WO2015048228A2 - Gels d'élastomère de silicone amélioré et procédés d'hydrosilylation associés - Google Patents

Gels d'élastomère de silicone amélioré et procédés d'hydrosilylation associés Download PDF

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Publication number
WO2015048228A2
WO2015048228A2 PCT/US2014/057365 US2014057365W WO2015048228A2 WO 2015048228 A2 WO2015048228 A2 WO 2015048228A2 US 2014057365 W US2014057365 W US 2014057365W WO 2015048228 A2 WO2015048228 A2 WO 2015048228A2
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Prior art keywords
lactate
silicone elastomer
gel
glyceryl
cross
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PCT/US2014/057365
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English (en)
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WO2015048228A3 (fr
Inventor
Juan R. Mateu
Michael R. BATKO
Nagi AWAD
Brianna BICHO
Michael R. MOSQUERA
Albert A. Zofchak
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Alzo International, Inc.
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Publication of WO2015048228A2 publication Critical patent/WO2015048228A2/fr
Publication of WO2015048228A3 publication Critical patent/WO2015048228A3/fr
Priority to US15/070,673 priority Critical patent/US20160194455A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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
    • C08L83/04—Polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the invention provides improved silicone elastomer gels and related hydrosilylation processes and cosmetics.
  • Cross-linked silicone elastomer gels made by processes of the invention exhibit superior characteristics, including improved organic solubility, consistent gelation, stability and enhanced lubricity.
  • Silicone elastomers are well known materials in the cosmetics and personal care products industries. These materials are typically prepared by reacting a
  • the properties of the final elastomer polymer will depend upon the number of hydrosilane and vinyl functional groups contained in each of the starting materials and the molecular weights of each starting polymer. As would be expected, the reaction greatly increases the overall molecular weight of the silicone polymer by forming cross-linking structures between the starting polymers. The cross links also impart elasticity, greatly improve the film forming properties, greatly improve the substantivity and greatly reduce the solubility of the final elastomer in many common solvents. In order to increase the organic solvent compatibility, an alpha olefin (with from 4 to 24 carbons) is often added to the vinyl terminated polydimethylsiloxane reaction component.
  • the alpha olefin can then react with the hydrosilane groups during the elastomeric cross-linking reaction to form pendant alkyl groups.
  • Other olefin containing compounds such as an ethoxylated allyl alcohol
  • w/o water-in-oil
  • the bis-divinyl polydimethylsiloxane becomes the bridging or cross-linking group between the polydimethylsiloxanes that have the hydrosilane groups.
  • this cross-linking reaction is very fast after addition of the catalyst and, as described in U.S. Patent No. 6,936,686, visible gelation occurs within about 5 to about 40 minutes after addition of the catalyst. This gelation is a critical point in the production of the polymer (as described in U.S. Patent No. 6,936,686) after which mixing is stopped to allow the reaction to proceed without disrupting the structure of the gelled matrix.
  • an organic substrate having multiple unsaturations such as a polybutadiene or an unsaturated vegetable oil such as soybean or olive oil
  • an organic substrate having multiple unsaturations such as a polybutadiene or an unsaturated vegetable oil such as soybean or olive oil
  • multi functional hydrosilane polydimethylsiloxanes to produce an elastomeric gel.
  • This is a well known reaction, but it can be difficult to control reproducibly and, due to compatibility issues between the unsaturated component and the multi functional hydrosilane polydimethylsiloxane, it may not make a clear gel.
  • polyorganohydrosiloxanes under mixing conditions that favor substantially uniform reactant cross-linking and the formation of elastomeric gels over a wide viscosity range, Newtonian or non-Newtonian properties, improved stability, as well as other favorable characteristics, including enhanced lubricity.
  • compositions according to the present invention exhibit characteristics of increased solubility, consistent gelation characteristics, gel clarity and enhanced stability, as well as increased organic solvent compatibility/solvency as otherwise described herein.
  • compositions according to the present invention may be modified to provide hydrophobic as well as hydrophilic materials and amines based upon additional chemical components which may be added to the present compositions.
  • the invention provides a cross-linked silicone elastomer gel product formed by a hydrosilylation reaction between:
  • reaction (1) is conducted in the presence of a hydrosilylation catalyst and, optionally, a solvent or diluent (2) is induced upon addition of the at least one unsaturated polyorganosiloxane and the at least one polyorganohydrosiloxane to a mixer at a temperature range of between about 25°C to about 80°C, more preferably between about 40°C to about 50°C, even more preferably between about 40°C to about 45°C and (3) occurs continuously from the gel point to a point of substantial product gelation.
  • the term "mixer” as used includes a “mixer-extruder” (e.g.
  • one or more screw mixer extruders e.g. one or more single twin-screw extruders (with multiple extruders arranged in series).
  • the mixer-extruder is the "Continuous Processor” (Readco Kurimoto, LLC, York, PA).
  • Representative continuous single and twin screw reactor-extruders are also described in U.S. Patent No. 4,420,603.
  • Mater includes high-shear (rotar/stator) mixers and multi-shaft mixers.
  • the term “mixer” includes two or more mixers of the same or different type that are arranged in series.
  • “Gel point” is defined in accordance with the Encyclopedia of Polymer Science and Technology (John Wiley & Sons, Inc. 2002) as a liquid-to-solid transition point at which long-range connectivity in the material diverges to infinite size as a result of network formation ("materials at their GP [gel point], called “critical gels” exhibit universal features that merge liquid and solid characteristics into a unique behavior: (1) stress requires an infinite time to relax and (2) relaxation occurs in a broad, self-similar distribution of shorter modes. These features become apparent in rheological experiments that probe the long-time behavior. The broadening of the spectrum has been attributed to two effects, the broadening of the cluster size distribution (molecular clusters, supramolecular clusters) and the branching of the clusters"; id.)
  • Substantial product gelation means the point at which the cross-linked silicone elastomer gel has one or more desired rheological properties (e.g. a viscosity of between about 1,000 to about 100,000 centistokes (est); a particular gel strength determined, e.g. by calculating the modulus of rigidity); Newtonian behavior (i.e. the gel exhibits constant viscosity irrespective of applied force)).
  • desired rheological properties e.g. a viscosity of between about 1,000 to about 100,000 centistokes (est); a particular gel strength determined, e.g. by calculating the modulus of rigidity); Newtonian behavior (i.e. the gel exhibits constant viscosity irrespective of applied force)
  • the hydrosilylation reaction may be conducted in the presence of a solvent or diluent, including, but not limited to the low viscosity silicone oils, hydrocarbon oils, and lower alkanols described in U.S. Patent No. 6,936,686.
  • a solvent or diluent including, but not limited to the low viscosity silicone oils, hydrocarbon oils, and lower alkanols described in U.S. Patent No. 6,936,686.
  • Solvents and diluents include, but are not limited to, amphiphilic solvents such as tetrahydrofuran (THF), dioxane, and ethylene glycol dimethylether, hydrocarbon solvents including aliphatic hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane, isooctane, and hydrogenated triisobutylene, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and the like, silicone solvents such as octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane; and the like.
  • amphiphilic solvents such as tetrahydrofuran (THF), dioxane, and ethylene glycol dimethylether
  • hydrocarbon solvents including aliphatic hydrocarbons such as hexane, heptane,
  • the at least one unsaturated polyorganosiloxane is a bis- divinyl polydimethylsiloxane and the at least one polyorganohydrosiloxane is a
  • polydimethylsiloxane having multiple pendant methylhydrosilane groups having multiple pendant methylhydrosilane groups.
  • hydrosilylation catalysts can be used. Non-limiting examples include the catalysts described in U.S Patent Nos. 3,715,334; 3,775,452 (Pt (O) complex with vinyl silicon siloxanes ligands); 3,576,027 (platinum (IV) catalyst prepared by reacting crystalline Platinum (IV) chloropatinic acid and organic silane or siloxanes to form a stable catalyst).
  • the polyorganosiloxane and optional vinyl ester and/or alpha olefin are pre-mixed prior to continuous addition to, and reaction with, the polyorganohydrosiloxane.
