spirits, or naphtha.
[0028] The amount of solvent can be up to 50 weight percent, but is typically from 20 to 50 weight percent, said weight percent being based on the total weight of components in the hydrosilylation reaction. The solvent used during the hydrosilylation reaction can be subsequently removed from the resulting silicone polyether by various known methods. [0029] Additional components can be added to the hydrosilylation reaction which are known to enhance such reactions. These components include salts such as sodium acetate which have a buffering effect in combination with platinum catalysts.
[0030] In a first embodiment ofthe present invention, the (AB)n SPEs of Formula I have a value of x (i.e. the degree of polymerization, DP, ofthe polysiioxane chain in the siloxane units) that ranges from 20 to 100, alternatively from 30 to 75. These structures form vesicles in aqueous media. Such vesicle compositions can be prepared by mixing the (AB)n SPEs with water using any technique known common in the state ofthe art for creating vesicle compositions. The type and extent ofthe mixing technique will depend on the specific structure ofthe (AB)n SPE chosen. For example, some (AB)n SPEs will form vesicle compositions spontaneously when mixed with water, while others (AB)n SPEs will require the presence of an optional water soluble solvent (Component B described infra) to facilitate the formation of vesicles.
[0031] Optional component B) is a water-miscible volatile solvent. As used herein "water- miscible" means the solvent forms a dispersion with water at room temperature for at least 1 several hours. "Volatile" means the solvent has a higher vapor pressure than water at various temperatures. As such, when the aqueous dispersion ofthe organopolysiloxane and solvent are subjected to conditions to remove the solvent, such as heating the dispersion under reduced pressures, the solvent is primarily removed first, allowing all or most ofthe water to remain in the composition. [0032] Suitable water-miscible volatile solvents as component B) include organic solvents such as alcohols, ethers, glycols, esters, acids, halogenated hydrocarbons, diols. The organic solvents should be miscible with water at the proportion and lower in order to effectively disperse silicones and maintain stable and uniform dispersion overtime. For the purpose of illustration, water-miscible alcohols include methanol, ethanol, propanol, isopropanol, butanol, and higher hydrocarbon alcohols; ethers include gylcol ethers, methyl-ethyl ether, methyl isobutyl ether (MIBK), etc; glycols include propylene glycols, esters include esters of triglycerol, the esterification products of acid and alcohol; halogenated hydrocarbons include chloroform. Typically water-miscible organic solvents are solvents with relatively low boiling points (<100°C) or high evaporation rate, so they may be removed under vacuum with ease. The most preferred water-miscible organic solvents for this invention are volatile alcohols including methanol, ethanol, isopropanol, and propanol. These alcohols can be removed from aqueous mixtures containing silicone dispersions via vacuum stripping at ambient temperature.
[0033] The aqueous compositions may further optionally comprise a silicone or organic oil, component C). The silicone can be any organopolysiloxane having the general formula RjSiO( .i)/2 in which i has an average value of one to three and R is a monovalent organic group. The organopolysiloxane can be cyclic, linear, branched, and mixtures thereof. [0034] Component C) may be a volatile methyl siloxane (VMS) which includes low molecular weight linear and cyclic volatile methyl siloxanes. Volatile methyl siloxanes conforming to the CTFA definition of cyclomethicones are considered to be within the definition of low molecular weight siloxane. [0035] When component C) is an organic oil, it may be selected from any organic oil known in the art suitable for use in the preparation of personal, household, or healthcare formulations. Suitable organic oils include, but are not limited to, natural oils such as coconut oil; hydrocarbons such as mineral oil and hydrogenated polyisobutene; fatty alcohols such as octyldodecanol; esters such as C12 -C15 alkyl benzoate; diesters such as propylene dipelarganate; and triesters, such as glyceryl trioctanoate. The organic oil components can also be mixture of low viscosity and high viscosity oils. Suitable low viscosity oils have a viscosity of 5 to 100 mPa-s at 25°C, and are generally esters having the structure RCO-OR' wherein RCO represents the carboxylic acid radical and wherein OR' is an alcohol residue. Examples of these low viscosity oils include isotridecyl isononanoate, PEG-4 diheptanoate, isostearyl neopentanoate, tridecyl neopentanoate, cetyl octanoate, cetyl palmitate, cetyl ricinoleate, cetyl stearate, cetyl myristate, coco-dicaprylate/caprate, decyl isostearate, isodecyl oleate, isodecyl neopentanoate, isohexyl neopentanoate, octyl palmitate, dioctyl malate, tridecyl octanoate, myristyl myristate, octododecanol, or mixtures of octyldodecanol, acetylated lanolin alcohol, cetyl acetate, isododecanol, polyglyceryl-3-diisostearate, or