  • the at least one unsaturated polyorganosiloxane is an a, ⁇ -di lower alkenyl terminated polyorganosiloxane havin the formula:
  • each R 2 is independently an alkyl of 1-3 carbon atoms.
  • the invention provides cross-linked silicone elastomer gels formed by a hydrosilylation reaction between:
  • reaction (1) is conducted in the presence of a hydrosilylation catalyst and, optionally, a solvent or diluent (2) is induced upon addition of the at least one alpha-olefin and the at least one polydimethylsiloxane to a mixer at a temperature range of between about 25°C to about 80°C, more preferably between about 40°C to about 50°C, even more preferably between about 40°C to about 45°C and (3) occurs continuously from the gel point to a point of substantial product gelation.
  • the invention provides cross-linked silicone elastomer gels formed by a hydrosilylation reaction between:
  • reaction (1) is conducted in the presence of a hydrosilylation catalyst and, optionally, a solvent or diluent (2) is induced upon addition of the at least one multi-vinyl functional hydrocarbon, the at least one bis-dihydrosilane polydialkylsiloxane and, optionally, the allyl alcohol ethoxylate to a mixer at a temperature range of between about 25°C to about 80°C, more preferably between about 40°C to about 50°C, even more preferably between about 40°C to about 45°C and (3) occurs continuously from the gel point to a point of substantial product gelation.
  • the multi-vinyl functional hydrocarbon has the formula:
  • the multi- vinyl functional hydrocarbon is a polybutadiene comprising at least about 90% by weight of cis olefins.
  • the bis-dih drosilane polydialkylsiloxane has the formula:
  • R 1 and R a are each H; each R 2 and R 3 is independently a Ci-Cio alkyl group; and n is from 5 to 50,000.
  • a cross-linked silicone elastomer gel of the invention can further comprise about 0.01% to about 7.5% by weight of allyl alcohol ethoxylate units (e.g. allyl alcohol ethoxylate units comprising about 5 to about 100 ethylene glycol units), and may also further comprise about 0.01% to about 7.5% by weight of a polyurethane.
  • allyl alcohol ethoxylate units e.g. allyl alcohol ethoxylate units comprising about 5 to about 100 ethylene glycol units
  • a polyurethane e.g. allyl alcohol ethoxylate units comprising about 5 to about 100 ethylene glycol units
  • a continuous processor (mixer) used in certain embodiments of the invention can act as an extruder that kneads or mixes the silicone elastomer until it is extruded into a holding vessel.
  • all mixing or agitation is stopped and the reaction proceeds for several hours in the vessel without mixing or agitation.
  • Continuous processing in accordance with the invention allows for mixing after the gelation point of the reaction. Once the gel is extruded out of the continuous processor (mixer), the gel is ready for further dilution, e.g. by using a homogenizer.
  • patient or subject is used to describe a mammal, including a human to which compositions according to the present invention may be applied.
  • ⁇ is used, in context, to describe an amount or concentration of a compound, composition or component, as otherwise described herein which is included or used to provide an intended effect or trait, such as emulsification (emulsifiers), emolliency, wettability, skin adherence, storage stability, viscosity and/or solubility to a formulation of a personal care product or are used to produce a compound or composition according to the present invention.
  • emulsification emulsifiers
  • emolliency emolliency
  • wettability wettability
  • skin adherence storage stability
  • viscosity and/or solubility e.g., viscosity and/or solubility
  • personal care product or “personal care composition” is used to describe a chemical composition used for the purpose of cleansing, conditioning, grooming, beautifying, or otherwise enhancing the appearance of the human body, especially keratinous tissue, including skin, nails and hair.
  • Personal care products include skin care products, cosmetic products, antiperspirants, deodorants, toiletries, perfumes, soaps, bath oils, feminine care products, hair-care products, oral hygiene products, depilatories, including shampoos, conditioners, hair straightening products and other hair care products, color cosmetics such as lipsticks, creams, make-ups, skin creams, lotions (preferably comprised of water-in-oil or oil- in-water emulsions), shave creams and gels, after-shave lotions and shave-conditioning compositions and sunscreen products, among numerous others.
  • Personal care products comprise an admixture of a silicone cross linked hydrocarbon elastomer as otherwise described herein alone or optionally in combination with an oil and water (to produce an emulsion which may be further added to other components to produce a personal care composition) in the weight percentages as otherwise disclosed herein and at least one or more additional component selected from the group consisting of an aqueous solvent (e.g.
  • a nonaqueous solvent emollients, humectants, oils (polar and non-polar), conditioning agents, surfactants, thickeners/thickening agents, stiffening agents, emulsifiers, including secondary emulsifiers, medicaments, fragrances, preservatives, deodorant components, anti-perspirant compounds, skin protecting agents, pigments, dyes, coloring agents, sunscreens and mixtures thereof, among others.
  • Preferred personal care products according to the present invention comprise about 0.01% to about 95% by weight of an emulsion which comprises a silicone cross-linked hydrocarbon elastomer as otherwise described herein, an oil and water, with the remainder of the composition comprising at least one additional component selected from the group consisting of an aqueous solvent (e.g.
  • emulsifiers including secondary emulsifiers, surfactants, thickeners, stiffening agents, medicaments, fragrances, preservatives, deodorant components, anti-perspirant compounds, skin protecting agents, pigments, sunscreens and mixtures thereof, among others.
  • silicone cross linked hydrocarbon elastomer or "silicone cross-linked hydrocarbon polymer” describes a multi alkene functional compound which may or may not be a polymer (preferably, polybutadiene or a multi-unsaturated polyurethane, more preferably polybutadiene) which is cross linked (or chain-extended) with a bis-hydrosilane terminated polysiloxane and exhibits favorable characteristics of gelation, solubility and stability.
  • the polyorganosiloxane polymer (bis-hydrosilane silicone polymer) which is cross linking (or chain-extending) the hydrocarbon according to the present invention may vary significantly in chemical composition but preferably is a polymeric composition comprised of R 2
  • R and R are each independently a Ci-Cto alkyl (preferably d-
  • Silicone cross linking agents (bis-hydrosilane terminated polyalkylsiloxanes) described herein may comprise as little as 2% and as much as 98% by weight of the final silicone cross-linked hydrocarbon elastomer, the remainder comprising the multifunctional hydrocarbon compound, but in preferred aspects the silicone cross-linking agent comprises about 50% to about 98% of the final silicone cross-linked hydrocarbon elastomer and the multifunctional hydrocarbon compound (e.g. polybutadiene) comprising about 0.1% to about 25%, about 0.25% to about 20%, about 0.5% to about 15%, about 1% to about 10% by weight of the final silicone cross-linked hydrocarbon elastomer.
  • the silicone cross-linking agent comprises about 50% to about 98% of the final silicone cross-linked hydrocarbon elastomer and the multifunctional hydrocarbon compound (e.g. polybutadiene) comprising about 0.1% to about 25%, about 0.25% to about 20%, about 0.5% to about 15%, about 1% to about 10% by weight of the final silicone cross-linked hydro
  • the multifunctional hydrocarbon comprises about 0.1% to about 10% by weight of the silicone cross-linking agent used in the preparation of the silicone cross-linked hydrocarbon elastomers of the present invention.
  • the silicone cross-linked hydrocarbon elastomers may also comprise allyl alcohol ethoxylate units and/or polyurethane units.
  • Silicone polymers according to the present invention which are used to produce silicone cross-linked hydrocarbon elastomers preferably comprise one Si-H group at each of the distil ends of the elastomer (e.g. bis-hydrosilane polydimethylsiloxane) which are capable of cross-linking with multi vinyl functional hydrocarbon as otherwise described herein (e.g. polybutadiene, unsaturated polyurethane, among others).
  • elastomer e.g. bis-hydrosilane polydimethylsiloxane
  • multi vinyl functional hydrocarbon as otherwise described herein (e.g. polybutadiene, unsaturated polyurethane, among others).
  • an allyl alcohol ethoxylate may optionally comprise (in the final polymer) an amount of about 0.01% to about 7.5%, about 0.05% to about 5%, about 0.1% to about 1% by weight of the monomers/polymers which ultimately form certain embodiments of the silicone cross-linked hydrocarbon elastomer according to the present invention.