mixtures thereof. The high viscosity surface oils generally have a viscosity of 200-1 ,000,000 mPa-s at 25°C, preferably a viscosity of 100,000-250,000 mPa-s. Surface oils include castor oil, lanolin and lanolin derivatives, triisocetyl citrate, sorbitan sesquioleate, CIO- 18 triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil, cottonseed oil, glyceryl triacetyl hydroxystearate, glyceryl triacetyl ricinoleate, glyceryl trioctanoate, hydrogenated castor oil, linseed oil, mink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, sunflower seed oil, tallow, tricaprin, trihydroxystearin, triisostearin, trilaurin, trilinolein, trimyristin, triolein, tripalmitin, tristearin, walnut oil, wheat germ oil, cholesterol, or mixtures thereof. Mention may be made, among the optional other non-silicone fatty substances, of mineral oils, such as liquid paraffin or liquid petroleum, of animal oils, such as perhydrosqualene or arara oil, or alternatively of vegetable oils, such as sweet almond, calophyllum, palm, castor, avocado, jojaba, olive or cereal germ oil. It is also possible to use esters of lanolic acid, of oleic acid, of lauric acid, of stearic acid or of myristic acid, for example; alcohols, such as oleyl alcohol, linoleyl or linolenyl alcohol, isostearyl alcohol or octyldodecanol; or acetylglycerides, octanoates, decanoates or ricinoleates of alcohols or of polyalcohols. It is alternatively possible to use hydrogenated oils which are solid at 25°C, such as hydrogenated castor, palm or coconut oils, or hydrogenated tallow; mono-, di-, tri- or sucroglycerides; lanolins; or fatty esters which are solid at 25°C. [0036] The formation of vesicles in the compositions ofthe present invention can be confirmed by techniques common in the state ofthe art. Typically, vesicles having a lamellar phase structure which exhibit birefringence when examined with a cross polarizing microscope. Alternatively, the formation of vesicles can be demonstrated by Cyro-
Transmission Electron Microscopy (Cryo-TEM) techniques. Particle size measurements can also be used to indicate that the organopolysiloxanes are sufficiently dispersed in aqueous medium typical of vesicle sizes For example, average particle sizes of less than 0.500 μm (micrometers), are typical for dispersed vesicles. Vesicles having a average particle size of less than 0.200 μm, or 0.100 μm are possible with the teachings of the present invention. [0037] The amount ofthe (AB)n block silicone polyether copolymer (Component A), optional water-miscible volatile solvent (Component B), and water can vary in the compositions ofthe present invention, but typically range as follows; A) 2 to 50 wt%, alternatively 2 to 25 wt %, or alternatively 2 to 15 wt%, B) 0 to 50 wt%, alternatively 2 to 30 wt %, or alternatively 2 to 20 wt%, C) 0 to 50 wt %, alternatively 1 to 20 wt %, or alternatively 2 to 10 wt%, and sufficient amounts of water to provide the sum ofthe wt% of A), B), and water to equal 100%.
[0038] Alternatively, the vesicle compositions can be prepared according to the methods of the present invention, as discussed infra.
[0039] The present invention also provides a process for making an aqueous composition comprising; I) combining, A) an (AB)n block silicone polyether copolymer having the average formula; -[R1(R2SiO)x(R2SiR1O)(CmH2mO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons, B) an optional water miscible volatile solvent, with water to form an aqueous dispersion, II) mixing the aqueous dispersion to form dispersed particles ofthe (AB)„ silicone polyether copolymer having an average particle size of less than 10 micrometers, III) optionally, removing the water miscible volatile solvent from the aqueous dispersion. [0040] Step I) involves combining an (AB)n SPEs, component A) and optional component
B), a water-miscible volatile solvent. Components A) and B) in step I) are the same as described above. The amount of components A), B), and water combined in step I) can vary in the process, but typically range as follows; A) 2 to 50 wt%, alternatively 2 to 25 wt %, or alternatively 2 to 15 wt%, B) 0 to 50 wt%, alternatively 2 to 30 wt %, or alternatively 2 to 20 wt%, and sufficient amounts of water to provide the sum ofthe wt% of A), B), and water to equal
100%.
[0041] Step II in the above process is mixing the aqueous dispersion formed in Step I to form dispersed particles ofthe (AB)„ silicone polyether copolymer having an average particle size of less than 10 micrometers. There are no special requirements or conditions needed to effect the mixing of step II). Mixing techniques can be simple stirring, homogenizing, sonalating, and other mixing techniques known in the art. The mixing can be conducted in a batch, semi-continuous, or continuous process.
[0042] Step III in the above process is optional, and involves removing the water miscible volatile solvent, component B). Typically, the water miscible volatile solvent is removed by known techniques in the art, such as subjecting the vesicle composition to reduced pressures, while optionally heating the composition. Devices illustrative of such techniques include rotary evaporators and thin film strippers.