  • the inclusion of allyl alcohol ethoxylate may increase the hydrophilicity of the final silicone cross-linked hydrocarbon elastomers according to the present invention.
  • a polyurethane polymer also may be added to the multifunctional unsaturated hydrocarbon crosslinkable agent and reacted with the bis-hydrosilane polyorganosiloxane polymer to provide final hydrophilic silicone cross-linked hydrocarbon elastomers.
  • the polyurethane polymer comprising (when optionally present) about 0.01% to about 15%, about 0.05% to about 10%, about 0.05% to about 5% or more by weight of the final polymeric composition in order to provide a further hydrophilic/skin adhering component, solubilizer or UV absorbing component.
  • the final silicone cross-linked hydrocarbon polymers (which may optionally include allyl alcohol ethoxylate and/or polyurethane units to increase hydrophilicity or, in the case of polyurethanes, hydrophilic, skin-adherent, solubilizing or UV absorbing qualities of the final polymers) according to the present invention are multifunctional unsaturated hydrocarbon compounds, including polybutadiene which are cross-linked with a bis-hydrosilane terminated polysiloxane compound (the reaction preferably occurring between the olefinic groups on the multiply unsaturated hydrocarbon and the Si-H groups and, in some cases, optional alkenyl groups on the cross-linking silicone polymer.
  • the cross-linking bis-hydrosilane polydimethylsiloxane may be reacted with an unsaturated polymeric silicone compound, an alpha olefin and/or an allyl alcohol ethoxylate prior to cross-linking with the multiply unsaturated hydrocarbon compound.
  • polydimethylsiloxanes with several pendant hydrosilane groups may be used to introduce an allyl alcohol ethoxylate (each allyl alcohol monomer preferably containing from 5 to about 100, about 10 to about 50, about 15 to about 45, about 10 to about 65, about 15 to about 25, about 50 to about 100, about 65 to about 85, about 75 ethoxylate/ethylene glycol units) monomer into the final silicone cross-linked hydrocarbon polymer.
  • hydrophilic silicone elastomer hydrophilic through introduction of allyl alcohol ethoxylate groups
  • polyurethane or polyester may simply be admixed without further cross- linking/polymerization.
  • the final silicone cross-linked hydrocarbon polymer is prepared from a reaction mixture which comprises a hydrosilane terminated polydimethylsiloxane polymer as described above (which may optionally further comprise an allyl alcohol ethoxylate group as described herein and/or a reactive polyurethane or polyester wherein the hydrosilane terminated polydimethylsiloxane and the allyl alcohol ethoxylate and/or polyurethane or polyester are covalently linked) as a cross-linking agent.
  • This cross-linking agent is then reacted with a multifunctional unsaturated hydrocarbon such as polybutadiene as described herein.
  • silicone cross-linked hydrocarbon polymers according to the invention comprise the reaction product of a cross-linking silicone polymer as otherwise described hereinabove that contains hydrosilane groups at the distil ends of the polysiloxane, as well as an optional allyl alcohol ethoxylate component and/or an optional polyurethane or polyester component.
  • Each of the optional allyl alcohol ethoxylate component and the optional polyurethane or polyester component independently comprise about 0.1% to about 75%, about 0.5% to about 50%, often about 0.5% to about 10% or 1%» to about 7.5% by weight of the bis-hydrosilane polydimethylsiloxane cross-linking agent which is reacted with the multifunctional hydrocarbon polymer backbone.
  • the final silicone cross-linked hydrocarbon elastomers comprise the reaction product of a cross-linking silicone polymer as otherwise described herein (i.e., without allyl alcohol ethoxylate and/or a polyurethane) with a multiply unsaturated hydrocarbon (e.g., polybutadiene) which may optionally include an allyl alcohol ethoxylate and/or a polyurethane as described above (preferably comprising about 0.01% to about 7.5%, about 0.05% to about 5%, about 0.1 % to about 1% by weight of the multifunctional hydrocarbon.
  • a cross-linking silicone polymer as otherwise described herein (i.e., without allyl alcohol ethoxylate and/or a polyurethane) with a multiply unsaturated hydrocarbon (e.g., polybutadiene) which may optionally include an allyl alcohol ethoxylate and/or a polyurethane as described above (preferably comprising about 0.01% to about 7.5%, about 0.05% to
  • the polyurethane compound comprises about 0.01% to about 7.5%, about 0.01% to about 5%, about 0.05% to about 1% of the final hydrocarbon silicone cross-linked hydrocarbon elastomer.
  • the bis-hydrosilane polydimethylsiloxanes (silicone polymer crosslinkers) which are used to prepare silicone cross-linked hydrocarbon elastomers according to the present invention have the following structure:
  • R 1 and R a are each independently H groups
  • Each R 2 and R 3 is independently a Ci-Cio alkyl group (preferably C C 3 alkyl, preferably methyl); and
  • n is from 5 to 50,000, about 10 to about 25,000, about 100 to about 10,000, about 100 to about 5,000, about 200 to about 5,000, about 500 to about 2,500.
  • Silicone cross-linked hydrocarbon elastomers are generally formed by reacting a polysiloxane polymer which contains two Si-H bonds at distil ends of the molecule (a bis hydrosilane polydialkylsiloxane as otherwise described herein) with a multifunctional hydrocarbon (e.g. polybutadiene), each of which is reactive with a Si-H group.
  • the multifunctional hydrocarbon may vary in size, but generally ranges in size from a molecular weight of several hundred to 25,000 or more, with a preferred molecular weight range of at least about 500 to about 10,000, about 1,500-7,500, about 2,000-5,000 or about 2,500.
  • cross-linking is used to describe the reaction of the silicone polymer with the multifunctional hydrocarbon backbone in the present compositions. It is noted that the silicone polymer often has only two functional groups, e.g. a Si-H group on each of the distil ends of the silicone polymer, the polymer may also be referred to as a chain extender or chain extending agent. However, it will be understood the term cross-linking may be used to refer to the silicone polymer or crosslinker used in the present invention.and the reaction of the silicone polymer or crosslinker with the (multiply unsaturated) hydrocarbon.
  • polybutadiene shall mean, within the context of its use, a polymeric material which is produced from butadiene monomers.
  • Polybutadiene polymers for use in the present invention have a structure according to the chemical formula:
  • polybutadiene polymers for use as multifunctional hydrocarbon polymer backbone herein comprise about 5% to about 50% by weight of olefmic character (also referred to as "vinyl content"- based upon the molecular weight of olefin within the polybutadiene molecule), about 5 to about 35% by weight olefin, about 15% to about 25% by weight olefin.
  • olefmic character also referred to as "vinyl content"- based upon the molecular weight of olefin within the polybutadiene molecule
  • Preferred polybutadiene polymers for use in the present invention comprise about 90+% cis olefins (of a mixture of cis and trans olefins within the polybutadiene molecule), about 95+% cis olefins, about 99+% cis olefins, about 99.5+% cis olefins, about 99.9+% cis olefins.
  • the polybutadiene component of the present invention contains a number of vinyl groups which may react with Si-H or other groups (as otherwise described herein) within the silicone elastomer cross-linking agents to produce silicone cross-linked hydrocarbon elastomers according to the present invention.
  • polybutadiene especially including polybutadiene functions as a hydrocarbon backbone in the silicone cross-linked hydrocarbon elastomer polymers according to the present invention.
  • Preferred polybutadiene polymers for use in the present invention comprise about 0.005% to about 7.5% by weight of the final silicone cross-linked hydrocarbon elastomer, about 0.05% to about 5% by weight, about 0.1% to about 2.5% by weight, about 0.25 to about 4%.
  • crosslinkers/chain extenders (of varying compositions as otherwise described herein) provides an easily and consistently manufactured silicone cross-linked hydrocarbon elastomer which can be varied quite markedly in final characteristics by incorporation of additional components (such as allyl alcohol ethoxylate and polyurethanes) as otherwise described herein.
  • polyurethane shall mean, within the context of its use, a polymeric urethane compound comprising at least one and preferably, two or more urethane linkages which are generally formed by reacting at least one compound containing a free alcohol (primary, secondary or tertiary), preferably at least one compound containing at least two alcohol groups (“polyol”) and a diisocyanate compound.
  • a free alcohol primary, secondary or tertiary
  • polyol preferably at least one compound containing at least two alcohol groups
  • polyurethane as used herein incorporates dimer urethanes (those compounds which contain two urethane bonds) which are formed from a diisocyanate and a monohydric alcohol of varying structure, which structure may contain, for example, an active group or a protected active group such as a silyl-protected hydroxyl group or amine group wherein the protecting group may be removed subsequent to formation of the polyurethane or an olefinic group (such as for example, a vinyl group, acrylate or methacrylate group) which can participate in a reaction with a silane group from the silicone polymer crosslinker to produce a silicone cross-linked hydrocarbon elastomer/polyurethane composition.
  • dimer urethanes such as a silyl-protected hydroxyl group or amine group wherein the protecting group may be removed subsequent to formation of the polyurethane or an olefinic group (such as for example, a vinyl group, acrylate or methacrylate group) which
  • polyurethanes according to the present invention preferably are formed by reacting at least one polyol (a compound which is either hydrocarbon or siloxane based and which contains at least two free hydroxy groups with a diisocyanate to produce a polyol (a compound which is either hydrocarbon or siloxane based and which contains at least two free hydroxy groups with a diisocyanate to produce a polyol (a compound which is either hydrocarbon or siloxane based and which contains at least two free hydroxy groups with a diisocyanate to produce a
  • polyurethane with the polyol optionally and preferably containing at least one functional group which does not participate in the polymerization reaction to form the polyurethane composition, but which, subsequent to the polymerization reaction, can be used to crosslink the polyurethane composition to a silicone elastomer in preferred compositions according to the present invention.
  • polyurethane compounds which are reacted with a silicone elastomer to produce hydrophilic silicone elastomers preferably have sufficient hydrophilic character (for example, by containing sufficient hydroxyl groups and/or ethoxylated- polyethylene oxide or PEG groups) to instill hydrophilic character to the final hydrophilic silicone elastomers according to the present invention.
  • Preferred urethane polymers according to the present invention have the general structure V: O H H
  • R is an optionally substituted hydrocarbon or optionally substituted siloxane group, preferably, an optionally substituted (with hydroxyl groups and/or PEG groups comprising from 1 to 100 or 2 to 25 ethylene oxide units) CrC 5 o hydrocarbon group containing at least one olefmic group or a polyethylene oxide group comprising between 1 and 500, 2 and 100, 5 and 25, 5 and 20, 5 and 15 ethylene oxide groups which may be optionally endcapped with or contain a polymerizable group such as an alkenyl or (meth)acrylate group, or
  • R is an optionally substituted hydrocarbon (which may contain hydroxyl and/or PEG groups as otherwise described here) or a siloxane group, preferably, an optionally substituted Ci-Cso hydrocarbon group, optionally containing at least one olefmic group, or a siloxane group according to the structure:
  • Y is absent, O or a -W-(OZ) r -Q-(CH 2 ) q -T- group;
  • X is absent or a-T-(CH 2 ) q -Q-(ZO)r-W'- group
  • X' is absent or a-W'-(OZ) r -Q-(CH 2 ) q -T- group;
  • Y' is absent or a -T-(CH 2 ) q -Q-(ZO) r -W 2 - group;
  • W is absent when r is an integer of 1 or more and W is absent or O when r is 0; Q is absent or O;
  • q is an integer from 0 to 10, preferably 1 to 6, preferably 1 to 3;
  • r is an integer from 0 to 100, 0 to 40, preferably 1 to 20 or 1 to 10, with the proviso that q or r is at least 1 ;
  • T is absent or O
  • W is absent when r is 0 and is a Z group when r is 1 or more;
  • W 2 is H
  • Z is independently an ethylene group, a propylene group or a mixture of ethylene and propylene groups
  • R 2b and R 3b are each independently a Q-Qo alkyl group (preferably both are a Q-C 3 alkyl group, preferably both are methyl groups), preferably R 2b and R 3b are both C Cio alkyl groups, preferably Ci-C 3 alkyl groups, preferably both are the same Ci-C3 alkyl group, preferably both are methyl groups;
  • R 2c and R 3c are independently selected from an optionally substituted Q-Q alkyl group (substitution with OH or a -C3 alkyl group which itself may be optionally substituted with a hydroxyl group) and optionally, an Si-H group, an alkenyl group and/or a hydroxyl group in small percentages of the total number of R 2c and R 3c substituents within the polymer.
  • R b , R 3b R 2c and R 3c optionally may comprise a small percentage (i.e., less than about 2%, 1.5%, 1.0%, 0.75%, 0.5%, 0.25%, 0.1%, 0.05% or 0.002%) of Si-H groups, alkenyl groups and/or hydroxyl groups of the total number of R 2b , R 3b R 2c and R 3c groups which are found in the silicone group;
  • R' is an optionally substituted C 2 through C 3 (preferably, C 6 through C 22 , most preferably an isophorone group) linear, cyclic or branch-chained saturated or unsaturated hydrocarbon group (which may be monomelic or dimeric, an aromatic group, including a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl or substituted alkylphenyl or alkylbenzyl group);
  • i is an integer from 0 to 50, preferably 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 (preferably 0 or 1);
  • k is an integer from 0 to 100, 1 to 100, about 5 to 50, about 10 to 45, preferably about 20 to 40;
  • the polyurethane according to the present invention is obtained by reacting a polyol (which may be hydrocarbon based or siloxane based and contains at least two hydroxyl groups) with a diisocyanate compound to produce a polyurethane composition accordingly.
  • a polyol which may be hydrocarbon based or siloxane based and contains at least two hydroxyl groups
  • R is a O-R group and R is a group where R 6 and R 6a are each independently an optionally substituted hydrocarbon or an optionally substituted siloxane group as set forth for R 5 and R 5a , respectively and generally described above.
  • One or more polyols and/or diisocyanates may be used to produce polyurethane polymers according to the present invention, with preferred polyols having, in addition to having at least two free hydroxy groups to participate in polymerization reactions to form polyurethanes, at least one reactive alkene (unsaturated hydrocarbon) group must be available for reaction with the hydrosilane terminated polydimethylsiloxane cross-linking agents of the present invention, and with the diisocyanate preferably being isophorone diisocyanate.
  • polyols contain multiple hydroxyl groups or alternatively, polyethylene oxide groups wherein the PEG groups contain from 2 to 100 ethylene oxide groups, preferably 3 to 50, 5 to 25 or 5 to 10.
  • Alternative polyurethanes according to the present invention also are prepared from a diisocyanate, preferably isophorone diisocyanate, glycerin and glycerin esters, propylene glycol and its esters, dipropylene glycol and its esters, alkyl amines, ethoxylated alkyl amines, propoxylated alkyl amines, silicone ethoxylates and silicone propoxylates, among others.
  • a diisocyanate preferably isophorone diisocyanate, glycerin and glycerin esters, propylene glycol and its esters, dipropylene glycol and its esters, alkyl amines, ethoxylated alkyl amines, propoxylated alkyl amines, silicone ethoxylates and silicone propoxylates, among others.
  • polyol refers to a hydrocarbon or siloxane based compound having at least two free hydroxyl groups which can participate in a reaction with diisocyanate to provide a polyurethane composition.
  • a polyol according to the present invention in addition to the two free hydroxyl groups which react with diisocyanate compounds, also contains an additional "reactive functional group" which, subsequent to the formation of the polyurethane compound, may participate in a cross-linking reaction with a reactive functional group on a silicone polymer admixed with the polyurethane, to produce silicone cross-linked hydrocarbon/polyurethane elastomer compositions.
  • monohydric alcohol refers to a compound containing a single hydroxyl group which may react with a diisocyanate compound to produce dimer urethane compounds according to the present invention.
  • Monohydric alcohols advantageously contain at least one reactive functional group which, after formation of the dimer urethane, can react with a reactive group on a silicone polymer admixed with the dimer urethane to produce a silicone cross-linked hydrocarbon/polyurethane elastomer compositions.