[0043] In a second embodiment ofthe present invention, the (AB)n SPEs of Formula I have a value of x (i.e. the degree of polymerization, DP, ofthe polysiioxane chain in the siloxane units) that ranges from 5 to 19, alternatively from 5 to 10. These structures form stable emulsions in aqueous media having a particle size of less than 10 micrometers. The stable emulsions can be prepared by mixing the (AB)n SPEs ofthe second embodiment with water, according to known techniques for preparing water continuous emulsions. Alternatively, the emulsion compositions can be prepared according to the methods ofthe present invention, as discussed infra.
[0044] The present invention thus provides a process for preparing a water continuous emulsion having an average particle size of less than 10 micrometers comprising; I) mixing A) an (AB)n block silicone polyether copolymer having the average formula; -[R1(R2SiO)x(R2SiR1O)(CmH2mO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons, B) an optional water miscible volatile solvent to form a hydrophobic phase, II) adding water to the hydrophobic phase to form the water continuous emulsion. [0045] The (AB)n SPEs, component A) and optional water-miscible volatile solvent, component B) in step II) ofthe above process are the same as described above. [0046] After forming a hydrophobic phase of A) and B), water is then added to the mixture in step II ofthe present process to prepare a water continuous emulsion. There are no special requirements or conditions needed for effecting the mixing of components A), B) in step I and subsequent mixing with water in step II). The mixing and water addition steps can be conducted in a batch, semi-continuous, or continuous process. [0047] The hydrophobic phase of step I) can also comprise a silicone or organic oil, as component C), and is the same as described above
[0048] The hydrophobic phase of step I) can also comprise optionally a personal, household, or healthcare active. A listing of possible personal, household, or health care ingredients is taught in WO 03/101412, which is incorporated herein by reference. The personal or health care ingredient can also be selected from a personal or health care "active", that is, any compound known to have either cosmetic and/or pharmaceutical activity. A representative listing of such personal or health care actives are disclosed in US Patent 6,168,782, which is hereby incorporated by reference. The common assignee's U.S. Patent 5,948,855 (September 7, 1999), also contains an extensive list of some appropriate oil soluble active ingredients such as vitamins and drugs which can be used in the oil phase ofthe oil in water emulsions, among which are vitamins, including but not limited to, Vitamin A \ , RETINOL, C2-C \ g esters of RETINOL, Vitamin E, TOCOPHEROL, esters of Vitamin E, and mixtures thereof. RETINOL includes trans-RETINOL, 13-cis-RETINOL, 11-cis-RETINOL, 9-cis-RETINOL, and 3,4-didehydro-RETINOL. Other vitamins which are appropriate include RETIN YL ACETATE, RETINYL PALMITATE, RETINYL PROPIONATE, α-TOCOPHEROL, TOCOPHERSOLAN, TOCOPHERYL ACETATE, TOCOPHERYL LINOLEATE, TOCOPHERYL NICOTINATE, and TOCOPHERYL SUCCINATE. The amount of components A), B), C), and D) can vary in the process to prepare the emulsions ofthe present invention, but typically range as follows; A) 2 to 60 wt%, alternatively 2 to 50 wt %, or alternatively 2 to 40 wt%, B) 0 to 50 wt%, alternatively 2 to 30 wt %, or alternatively 2 to 20 wt%, C) 0 to 30 wt%, alternatively 0 to 25 wt %, or alternatively 0 to 20 wt%, D) 0 to 30 wt%, alternatively 0 to 25 wt %, or alternatively 0 to 20 wt%, where sufficient amount of water is added to provide the sum ofthe wt% of A), B), C), D), and water to equal 100%. The present invention also relates to vesicle compositions further comprising a personal, household, or health care ingredient. Thus, the vesicle compositions can be used to entrap, and subsequently deliver after application, a personal, household care, or health care ingredient. A listing of possible personal, household, or health care ingredients is taught in WO 03/101412, which is incorporated herein by reference. The personal or health care ingredient can also be selected from a personal or health care "active", that is, any compound known to have either cosmetic and/or pharmaceutical activity. A representative listing of such personal or health care actives are disclosed in US Patent 6,168,782, which is hereby incorporated by reference. Compositions prepared according to the invention can be used in various over-the- counter (OTC) personal care compositions, health care compositions, and household care compositions, but especially in the personal care arena. Thus, they can be used in antiperspirants, deodorants, skin creams, skin care lotions, moisturizers, facial treatments such as acne or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colognes, sachets, sunscreens, pre-shave and after-shave lotions, liquid soaps, shaving soaps, shaving lathers, hair shampoos, hair conditioners, hair sprays, mousses, permanents, depilatories, hair cuticle coats, make-ups, color cosmetics, foundations, blushes, lipsticks, lip balms, eyeliners, mascaras, oil removers, color cosmetic removers, nail polishes, and powders.