  • the polyol(s) used to polymerize with diisocyanate may vary widely in character from hydrophilic (polar) to hydrophobic (non-polar), but are preferably hydrophilic in nature.
  • preferred polyols include triglycerides which contain fatty acids having free hydroxyl groups and/or olefinic groups such as castor oil triglycerides or other triglycerides, glycerol, substituted glycerols or polyglycerols such as C 10 -C 24 di-fatty polyglycerol (preferably, polyglycerol-2-diisostearate), di-fatty alkanolmonoglycerol, such as glycerol diricinoleate, polyethylene glycol alkylamines, especially polyethyleneglycol fatty amines, such as PEG- 15 cocamine, or di-PEG-15 soyamine or related dipo
  • polyethyleneglycol polydialkylsiloxane such as polydimethylsiloxane (e.g.dimethicone), or a di-polyethyleneglycol dimethicone, or related polysiloxane and bis-hydroxy terminated polybutadienes.
  • Polyols are polymerized with a diisocyanate compound, preferably isophorone diisocyanate.
  • multiply unsaturated polyols such as hydroxyl- terminated polybutadiene may be reacted with a diisocyanate to form a multiply unsaturated hydrocarbon/polyurethane that can then be cross-linked with ⁇ , ⁇ -hydrosilanepolydimethyl siloxane to form a silicone cross-linked polyurethane elastomer.
  • the hydroxyl terminated polybutadiene may be reacted with an acid, acid anhydride or acid halide to form a diester that can then be cross-linked with ⁇ , ⁇ -hydrosilanepolydimethyl siloxane to form a silicone cross-linked hydrocarbon/ester elastomer.
  • the hydroxyl terminated polybutadiene may be reacted with ethylene oxide, propylene oxide and the like to form a polyether that can then be cross-linked with ⁇ , ⁇ -hydrosilanepolydimethyl siloxane to form a silicone cross-linked hydrocarbon/polyether elastomer.
  • polyether is used throughout the specification to describe a polymer which may be incorporated into compositions herein, in addition to a polyurethane as otherwise ssdescribed herein or as an alternative to a polyurethane.
  • Polyesters may be formed by reacting monomeric compounds which are diols (of a wide variety including silicone containing diols) with diacids (varying widely, but often an organic acid having between 2 and 20 carbon atoms) or alternatively one or more monomers which contain a hydroxyl group and an acid, such that an ester group may be formed by the reaction of a hydroxyl group with an acid, thus forming a polyester.
  • diacids varying widely, but often an organic acid having between 2 and 20 carbon atoms
  • one or more monomers which contain a hydroxyl group and an acid such that an ester group may be formed by the reaction of a hydroxyl group with an acid, thus forming a polyester.
  • Polyesters which may be used according to the present invention may vary widely depending upon the physicochemical characteristics which are to be included into compositions according to the present invention.
  • Polyesters may be incorporated into compositions according to the present invention at a free hydroxyl group or free carboxyl acid group which may be used to start a polymerization reaction to produce a polyster sidechain.
  • Alternative approaches include, for example, reacting an allyl alcohol moiety with one or more of the functional groups on the cross-linked silicone polymer and then forming a polyester off of the free alcohol group from the reacted allyl alcohol.
  • diisocyanate is used throughout the specification to describe a linear, cyclic or branch-chained hydrocarbon having two free isocyanate groups.
  • diisocyanate also includes halogen substituted linear, cyclic or branch-chained
  • diisocyanates include, for example, isophoronediisocyanate, m-phenylene-diisocyanate, p-phenylenediisocyanate, 4,4- butyl-m-phenylene-diisocyanate, 4-methoxy-m-phenylenediisocyanate, 4-phenoxy-m- phenylenediisocyanate, 4-chloro-m-phenyldiisocyanate, toluene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 1,4-napthalene diisocyanate, cumene-l,4-diisocyanate, durene diisocyanate, 1,5-napthylene diisocyanate, 1,8-napthylene diisocyanate, 1,5- tetrahydronapthylene diisocyanate
  • Isophorone diisocyanate is the preferred diisocyanate used in the present invention.
  • the term un-substituted when used in context is used to describe a hydrocarbon moiety such as an alkyl group or alkene or other group which contains only hydrogen atoms bonded to carbons within the moiety. It can include aryl (aromatic groups such as phenyl) groups, as well.
  • un-substituted is used in context to describe a hydrocarbon moiety which is substituted, i.e., it contains, within the context of its use, a pendant hydroxyl group (in preferred aspects numerous alcohol groups, an ether group (such as within a glycol or polyglycol/(PEG), glycerol or polyglycerol or other group), a keto group, an amine (which may itself be substituted with alkyl groups, including fatty (C 8 -C 30 ) alkyl groups or alkanol groups, for example), an alkyl or alkene group attached to a carbon atom of the moiety.
  • a pendant hydroxyl group in preferred aspects numerous alcohol groups, an ether group (such as within a glycol or polyglycol/(PEG), glycerol or polyglycerol or other group), a keto group, an amine (which may itself be substituted with alkyl groups, including fatty (C 8 -C 30 ) alkyl groups or alkano
  • the number of carbon atoms within a substituent group may vary from 0 to 30 or more, 0 to 24 or more, 0 to 18, 0 to 12, 0 to 10, 1 to 8, and 1 to 6 and may contain 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or more carbon atoms, depending upon the context of the use of the compound to which the substituent is attached.
  • the term "optionally” means that a particular component, substituent or the like may or may not be present, depending upon the context within which the component, substituent or the like is used.
  • oil is used throughout the specification to describe any of various lubricious, hydrophobic and combustible substances obtained from animal, vegetable and mineral matter. These are used in combination with silicone cross-linked hydrocarbon elastomers to provide emollient characteristics (with from 1% by weight to 99% by weight of a combination of hydrocarbon elastomer and oil).
  • the hydrocarbon elastomers may be used to form emulsions of the present invention by combining an effective amount of an oil and water with the silicone cross-linked hydrocarbon elastomers according to the present invention to provide oil-in-water or water-in-oil emulsions which may be used alone or in lotions or creams in certain aspects of the invention.
  • the amount of hydrocarbon elastomer in emulsions will range from about 0.1% to about 50%, about 0.25% to about 25%, about 0.5% to about 20%, about 1% to abut 15%, about 2% to about 10%, about 0.75% to about 5% by weight; the amount of oil will range from about 0.1% to about 50%, about 0.25% to about 25%, about 0.5% to about 20%, about 1% to about 15%, about 2% to about 10%, about 0.75% to about 5% by weight and the amount of water will range from about 0.25% to about 95%, about 0.5% to about 85%, about 0.75% to about 80%, about 1% to about 75%, about 2% to about 70%, about 5% to about 65%, about 1% to about 15%, about 2% to about 10%, about 0.75% to about 5% by weight; about 45% to about 99% by weight of the emulsion produced.
  • Emollient oils for use in the present invention may include petroleum-based oil derivatives such as purified petrolatum and mineral oil.
  • Petroleum-derived oils include aliphatic or wax-based oils, aromatic or asphalt-based oils and mixed base oils and may include relatively polar and non-polar oils.
  • Non-polar oils are generally oils such as petrolatum or mineral oil or its derivatives which are hydrocarbons and are more hydrophobic and lipophilic compared to synthetic oils, such as esters, which may be referred to as polar oils.
  • non-polar and polar are relative within this very hydrophobic and lipophilic class, and all of the oils tend to be much more hydrophobic and lipophilic than the water phase which is used to produce the water-in- oil emulsion of the present invention.
  • Preferred hydrophobic oils for use in the present invention include mineral oil and petrolatum.
  • Preferred less hydrophobic (i.e., more polar) oils for use in the present invention include a number of maleates, neopentanoates, neopentanoyls, citrates and fumarates, and any other cosmetically acceptable ester emollient.
  • oils in addition to the above-described oils, certain essential oils derived from plants such as volatile liquids derived from flowers, stems and leaves and other parts of the plant which may include terpenoids and other natural products including triglycerides may also be considered oils for purposes of the present invention.