EXAMPLES
[0049] The following examples are presented to further illustrate the compositions and methods of this invention, but are not to be construed as limiting the invention. All parts and percentages in the examples are on a weight basis and all measurements were obtained at 23 °C, unless indicated to the contrary.
Materials
[0050] The representative (AB)n silicone polyethers, herein designated as (AB)n SPE, used in the emulsion compositions ofthe present invention were prepared from the hydrosilylation reaction of M'DXM' siloxanes (dimethyl-hydrogen terminated (Me2HSiO) linear polydimethylsiloxanes of varying degree of polymerizations (as designated by x and prepared using well known siloxane polymerization techniques) and allyl terminated polyethers (alpha, omega-diallyloxy polyethers having the average formula, (CH2=CHCH2O(CH2CH2O)mCH2CH=CH2). Polyglycol AA600, AAl 200, and AA2000 were used as obtained from Clariant (Mt. Holly,
NC), and contained on average 12, 25, and 44 ethylene oxide units (designated as EO, i.e. m
= 12, 25, and 44 in the above formula).
Testing Procedures
Particle Size
Cyro-Transmission Electron Microscopy (TEM) [0051] The vesicle compositions were analyzed via Cyro-TEM techniques according to the following procedure. Around 2.3 μl of aqueous sample solution was loaded using a' micropipette on a lacey carbon film coated Cu TEM grid that was cleaned and rinsed with acetone and chloroform. The samples were diluted to 5% solution with de-ionized water. The excess fluid on the grid surface was removed by blotting the surface with a filter paper for 1.5 second to make an aqueous thin film for TEM. The grid was then plunged into a liquid ethane contained in a small vessel located in a larger liquid nitrogen vessel under -175 °C atmosphere in the cryo-plunge system to vitrify the water film on the grid and to avoid water crystallization. The quenched sample grid was transferred in to the cryo-grid box in the cryo- plunge system. The grid box containing the sample was transferred into a Gatan cryo-transfer system filled with liquid nitrogen and loaded in a cryo-TEM stage, which has been positioned in the cryo-transfer system and cooled down to below -160 °C. The sample was loaded in TEM (JEOL 2000FX) and the images were observed at below -160 °C. A much colder finger, cooled to -180 °C in TEM using liquid nitrogen, was present to reduce any possible contamination on the cold specimen surface under high vacuum during TEM analysis. The digital images, as shown herein, were taken using a Gatan CCD camera attached at the bottom ofthe TEM column and Digital Micrograph software.
Examples 1 - 6 (Referenced
[0052] Various (AB)n SPEs, as summarized in Tables 1 were prepared via the platinum catalyzed hydrosilylation ofthe SiH siloxanes with the allyl polyethers utilizing the following general procedure.
Procedure to Prepare SPEs
[0053] A 1000 ml three neck round bottom flash equipped with temperature probe, electrical stirrer, and condenser was charged with an amount (as indicated in Table 1) of a polyethylene glycol diallyl ether (Clariant Corp., Mt. Holly, NC), 61 gram of xylene and 0.28 gram of sodium acetate. The contents ofthe flask were then heated to 100 °C. A dimethylhydrogen endblocked polydimethyl siloxane was added dropwise via an addition funnel (amount and structures shown in Table 2). After adding 5 gram ofthe siloxane, 0.60 gram of platinum catalyst (l,3-diethenyl-l,l,3,3-tetramethyldisiloxane platinum complex in dimethyl siloxane) was added to the mixture.. When half ofthe siloxane was added, an additional 0.69 gram of Pt catalyst was added, followed by 0.71 gram of Pt when all the siloxane addition was complete. The reaction mixture was allowed to mix for 1 hour for the polymer to grow. The xylene solvent was then removed via vacuum stripping at 150 °C. [0054] Multiple batches of (AB)n SPEs block copolymers were made, in some cases, to create molecular weight variations ofthe same (AB)n SPEs block copolymers from a given siloxane and polyether combinations. These also demonstrate the suitability of (AB)n copolymers having different chain lengths (i.e. n values) to prepare the vesicle compositions.
Table 1
Figure imgf000021_0001
Examples 12 - 16
Vesicle Compositions from (AB)„ SPE 2 [0055] The following procedure was used to prepare the vesicle compositions summarized in Table 3 as Examples 12 and 13.
[0056] Isopropanol (IPA) was added to (AB)„ SPE 2, (a (AB)n block copolymer of M'D50M' siloxane and polyglycol AAl 200 polyether, having a weight-average molecular weight Mw of 50,108 g/mole), to provide a homogeneous mixture. With continuous mixing, water was added slowly to form a homogeneous dispersion having an average particle size of 0.208 μm. The IPA in the dispersion was then removed using a Rotovapor under vacuum at ambient temperature, to yield an alcohol-free, homogeneous dispersion having an average particle size of 0.223 μm, designated as Example 13. [0057] Three additional vesicle compositions using (AB)n SPE 2 block copolymer were made, following the procedure of Example 12, except an optional homogenization step was introduced after the mixture was made and before the vacuum strip. Ethanol (EtOH) was used in place of IPA as the alcohol. The compositions are summarized in Table 3. As the data indicates, the homogenization step reduced the average particle size and maintained the homogeneity ofthe dispersion. Removal ofthe volatile alcohol (EtOH) did not compromise the quality ofthe dispersion.
[0058] The particle size distributions ofthe compositions for Example 14 - 16 are shown in figure 1. The cyro TEM images ofthe compositions of Examples 13 - 16, as shown in Figures 2 - 5, confirm the presence ofthe vesicle structures.
Table 3
Figure imgf000023_0001
Examples 17 -19
Vesicle Compositions from (AB)„ SPE 1
[0059] Vesicle compositions of (AB)n SPE 1 an (AB)n block copolymer of M'D30M' siloxane and polyglycol AAl 200 polyether, having a weight-average molecular weight Mw of 19486 g/mole were prepared following the procedure of Examples 12-13. These vesicle compositions are summarized in Table 4 as Examples 17 - 19. All three compositions had an average particle size distribution of less than 40 nm (0.040 μm). These examples demonstrate that the removal of alcohol did not affect the quality of dispersion and the homogenization step is optional.
Table 4
Figure imgf000024_0001
Examples 20 - 23
Vesicle Compositions from (AB)„ SPE 3 A & B
[0060] Nesicle compositions were prepared from (AB)„ SPE 3 A andB, (AB)n silicone polyether block copolymers of M'D 5M' siloxane and polyglycol AA1200 polyether having a weight-average molecular weight Mw of 40, 158 and 44,885 g/mole, respectively. These dispersions were made following the procedure described in Examples 12 - 13 and are summarized in Table 5.
Table 5
Figure imgf000025_0001
Examples 24 - 25
Alcohol free vesicle compositions from (AB)„ SPE 3 B
[0061] Alcohol-free vesicle compositions were prepared from (AB)„ SPE 3 B an (AB)n silicone polyether block copolymer of M'D75M' siloxane and polyglycol AA1200 polyether, having a weight-average molecular weight Mw of 44,885 g/mole following the procedure of Examples 12 -13, and removing the alcohol under reduced pressure. The compositions are summarized in Table 6.
Table 6
Figure imgf000026_0001
Example 26 - 27
Vitamin A palmitate loaded in vesicles from (AB)n SPE 1
[0062] Nitamin A palmitate was first mixed with isopropanol at 50/50 ratio. The vitamin / IPA mixture was then mixed with (AB)n SPE 1, a (AB)n block copolymer of M'D3oM' siloxane and polyglycol AA1200 polyether, having a weight-average molecular weight Mw of 19486 g/mole to homogenous. Ethanol was then admixed to form a homogeneous mixture. While under continuous mixing, de-ionized water was slowly and gradually incorporated into the SPE / vitamin / alcohol mixture, till homogenous. The mixture was homogenized, using an APN-2000 Gaulin homogenizer, producing a homogeneous dispersion with sub-micron particle size, identified as Example 26 in Table 8. The Example 26 composition was then further homogenized. The alcohol was removed under reduced pressure at ambient temperature to produce a composition having an average particle size of 0.54 um, listed as Example 27 in Table 8. The removal of alcohol processing aid did not affect the dispersion quality and the particle size.
Table 8
Figure imgf000028_0001
Example 28
[0063] The following vitamin A palmitate loaded (AB)n SPE vesicles in water dispersion was prepared according to the method shown in the previous examples of this invention. The (AB)n SPE is a copolymer of 50 dp siloxane and Polyglycol AA1200 polyether. The final composition ofthe vesicle dispersion is shown in Table 9.
Table 9
Figure imgf000029_0001
[0064] The vitamin-loaded SPE vesicles can easily be formulated into skin care formulations. Oil-based vitamins can be easily incorporated into water-based formulations. The following examples provide such illustrations.