  • Petrolatum mineral fat, petroleum jelly or mineral jelly
  • mineral oil products for use in the present invention may be obtained from a variety of suppliers. These products may range widely in viscosity and other physical and chemical characteristics such as molecular weight and purity.
  • Preferred petrolatum and mineral oil for use in the present invention are those which exhibit significant utility in cosmetic and pharmaceutical products.
  • Cosmetic grade oils are preferred oils for use in the present invention.
  • Additional oils for use in the present invention may include, for example, mono-, di- and tri- glycerides which may be natural or synthetic (derived from esterification of glycerol and at least one organic acid, saturated or unsaturated, such as for example, such as butyric, caproic, palmitic, stearic, oleic, linoleic or linolenic acids, among numerous others, preferably a fatty organic acid, comprising between 8 and 26 carbon atoms).
  • mono-, di- and tri- glycerides which may be natural or synthetic (derived from esterification of glycerol and at least one organic acid, saturated or unsaturated, such as for example, such as butyric, caproic, palmitic, stearic, oleic, linoleic or linolenic acids, among numerous others, preferably a fatty organic acid, comprising between 8 and 26 carbon atoms).
  • Glyceride esters for use in the present invention include vegetable oils derived chiefly from seeds or nuts and include drying oils, for example, linseed, iticica and tung, among others; semi-drying oils, for example, soybean, sunflower, safflower and cottonseed oil; non-drying oils, for example castor and coconut oil; and other oils, such as those used in soap, for example palm oil.
  • drying oils for example, linseed, iticica and tung, among others
  • semi-drying oils for example, soybean, sunflower, safflower and cottonseed oil
  • non-drying oils for example castor and coconut oil
  • other oils such as those used in soap, for example palm oil.
  • Hydrogenated vegetable oils also may be used in the present invention.
  • Animal oils are also contemplated for use as glyceride esters and include, for example, fats such as tallow, lard and stearin and liquid fats, such as fish oils, fish-liver oils and other animal oils, including sperm oil, among numerous others.
  • a number of other oils may be used, including C 12 to C 30 (or higher) fatty esters (other than the glyceride esters, which are described above) or any other acceptable oil.
  • a cosmetic ester is used to describe any ester which is cosmetically compatible, i.e., may be safely incorporated into cosmetic products.
  • a cosmetic ester has between 12 and 26 carbon atoms, about 14 and 20 carbon atoms within the ester compound, even more preferably about 16 and 19 carbon atoms within the ester compound, with a preferred cosmetic ester having at least one of the two chains, i.e., either the ether portion of the ester or the acyl portion of the ester being an optionally substituted (with alkyl or hydroxyl), preferably an unsubstituted branched-chain alkyl group.
  • Preferred alkyl chains which correspond to the ether portion of the cosmetic ester include, for example, C 3 -C 18 branched-chain alkyl groups (including alkyl groups having sany number of carbon atoms within that range), such as, for example, isopropyl, isobutyl, tert-butyl, isopentyl, neo-pentyl, branched-chain hexyl, branched-chain heptyl, branched-chain octyl, branched-chain nonyl, branched-chain decyl, branched-chain undecyl, branched-chain dodecyl, branched-chain tridecyl, branched-chain tetradecyl, branched-chain pentadecyl, branched-chain hexadecyl, branched-chain heptadecyl and branched-chain octadecyl groups
  • the acyl group may be a branched-chain acyl group and the ether group may be an unbranched, straight chain, alkyl group. Both ether and acyl groups may comprise branched-chain alkyl groups as well.
  • Exemplary cosmetic esters for use in the present invention include ethyl acetate, ethyl lactate, isopropylstearate, isopropylpalmitate, isopropylmyristate, isopropyllaurate, isopropyloleate, isopropylisostearate, isononylisononanoate, isononylisoheptanoate, isononylisooctanoate, isododecylisononanoate, isooctyldodecylisononanoate,
  • isooctyldodecylisononanoate isododecylneopentanoate, isooctyldodecylneopentanoate, butylmyristate, myristylbutanoate, isostearylisostearate, isostearylisononanoate,
  • the silicone cross-linked hydrocarbon elastomer compositions prepared above may be added to a number of additional components to produce favorable characteristics in personal care products, including skin care products, cosmetic products, antiperspirants, deodorants, perfumes, toiletries, soaps, bath oils, feminine care products, hair-care products, oral hygiene products, depilatories, including shampoos, conditioners, hair straightening products and other haircare products, color cosmetics such as lipsticks, creams, make-ups, skin creams, lotions and sunscreen products, among numerous others.
  • skin care products including skin care products, cosmetic products, antiperspirants, deodorants, perfumes, toiletries, soaps, bath oils, feminine care products, hair-care products, oral hygiene products, depilatories, including shampoos, conditioners, hair straightening products and other haircare products, color cosmetics such as lipsticks, creams, make-ups, skin creams, lotions and sunscreen products, among numerous others.
  • Compounds/compositions of the present invention may be used as thickening agents and emulsifiers having a number of additional characteristics including emollient and adherence characteristics for the skin and epithelial tissue such as hair, ungual tissue (nails), skin and related mucous membranes, especially given the combined attributes of emolliency (from the silicone elastomer) and skin adherence, viscosity enhancement and favorable skin interaction (generally) and wettability, enhanced solubility, UV absorbing characteristics, etc. and other attributes (which can be formulated into the polymer depending upon the inclusion of which allyl alcohol ethoxylate and/or polyurethane is chosen).
  • emollient and adherence characteristics for the skin and epithelial tissue such as hair, ungual tissue (nails), skin and related mucous membranes, especially given the combined attributes of emolliency (from the silicone elastomer) and skin adherence, viscosity enhancement and favorable skin interaction (generally) and wettability,
  • emulsion formulations which may be included in personal care products, including cosmetic and toiletry products will acquire a soothing and favorable interaction which promotes skin adherence, moisturization, wettability and favorable viscosity attributes of the final personal care formulation.
  • the size of the silicone elastomer and polyurethane can be varied substantially, numerous characteristics may be "dialed in” to the final hydrophilic silicone elastomers in addition to the basic emulsifier characteristics and incorporated into personal care products ranging from lotions and creams to thickened formulations to be used in stick deodorants and related products can be readily formulated.
  • Effective amounts of the present compositions may also serve a dual function, for example, as emulsifiers exhibiting gloss-producing characteristics for lipsticks and lip balm formulations in the personal care, cosmetic and toiletry industries as a substitute(s) for castor oil normally used in such formulations, especially where the polyurethane is made from castor oil.
  • the compounds of the present invention exhibit outstanding solubility
  • characteristics for producing water-in-oil or oil-in-water emulsions and may form the basis for numerous and varied personal care compositions, depending upon the components of the final silicone cross-linked hydrocarbon elastomer composition.
  • Silicone cross-linked hydrocarbon elastomers according to the present invention exhibit one or more of a number of unexpected characteristics including providing compositions containing polyurethanes which do not exhibit a typical "sticky tactile" sensation when deposited on the skin of a subject (such as an animal, including a human) and provide a smooth, non-tacky feel which is especially advantageous for bodycare lotions and other personal care compositions used on the skin and hair of a subject.
  • the compositions of the present invention provide "substantivity" to personal care products and can be used to accommodate functional ingredients, especially including hydrophilic functional ingredients such as polar hydrophilic materials.
  • silicone cross-linked hydrocarbon elastomers which comprise allyl alcohol ethoxylate and/or hydrophilic polyurethane components
  • silicone cross-linked hydrocarbon elastomer compositions according to the present invention may be used advantageously as couplers (in emulsions or in
  • a hydrophilic or hydrophobic component such as water and an aliphatic component (such as an oil, fatty waxes and esters)
  • an aliphatic component such as an oil, fatty waxes and esters
  • silicone cross-linked hydrocarbon elastomer compositions according to the present invention are included in personal care products/formulations in effective amounts, i.e., amounts which produce an intended effect.
  • the amount of composition generally ranges from about 0.01% to about 50% by weight or more of personal care formulations according to the present invention.
  • compositions according to the present invention may be included in final personal care compositions in amounts ranging from about 0.05% to about 45% by weight, about 0.1% to about 40% by weight, about 0.25% to about 30% by weight, about 0.25% to about 20% by weight, about 0.5% to about 15% by weight, about 0.75% to about 10% by weight, about 1% to about 7.5% by weight, about 1% to about 5% by weight and about 1% to about 3% by weight of the final personal care composition.
  • compositions according to the present invention are included in amounts ranging from about 0.1% to about 25% by weight, in addition to the oil and water and optionally, other components.
  • Emulsions according to the present invention may be used in any number of personal care products, but find particularly useful applicability in formulations which are based upon lotions and/or skin creams.
  • compositions according to the present invention may be used in numerous additional compositions.
  • compositions according to the present invention are included in amounts ranging from about 0.1% to about 15% by weight of the formulation, in certain cases to instill conditioning attributes in addition to surfactant-like qualities.
  • the compositions according to the present invention preferably comprise about 0.1% to about 20% by weight, more preferably about 0.25% to about 5% by weight of the final end-use hair-care composition.
  • hair-care formulations include, for example, a solvent or diluent such as water and/or alcohol, other surfactants, emulsifiers, thickeners, coloring agents, dyes, preservatives, additional conditioning agents and humectants, among numerous others.
  • compositions according to the present invention are included in amounts ranging from about 0.25% to about 15% or more by weight, more preferably about 0.5% to about 10% by weight.
  • Other components which may be included in these end-use compositions include, for example, water, and at least one or more of emollients, humectants and emulsifiers, thickeners and optionally, other conditioning agents, medicaments, fragrances and preservatives.
  • the present compositions are included in amounts ranging from about 0.25% to about 45% by weight, more preferably, about 0.5 to about 25% by weight. Additional components which may be employed in these
  • compositions include, for example, water, emollients and emulsifiers, surfactants, oils, and optionally, other conditioning agents, thickeners, medicaments, fragrances and preservatives.
  • the present compositions are included in amounts ranging from about 0.25% to about 45% or more by weight, preferably about 0.5% to about 25% by weight of the final formulations.
  • These compositions form the basis of lotions or skin creams which may be used to deliver pigments and/or sunscreen components in compositions according to the present invention.
  • Additional components which may be employed in these compositions may include, for example, a UV absorbing composition such as para-amino benzoic acid (PABA) or a related UV absorber or a pigment such as Ti0 2 and optional components including, for example, one or more of an oil, water, suspending agents, other conditioning agents and emollients, among others.
  • PABA para-amino benzoic acid
  • Ti0 2 optional components including, for example, one or more of an oil, water, suspending agents, other conditioning agents and emollients, among others.
  • compositions according to the present invention are included for their surfactant and emollient-like qualities in amounts ranging from about 0.25% to about 20% by weight or more, preferably about 0.5% to about 10% by weight.
  • Additional components which may be included in bar and liquid soaps include water and surfactants and optionally, bactericides, fragrances and colorants, among others.
  • Other personal care products not specifically mentioned, generally comprise about 0.1% to about 50% by weight of a composition according to the present invention and other components of personal care products as otherwise set forth in detail herein.
  • the invention provides a cross-linked silicone elastomer gel which has a viscosity of between about 1,000 to about 100,000 centistokes (est) and which is formed by a hydrosilylation reaction between:
  • n is about 265 to about 340 (preferably about 275 to about 330, more preferably about 285 to about 320, even more preferably about 295 to about 305, still more preferably about 300) and each 3 ⁇ 4 being independently H, or an alkyl group of 1 or 3 carbons; least one polyorganoh drosiloxane having the formula:
  • each R 2 is independently an alkyl of 1-3 carbon atoms; (c) at least one vinyl ester selected from the group consisting of cetyl ricinoleate, diisopropyi dimer dilinoleate, decyl oleate, glyceryl monooleate, isostearyl erucate, methyl acetyl ricinoleate, oleyl erucate, oleyl lactate, oleyl oleate, propylene glycol ricinoleate, arachidyl propionate, arachidyl behenate, dicapryl maleate, di-C 12 - 15 alkyl
  • the invention provides a cross-linked silicone elastomer gel which has a viscosity of between about 1,000 to about 100,000 centistokes (est) and which is formed by a hydrosilylation reaction between:
  • R 1 and R a are each H; each R 2 and R 3 is independently a Ci-C 10 alkyl group and n is from 5 to 50,000;
  • a, ⁇ -di lower alkenyl terminated polyorganosiloxanes and polyorganohydrosiloxanes are reacted with either at least one vinyl ester or at least one alpha- olefin.
  • multi-vinyl functional hydrocarbons and bis-dihydrosilane polydialkylsiloxanes are reacted with either at least one vinyl ester or at least one alpha- olefm.
  • This cross linked elastomer cannot be diluted to lower solid levels such as 5%. Diluting this elastomer will yield a gel that contains large particulates of said elastomer.
  • the same reactant blend reacted at 20% solids level in a diluent containing ⁇ 2% vinyl or alkene containing reactant will yield a softer less cross linked elastomer. This softer elastomer can be easily diluted to 10% and yield a very smooth gel free of large particulates of the elastomer.
  • the current invention utilizes a continuous process in which the reaction occurs as the reactants come into contact with each other, e.g. on the surface of a 2- 24 inch mixing trough. Once the reaction is complete the next step of the process, milling to a smaller particle size or milling and dilution of the concentrate can occur. This is done without the waiting period described in current processes. Analysis confirms that there is no need to allow the cross- linked silicone elastomer to sit without mixing so that the reaction comes to completion. Iodine values in conjunction with NMR analysis confirm total consumption of all reactants containing vinyl or alkenyl functional groups. If all reactants are consumed, a resting period of the gel is unnecessary.
  • the current invention describes a mixing of the alkenyl esters and or vinyl containing compounds and catalyst in one vessel.
  • This blend can be called "Blend A”.
  • Blend A can be 100% mixture of reactants and catalyst.
  • This blend can also contain a solvent or diluent. Solvent or diluent for the purpose of this description can be further defined by its non- reactive state.
  • the preferred embodiment contains no solvent or diluent but not limited to a non-solvent reaction.
  • a second vessel containing silanic hydrogen is required.
  • This second reactant blend can be called "Blend B”.
  • the current process can react and yield a product at temperature ranges of 25-80°C. Preferred temperature range utilizing the continuous manufacturing process is 40-50°C.
  • the reactants contained in "Blend A” and “Blend B” are mixing while maintaining a 40-45 °C temperature.
  • the Blends, A and B do can be mixed and reacted at room temperature ⁇ 25°C.
  • Hydrosilylation typically requires elevated temperatures so that the reaction can proceed quickly.
  • the current invention utilizes a continuous process reactor that can heat the reactants as they mix on the surface of the reactor vessel.
  • the two blends are dosed into a "Continuous Processor" such as the ones
  • the reaction vessel can be described as a vertically aligned trough.
  • This trough can be a 2 inch diameter up to a 24 inch diameter.
  • the trough contains two screw shafts that can be configured with mixing paddles. These paddles can be configured to mix or extrude.
  • the trough also has the flexibility to allow for the addition of reactants, solvents, and other ingredients in a liquid or solid state.
  • the trough can be segmented to have a half that can be heated while the second half of the trough can be cooled. Dosing of Blend A + B are performed in such a manner as to achieve complete reaction of the reactants.
  • This reaction produces a rubber gel that can be continuously mixed and extruded out the other end of the continuous process mixer.
  • Prior art and the utilization of common mixing vessels will not allow for the continuation of mixing or agitation.
  • Current practice typically describes a rest period wherein the product of this reaction is allowed to sit with no mixing to complete the reaction.
  • the reaction environment is small in the invention described herein.
  • Point of mixing is the point of reaction. Reaction time occurs at the point of mixing on the surface of the reactor vessel or reactor "trough".
  • the manufacturing/reaction process defined in this invention has led to surprising results.
  • gels were made using higher viscosity Dimethicone than were thought possible utilizing the conventional manufacturing method.