Example 29
Oil-in-ΛVater body lotion
Ingredients Parts
Part A
Cetearyl Alcohol 3
Diisopropyl Adipate (Crodamol DA) 5
Dimethicone (Dow Coming Silicone 200 / 100 cstks) 0.5
Potassium cetyl phosphate 1.5
Buthylated hydroxytoluene 0.05
Cheating agent (EDTA) 0.1
Phenoxyethanol 0.6
Par B
Water up to 100
Carbomer 980 thickener 30
Potassium hydroxyde 1.5
Par C
Vitamin A palmitate loaded SPE vesicles 19.88
[0065] To prepare the body lotion, the following procedure was followed: The ingredients in
Part A were mixed and heated to 85 °C to homogeneous. Cool the part A mixture to 40 °C, then incorporate the part B ingredients. Cooled the mixture to ambient temperature.
Incorporate vitamin A palmitate-loaded SPE vesicles into the mixture and mix to homogeneous. The final mixture is a smooth, slightly yellowish creamy lotion.
Example 30
Simple Moisturing Gel for Skin
[0066] The (AB)n type SPE vesicles can be easily formulated into aqueous based gel formulations. SPE vesicles provide a convenient means to incorporate oil-soluble vitamins into water-rich gel formulations.
Ingredients Parts
Part A
Water to 100%
Preservative 0.30%
Polyacrylamide, C13-14 Isoparaffin, 1% laureth-7 (Sepigel 305)
Part B
Vitamin A palmitate-loaded SPE 19.88 vesicles To prepare the gel, the following procedure was followed: The ingredients in Part A were mixed to homogeneous. Nitamin A palmitate-loaded SPE vesicles dispersion was then incorporated and mixed to homogeneous. The final product is a beige, smooth gel. [0067] To further demonstrate the integrity of vesicles in formulations, cryo-TEM images of the "as formulated" products were taken. An image ofthe gel from the above example is shown figure 6. As illustrated, the vesicles and aggregates of vesicles were well preserved. [0068] A cryo-TEM image ofthe "as prepared" body lotion illustrated in Example A, prepared from (AB)n SPE vesicle is shown in figure 7. The characteristic vesicles and aggregate structures uniquely associated with the (AB)n SPE vesicles shown in figure 7.
Examples 31 - 32 (Reference')
[0069] A series of (AB)n SPEs, as listed below, were prepared according to the procedures described in Examples 1 - 6.
(AB)n SPE 31 A - reaction product from M'D15M' and AA2000, Mw = 16,022 (AB)„ SPE 3 IB - reaction product from M'D15M' and AA2000, Mw = 24,426. (AB)n SPE 32A - reaction product from M'Dι5M' and AA1200, Mw = 33,552. (AB)„ SPE 32B - reaction product from M'D.5M' and AA1200, Mw = 35,352.
Example 33
(AB)n SPE 31 A dispersion in water
[0070] (AB)n SPE 31 A (reaction product of M'D15M' siloxane and polyglycol AA2000 polyether) was a solid, waxy material with a melting point of 45-47 °C. A dispersion of this polymer was made by dispersing this solid polymer in water using a low shear mechanical mixing device. The dispersion had an average particle size of 1.867 μm.
Example 34-36 (AB)n SPE 31 A dispersions in alcohol-containing water
[0071] Dispersions of (AB)n SPE 31 A copolymer were prepared in alcohol-water mixture. The solid (AB)n SPE copolymer was dispersed, via a mechanical shear device, into isopropanol / water mixtures at a ratio of 5/85, and 20/70, respectively, as summarized in Table 10. Additionally, a dispersion of sub-micron size in water was also obtained by vacuum stripping IPA off the mixture.
Table 10
Figure imgf000033_0001
Example 37
Vitamin A palmitate loaded (AB)n SPE particle dispersions.
[0072] Nitamin A palmitate is not soluble in water and can not be dispersed in water directly. The example shows that particle dispersion forming (AB)n SPE block copolymer can be used to incorporate water-insoluble vitamins and form a stable dispersion in water. The dispersion was prepared as followed: A 50/50 by weight pre-mixture of vitamin A palmitate and Dow Corning® DC 1-2287 vinyl silicone fluid was prepared. The premix was incorporated to form a homogeneous mixture with (AB)n SPE 31A copolymer. Deionized water was slowly incorporated into the above mixture while under continuous mixing. As shown in Table 11, a dispersion having an average particle size of 1.68 μm was obtained in water. The vitamin A palmitate payload in the dispersion particles was 17%.
Table 11
Figure imgf000034_0001
Examples 38-40
Si/W emulsions from (AB)n SPE
[0073] Three Si/W emulsions of different compositions were prepared via high shear emulsification process. The method of preparation includes the following steps: the silicone fluids were incorporated into (AB)n SPE 32A copolymer to form a homogeneous mixture. A small amount of water was incorporated into the phase A mixture, followed by high shear mixing to disperse the water using a Speed Mixer. Water additions in small quantity continued until the mixture inverted or form a continuous, smooth cream (called inverted into a water-continuous emulsion concentrate). The remaining water was added to further dilute the emulsion to desired concentration and consistency. The final emulsions had an average particle size between 1.3 and 2.1 μm.
[0074] These Si/W emulsion examples illustrated that it is possible to prepare emulsion particles of desirable compositions comprising the (AB)n SPE polymer and silicone oils. The compositions are summarized in the Table 12.
Table 12
Figure imgf000035_0001
Examples 41 -42
Sub-micron (AB)n SPE 3 IB copolymer particle emulsions in water
[0075] Another (AB)n SPE block copolymer was used to prepare Si/W emulsions. (AB)n SPE 31B is the block copolymer reaction product of M'Dι5M' siloxane and polyglycol AA2000 polyether (segment length of 44 EO units) and has a melting temperature 45 - 47 °C. These Si/W emulsions Examples were made by mechanical emulsification using a high-shear mixer (Speed Mixer), similar to the ones described above. The step-wise procedures can be found in the previous examples. The final Si/W emulsions had an average particle size of 0.394 μm and 0.725 μm, respectively, as summarized in Table 13.
Table 13
Figure imgf000036_0001
Examples 43 - 45
Si/W emulsions and vitamin loaded (Si+0)/W emulsions
[0076] (AB)n SPE block copolymer in Si/W emulsion form can be used to carry and protect water-insoluble oils and substances. These emulsions can subsequently be incorporated into water-based end products and formulations.
[0077] Nitamin A palmitate is water-insoluble and cannot be incorporated directly into water-based formulations. These examples showed that stable Si/W emulsions containing various amount of vitamin A palmitate were successfully prepared from (AB)n SPE block copolymer.
[0078] The Si/W emulsions were prepared using SPE 32 A copolymer, an (AB)n block copolymer product of M'Dι5M' siloxane and polyglycol AA1200 polyether and has a melting temperature of 27 - 32 °C. DC 245 silicone cyclics and DC 1-2287 vinyl silicone fluids were used to prepare the following Si/W and (Si+O)/W emulsions.
[0079] These emulsions were prepared following the following procedures: vitamin A palmitate was first mixed with DC 1-2287 vinyl silicone fluid to form a homogeneous mixture, then incorporated into the (AB)n SPE 32 A copolymer with mixing to yield a homogeneous premixture. De-ionized water was slowly and gradually incorporated into the phase A mixture using a high-shear mixer (Speed Mixer) till the mixture inverted into water- continuous mixture. The remaining water was added, under shear to complete the dilution to desired composition. The final emulsions are smooth, milky white emulsions, as summarized in Table 14. [0080] The two vitamin A palmitate loaded (AB)n SPE block copolymer emulsions had a particle size of 1.62 μm and 1.02 μm, respectively. The vitamin payload was 13.4 % and 20.3%, respectively. Table 14
Figure imgf000038_0001
Examples 46 - 47
Vitamin loaded emulsions formulated into skin care products
[0081] Vitamin A palmitate loaded (AB)n SPE particle dispersions in water were prepared according to the method shown in the previous examples. Example 46 was prepared from (AB)n SPE copolymer of 15 dp silloxane and Polyglycol AA2000 polyether, and Example 47 dispersion from (AB)n SPE copolymer of 15 dp siloxane and Polyglycol AA1200 polyether. The final compositions of these dispersions are shown in Table 15.
Table 15
Figure imgf000039_0001
The vitamin-loaded SPE particle dispersions were formulated into skin care formulations.
Oil-in-water body lotion
Ingredients Parts
Part A
Cetearyl Alcohol 3
Diisopropyl Adipate (Crodamol DA) 5
Dimethicone (Dow Coming Silicone 200 / 100 cs) 0.5
Potassium cetyl phosphate 1.5 Buthylated hydroxytoluene 0.05 Cheating agent (EDTA) 0.1 Phenoxyethanol 0.6
Part B
Water up to 100
Carbomer 980 thickener 30
Potassium hydroxide 1.5
Part C
Vitamin A palmitate loaded SPE particle dispersions 19.88
[0082] To prepare the body lotion, the following procedure was followed: The ingredients in Part A were mixed and heated to 85 °C to homogeneous. Cool the part A mixture to 40 °C, then incorporate the part B ingredients. Cooled the mixture to ambient temperature. Incorporate vitamin A palmitate-loaded SPE particle disperison into the mixture and mix to homogeneous. The final mixture is a smooth, slightly yellowish creamy lotion. [0083] A cryo-TEM image of the "as prepared" body lotion illustrated in this Example confirmed the dispersed particles remained in tack and stable following the preparation ofthe formulation.