  • the new process can make gels diluted in Dimethicone that are 1,000 -100,000 est.
  • Current conventional process could not make a gel higher than 300 est.
  • the viscosity of the diluent had a limiting effect on the cross linking reaction.
  • viscosity will increase.
  • the viscosity of the diluent allows the crosslinking to occur throughout the reaction vessel. If the viscosity is high enough( >300 est using the conventional process in a large reaction vessel) the cross linking will not spread throughout the vessel.
  • the reaction using a continuous processor is not hindered by the viscosity of the diluent or even the viscosity of the reactants.
  • the viscosity of the product as the reactants react will not be a limiting factor as well.
  • the reaction environment in the continuous processor is very small. To make 1,000 lbs. of a cross linked silicone elastomer in the conventional manner. We would need a vessel that can hold the l,0001bs. The reactants need to be mixed or agitated at a certain
  • the continuous processor has the ability to produce up to but not limited to 1,000 lbs. of material with solvent or without solvent.
  • the continuous process splits the reactant blend into 2 parts.
  • One part contains vinyl silicones, alkenyl esters and or alpha olefins and catalyst.
  • the second part contains silanic hydrogen. These are dosed into the continuous processor at a certain rate.
  • the reaction and therefore cross linking reaction occurs as the two reactant blends come into contact with each other. This reaction is occurring at but not limited to 1 -5 lbs. a second.
  • the throughput of material noted utilized a 5 inch trough/reactor manufactured by Readco Kurimoto. The larger diameter reactors would increase this throughput.
  • the continuous processor acts as an extruder and continuous to knead or mix the silicone elastomer until it is extruded into a holding vessel.
  • all mixing or agitation is stopped and the reaction proceeds for several hours in the vessel without mixing or agitation. This is common practice for achieving complete cross linking.
  • Continuous process allows for mixing after the gelation point of the reaction. Once the gel is extruded out of the continuous processor the gel is ready for further dilutions. This can be accomplished with a homogenizer such as those made by Silverson. Preferably an inline homogenizer which ensures an efficient and homogenous particle distribution of the silicone cross linked gel.
  • alkenyl esters or vinyl compounds can be used to not only affect compatibility parameters but the physical properties of the gel itself.
  • the following is a listing of possible reactant mixtures.
  • Combination #9 same as in Combinations 2-4 including mixed molecular weights and isomers of esters containing alkenes. Ratios of the esters containing alkenes can be >l
  • Combination #11 same as in Combinations 2-4 including mixed molecular weights and isomers of the polyenes.
  • Ratios of the polyenes containing alkenes can be >1 Bis-vinyl silicones + Silicon-hydride containing polysiloxanes + Vinyl silicones (each reactant is available at different molecular weights)
  • Combination #13 mixed molecular weights, same as in Combinations 2-4 including mixed molecular weights.
  • Ratios of the vinyl silicones can be >1
  • Combination #17 mixed molecular weights, same as in Combinations 2-4 including mixed molecular weights.
  • Ratios of the polyvinyl allyl alcohols can be >1 19.
  • Silicon-hydride containing polysiloxanes can be used that contain pendant, terminal, and hybrids containing both terminal and pendant functionality.
  • Terminal functionality is used as chain extenders.
  • Pendant functionality is used as cross linkers.
  • Hybrids which contain terminal and pendant functionality increase cross linking density.
  • Experiment # BB1-34B describes a cross linked silicone elastomer that contains 3.5% ⁇ -olefin grafted onto the silicone elastomers backbone.
  • This elastomer has a clear appearance.
  • the elastomer is non-Newtonian and very tacky to the touch.
  • This elastomer can be diluted to 50% in Isododecane and behave as a Newtonian fluid.
  • the fluid is clear and has a viscosity of 1,000 cps.
  • This elastomer diluted in Isododecane can be applied to a substrate leaving a shiny adhesive film on the skin, hair, nail, woven and no-woven fabrics, leather, and wood, plastic, stone or other substrates. It has a great adhesion, water proofing as well as conditioning properties.
  • Experiment # MB1-225E describes a cross linked silicone elastomer that contains 7.25% Mango Butter Dimer Dilinoleyl Esters/Dimer Dilinoleate Copolymer. This elastomer is opaque and white in appearance. It is a hard non tacky rubber. This elastomer when diluted to 12% in Isododecane yields a thick flow able paste with a viscosity of 30,000 cps.
  • particle size rubber ready for dilution and further reduction of the particle size.
  • a cross linked silicone elastomer containing an, a-olefin and MB1-225E a cross linked silicone elastomer containing an alkene containing ester is the location of the alkene functionality.
  • a-olefin contains an alkene at the end of the molecule whereas the ester's alkene functionality is located somewhere along the middle of the molecule.
  • the ⁇ -olefin once grafted onto the silicon hydride is a single linear pendant group. The ester will react along the middle of the molecule and will produce two linear
  • Experiment MB 1-227 A is a cross-linked silicone elastomer that contains 4% CI 8 a-olefin and 3.25% Dimer Diliniloeate grafted onto the elastomer. This reaction produces a clear soft tacky rubber. This elastomer is a clear viscous, 3,000 cps, liquid.

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Abstract

L'invention concerne des gels d'élastomère de silicone améliorés, des procédés d'hydrosilylation et des cosmétiques associés. Les gels d'élastomère de silicone réticulés fabriqués par les procédés de l'invention présentent des caractéristiques supérieures, dont une meilleure solubilité organique, une gélification conforme, de la stabilité et un pouvoir lubrifiant amélioré.
PCT/US2014/057365 2013-09-25 2014-09-25 Gels d'élastomère de silicone amélioré et procédés d'hydrosilylation associés WO2015048228A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106589967A (zh) * 2017-01-25 2017-04-26 林建光 一种导电橡胶及其制备方法
JP2018115288A (ja) * 2017-01-20 2018-07-26 信越化学工業株式会社 水性シリコーン分散液、皮膜及び化粧料
CN109054730A (zh) * 2018-07-23 2018-12-21 深圳天鼎新材料有限公司 一种加成型灌封胶及其制备方法和使用方法
JP2020033339A (ja) * 2018-08-24 2020-03-05 株式会社コーセー 二次付着防止用油性化粧料

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US5110882A (en) * 1986-11-28 1992-05-05 Dow Corning Toray Silicone Company, Ltd. Silicone pressure-sensitive adhesive composition
US6703120B1 (en) * 1999-05-05 2004-03-09 3M Innovative Properties Company Silicone adhesives, articles, and methods
US6936686B2 (en) * 2002-12-11 2005-08-30 Nutech Corporation Cross-linked silicone gels; products containing the same; and methods of manufacture thereof
FR2848215B1 (fr) * 2002-12-04 2006-08-04 Rhodia Chimie Sa Composition elastomere silicone, adhesive, monocomposante et reticulable par polyaddition
FR2856072B1 (fr) * 2003-06-16 2005-08-05 Rhodia Chimie Sa Composition silicone reticulable en gel adhesif.
JP2005075959A (ja) * 2003-09-01 2005-03-24 Dow Corning Toray Silicone Co Ltd 粘着性シリコーンエラストマーシート
TWI440682B (zh) * 2007-03-30 2014-06-11 Shinetsu Chemical Co 無溶劑型聚矽氧感壓接著劑組成物
TW201319198A (zh) * 2011-06-02 2013-05-16 Dow Corning 厚膜之壓敏黏著劑及從其製成的層狀結構

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018115288A (ja) * 2017-01-20 2018-07-26 信越化学工業株式会社 水性シリコーン分散液、皮膜及び化粧料
CN106589967A (zh) * 2017-01-25 2017-04-26 林建光 一种导电橡胶及其制备方法
CN109054730A (zh) * 2018-07-23 2018-12-21 深圳天鼎新材料有限公司 一种加成型灌封胶及其制备方法和使用方法
JP2020033339A (ja) * 2018-08-24 2020-03-05 株式会社コーセー 二次付着防止用油性化粧料
JP7291034B2 (ja) 2018-08-24 2023-06-14 株式会社コーセー 二次付着防止用油性化粧料

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