Moisturing Gel for Skin
[0084] The (AB)n type SPE particle dispersions can be formulated into aqueous based gel formulations. SPE vesicles provide a convenient means to incorporate oil-soluble vitamins into water-rich gel formulations.
Ingredients Parts
Part A
Water to 100%
Preservative 0.30%
Polyacrylamide, C 13-14 Isoparaffln, 1% laureth-7 (Sepigel 305)
Part B
Vitamin A palmitate-loaded SPE 19.88 particle dispersions To prepare the gel, the following procedure was followed: The ingredients in Part A were mixed to homogeneous. Vitamin A palmitate-loaded SPE particle dispersion was then incorporated and mixed to homogeneous. The final product is a beige, smooth gel. [0085] To further demonstrate the integrity ofthe dispersion particles in formulations, cryo- TEM images ofthe "as formulated" products were taken. The resulting image ofthe gel from the above example confirmed the dispersion particles were well preserved.
Examples 48-49
[0086] The following vitamin A palmitate loaded (AB)n SPE particle dispersions in water were prepared according to the method shown in the previous examples of this invention. An
The emulsion labeled as Example 48 was prepared from (AB)n SPE 32A, a copolymer of 15 dp siloxane and Polyglycol AA2000 polyether, and the emulsion labeled as Example 49 from (AB)n SPE 3 IB, a copolymer of 15 dp siloxane and Polyglycol AA2000 polyether. The final compositions of these dispersions are shown in the following table. In this case, no water- miscible solvent was required. DC 1-2287, a methylvinylsilicone cyclics (from Dow Corning Corp.) was used. The compositions of these two emulsions are shown in Table 16 below. [0087] The stability ofthe emulsions prepared from (AB)n SPE copolymers are also shown. The particle sizes of these emulsions after 5 weeks aging @ 40°C were found comparable to their initial values, as illustrated in Table 16.
Table 16
Figure imgf000042_0001

Claims

1. An aqueous composition having dispersed particles wherein the dispersed particles comprise an (AB)„ block silicone polyether copolymer having the average formula;
-[R1(R2SiO)x(R2SiR1O)(CmH2mO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons.
2. The aqueous composition of claim 1 wherein the (AB)n block silicone polyether copolymer average formula value for m is 2, R is methyl, and R1 is propylene, and the weight average molecular weight is from 1,500 to 150,000.
3. The aqueous composition of claim 1 or 2 wherein the dispersed particles have an average particle size of less than 10 micrometers.
4. The aqueous composition of claim 3 wherein the value of x/(x+y) ranges from 0.2 to 0.9.
5. The aqueous composition of claim 3 wherein the dispersed particles are vesicles.
6. The aqueous composition of claim 3 wherein x ranges from 20 to 100.
7. The aqueous composition of claim 3 wherein the composition is an emulsion.
8. The aqueous composition of claim 3 wherein x ranges from 5 to 19.
9. The aqueous composition of claim 3 further comprising a water miscible volatile solvent.
10. The aqueous composition of claim 3 further comprising a volatile methyl siloxane.
11. A process for making an aqueous composition comprising; I) combining, A) an (AB)n block silicone polyether copolymer having the average formula; -[R1(R2SiO)x(R2SiR1O)(CmH2mO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons, B) an optional water miscible volatile solvent, with water to form an aqueous dispersion, II) mixing the aqueous dispersion to form dispersed particles of the (AB)n silicone polyether copolymer having an average particle size of less than 10 micrometers, III) optionally, removing the water miscible volatile solvent from the aqueous dispersion.
12. The process according to claim 11 wherein the dispersed particles are vesicles.
13. The vesicle composition produced by the process of claim 11.
14. The vesicle composition of claim 13 further comprising a personal, household, or healthcare active ingredient.
15. A process for preparing a water continuous emulsion having an average particle size of less than 10 micrometers comprising; I) mixing A) an (AB)n block silicone polyether copolymer having the average formula; -[R1(R2SiO)x(R2SiR1O)(CmH2mO)y ]z - where x and y are greater than 4, m is from 2 to 4 inclusive, z is greater than 2, R is independently a monovalent organic group, R1 is a divalent hydrocarbon containing 2 to 30 carbons, B) an optional water miscible volatile solvent to form a hydrophobic phase, II) adding water to the hydrophobic phase to form the water continuous emulsion.
16. The process of claim 15 wherein a silicone or organic oil is included in the mixing of step I).
17. The process of claim 15 wherein the silicone is a volatile methyl siloxane.
18. The process of claim 15 wherein the silicone is a vinyl functional organopolysiloxane.
19. The process of claim 15, 16, 17, or 18 wherein step I further comprises a personal, household, or healthcare active.
20. The product produced by any one of claims 15 to 19.
21. A personal, household, and healthcare composition comprising the composition of claim 20.
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